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WO-1979000537-A1 | 1,979,000,537 | WO | A1 | EN | 19,790,809 | 1,979 | 20,090,507 | new | G08B21 | null | H01H71, H01H73 | H01H 71/04, H01H 73/14 | INDICATOR FOR BLOWN CIRCUIT BREAKER | A blown circuit breaker indicator is used with a conventional circuit breaker (9). The blown circuit breaker indicator includes a circuit including a light emitting diode (50), in series with a second switch (57) and a grounded connection (55) that diverts the flow of current away from the load (49) that allegedly caused the overload condition of breaker (9) with the light emitting diode being positioned at the front (12) of the casing (10) for the circuit breaker (9) so as to provide a visible indication of when the circuit has been blown. In one embodiment, the light emitting diode (50) will be activated by a second switch (57) when the circuit has been blown, and in the other embodiment, which contemplates the use of a plurality of circuit breakers, the light will be deactivated by a second switch (57) on only those circuit breakers that have been blown. | DESCRIPTIONTITLE: I. INDICATOR FOR BLOWN CIRCUIT BREAKER II. TECHNICAL FIELD The present invention relates to circuit breakers and more specifically to means of indicating that a circuit breaker has blown. III. BACKGROUND ART As commonly used, conventional circuit breakers are placed in banks of several side by side units, with each circuit breaker having an operating handle extending outward from the front of the casing of the circuit breaker. Normally, the handle has two extreme positions, an On position in which the circuit breaker completes the circuit, and another extreme position or Off position, in which the circuit is interrupted or opened. When this load circuit is overloaded, it will blow , or more specifically, the load circuit is interrupted by a circuit overload response member. -When this circuit overload response member interrupts or opens the circuit, simultaneously the operating handle moves to an intermediate position between the two above described extreme positions. With the standard circuit breakers presently on the market, it is difficult to determine whether or not a breaker is in this intermediate position or blown position, and not in one of the two extreme positions. This problem is made substantially worse when a plurality of circuit breakers are positioned in side-by-side relationship, as they commonly are in conventional practice. When one of the circuit breakers has its operating handle in the blown position, it is particularly hard to /-^gU t'A^ determine that this condition exists, especially where the circuit breakers are located in cellars or other dark locations. This makes it difficult for the cause of the overload to be found and corrected by resetting the breaker. As is common practice with the prior art circuit breakers, resetting consists of moving the operating handle to the off position, and then subsequently moving the same to the on position. Conventional type circuit breakers found in the prior art are illustrated in U.S. Patents Nos. 2,618,716; 2,663,773; 2,781,433; 2,924,683; 2,989,604; 3,636,482; and 3,930,211. This application is a continuation application of U. S. application serial number 871,487, filed January 23, 1978, which is a continuation-in-part of U.S. application serial number 847,007, filed October 31, 1977 (now abandoned) which in turn was a continuation- in-part of U.S. application serial number 729,664, filed October 5, 1976 which is now U. S. Patent number 4,056,816 issued on November 1, 1977.IV. DISCLOSURE OF THE INVENTIONThe present invention is directed to a blown circuit indicator to be used in combination with a conventional circuit breaker. The conventional circuit breaker load circuit normally comprises first switch means for opening or closing the load circuit, and a tripping means for triggering the first switch means to interrupt the load circuit in response to an overload condition of the load circuit. The problem found with conventional circuit breakers, including the device described and claimed by this inventor in U. S. patent number 4,056,816, is that when a light indicator is used there is a small current flowing through the light indicator circuit, which is in parallel with the load circuit, and through the load. refers- to the circuitry outside the circuit breaker that is being fed. Load circuit refers to the circuit inside the circuit breaker comprising a first switch means and a tripping means) . This small current that continues to flow through the load may be hazardous since it forfeits the original purpose of the circuit breaker, namely, to cut off the current to the load in response to an overload condi- tion. Consequently, there are a number of safety agencies that would not approve the use of circuit breakers with overload indicators of this type. The improvement of the present invention comprises a blown breaker indicator circuit having a second switch means and a connection to a third neutral contact thereby eliminating the above mentioned flow of current through the load. It is a primary object of the present invention to provide a light indicator for a conventional circuit breaker that can be used safely to facilitate the locating of a circuit breaker that has blown. A further object of the present invention is' to provide a light indicator for a conventional circuit breaker, which will activate a light emitting diode in the front panel of the breaker casing, so that there will be visible indication that a particular circuit breaker has blown. A related object of the present invention is to provide another embodiment of the present invention in which a light emitting diode is deactivated so as to visually indicate that a particular curcuit breaker has blown. Yet another object of the present invention is to provide an indicating light in the front' panel of the circuit breaker which is either activated or deactivated and stays in such a condition until the blown breaker has been reset, presumably after the cause of the overload on the circuit has been corrected. Yet another object of the present invention is to provide a blown circuit indicator using light means located in a readily visible location remote from the location of the overload responsive component so that if any heat caused by the overload responsive component will be sufficiently distant from the light means so as not to cause damage to the same. Yet another object is to provide a light indicator means for a circuit breaker whereby one can quickly determine which circuit breaker out of a plurality of side-by-side circuit breakers have been blown.V. BRIEF DESCRIPTION OF DRAWINGSWith the above and other related objects in view, this invention consists in the details of construction and combination of parts as will be more fully understood from the following description, when read in conjunction with the accompanying drawings, in which: FIG. 1 is an elevation view of the second embodiment of the present invention having the conventional bimetallic circuit breaker to which the blown breaker indicator circuit of this invention has been added, with the circuit breaker being on , the face or cover of the casing being omitted. FIG. 2 is an elevation view of the embodiment shown in FIG. 1, with the circuit breaker being blown . FIG. 3 is an elevation view of the first embodiment of the present invention having the conventional bimetallic circuit breaker to which the blown breaker indicator circuit of this invention has been added, the circuit breaker being on . FIG. 4 is an elevation view of the embodiment of FIG. 3 with the circuit breaker being blown . FIG. 5 is a schematic diagram of the first embodiment of the present invention shown in FIG. 4. FIG. 6 is a schematic diagram of the second embodiment of the present invention of FIG. 2. FIG. 7 is a diagramical view of the circuit breaker of the present invention interconnected with the load of a power system. VI. BEST MODE OF CARRYING OUT THE INVENTION A conventional blown circuit breaker, generally indicated as 9, is shown having a housing or case 10 suitable insulating material and in which the side cover or face is omitted from the illustration to enable the interior, parts to be illustrated. The case and cover are typically of molded insulating plastic. The various elements of a conventional circuit breaker mechanism, and also the elements of this invention, are mounted with the case 10. The case 10 has a front panel 12 through which an operating handle 13 extends. In FIG. 1 the handle 13 is shown in load circuit ON position 14 and in dotted outline, the handle 13 is shown in OFF position 15. In FIG. 2 the handle 13 is shown in its blown position 17. The circuit breaker 9 has first and second line terminals 18 and 34 which electrically connect the breaker 9 to the load to be protected. A load circuit 8 including first switch means 25 is electrically connected at one end to line terminal 18 and at the other end to line terminal 34. As commonly provided in conventional circuit breakers, the first line terminal 18 provides ideally a fixed contact 16 mounted in the casing 10 to engage a main bus bar 19 when the circuit breaker is inserted into a distribution panel (not shown) . As illustrated in FIG. l,a lever 22 having a movable contact 20 is shown in its circuit completing position 21 and in dotted outline, its open posi- tion 23. On the opposite end of lever 22 relative to movable contact 20 there is integrally formed the handle 13. The first switch means 25 is defined to include the first line terminal 18 and lever 22 which forms a circuit interrupting switch. The specific structural design of first switch means 25 is of conventional design and can take many different forms. The conventional circuit breaker 9 is of the type which is normally provided with overload tripping means 31 having a trip arm 24 pivoted on a boss 26 secured to the case 10, whereby the arm 24 is pivoted between a set position 27 shown in FIG. 1 and a tripped position 29 shown in FIG. 2. An overcenter tension spring 28 has one end connected to the lever 22 and the other end connected to the trip arm 24. The handle 13, lever 22 and spring 28 form an over- center arrangement, or toggle, and urges the movable contact 20 towards the fixed contact 16 when the spring 28 is on one side of the pivot point 30 shown in FIG. 1 and urges the movable contact 20 to the open position when the spring 26 is on the other side at the pivot point 30, as shown in FIG. 2. The current responsive member of the overload tripping means 31 is a thermally responsive or bimetallic latching member 38 which retains said tripping means in its set position 27. The specific structural detail of the overload tripping means 31 is known to the art, and can take numerous forms when combined with the present invention. Ideally, a load terminal connecting screw 32 mounted in a busOMPI _. niIrPOu t 1 bar 35 is provided for connecting the circuit breaker 9 to the2 load (not shown) . The load terminal connecting screw 32 defines3 the second line terminal 34, and is preferably riveted or screwed4 to case 10 at 36. The thermally responsive latching member 385 is a generally hook shaped thermostat element of at least two layers6 of metal having different coefficients of thermal expansion so that7 the element bends as its temperature increases. Furthermore, the8 end of the bimetallic member 38 is connected through second line9 terminal 34. The structure recited in this paragraph is of conven-10 tional design. .11 The circuit breaker operates in the customary manner for12 opening and closing the contacts, and also for tripping under the13 action of an overload. As thus far described, this circuit breaker14 is conventional and operates in the customary manner. This conven-15. tional construction is the same as disclosed in U. S. Patent No.16 3,930,211 and also in many other prior patents in this art. This17 particular conventional circuit breaker 9 is incorporated in the18 preferred embodiment of the present invention only for the purposes19 of illustration. Furthermore, the present invention could be practiced20 with other types of conventional circuit breakers. For instance, the21 present invention could be used in combination with a conventional22 magnetic circuit breaker as described in the parent U. S. application23 and U. S. -patent for this application, serial No. 847,007, filed24 October 31, 1977 and Patent No. 4,056,816. In such a breaker the25 tripping means 31 would comprise primarily a magnetic coil with its26 associated armature.27 In the first embodiment of this invention, light means 50,28 preferably in the form of a light emitting diode, is activated when the circuit breaker 9 has blown. In another embodiment of the present invention, the light means 50 will be deactivated when the circuit breaker is blown. The first embodiment is illustrated in FIGS. 3 and 4 and the second embodiment is illustrated in FIGS. 1 and 2. In both embodiments, the light means 50 is positioned at the front of the casing 10 on front panel 12 so as to provide a visual indication of when the circuit has been blown. In both embodiments of the present invention as shown in FIGS. 3 and 4, the blown breaker indicator circuit 33 includes in series a second switch means 57, resistor means 44 and light means 50. The blown breaker indicator circuit 33 »is electrically interconnected at one end to the third line terminal 37 which is a neutral line. At the other end, the blown breaker indicator circuit 33 is electrically interconnected to the first line terminal 18. The first line terminal 18 is electrically connected to the main bus bar 19. The third line terminal 37 is electrically connected to the neutral. As with all embodiments of the present invention, the first and second line terminal 18 and 34 connect with the load 49. The order of the second switch means 57, resistor means 44 and light means 50 in their series relationship can be changed as long as they are in series. Both the embodiment of FIG. 1 and the embodiment of FIG. 3 can be utilized in conventional DC or AC power systems, whether it is a single phase, two phase or three phase system. Likewise, it is immaterial whether the power system is having drawn therefrom 110 volts or 220 volts. More specifically, the circuit breaker 9 is electrically inserted in series with the hot phase line 51 by first and second line terminals 18 and 34, as shown in FIG. 7. The blown breaker indicator circuit 33 is electrically coupled to a neutral or ground 55 of the power distribution system so as not to be in series with load 49. In a conventional 220 volt power distribution system, there would be two breakers 9 inserted in the two hot phase lines 51 with the blown breaker indicator circuit 33 of each of the breakers 9 electrically connected to normally a single neutral line 55. Likewise, in a three phase power source system there would normally be three circuit breakers 9 inserted in each of the three hot phase lines 51 with three blown breaker indicators circuit 33 interconnected with a single neutral ground 55. Therefore, the above illustrated examples of conventional power systems is provided merely to emphasize the fact that the present breaker 9 with the associated invention can be incorporated into any conventional power system. In each case, the circuit 33 would be interconnected with the phase line 51 at a point intermediate to the power supply 53 and the first switch means 25. In both embodiments of the present invention as shown in FIG. 1 and FIG. 3, there is provided the thermal responsive member 38, prefer- ably in the form of a bimetal strip which is mechanically linked to second switch means 57. In a conventional manner when the current exceeds a predetermined or dangerous rate, the thermal responsive member 38 will activate second switch means 57 substantially at the same time that the first switch means 25 is opened. For purposes of illustration, the thermal responsive member 38 is shown in its non- activated position 45 and its activated position 47, as shown in FIGS. 1 and 2. When the excessive current in load circuit 8 exceeds the predetermined danger value, the excessive heat thereby generated triggers the thermal responsive member 38 from its non-activated position 45 to its activated position 47. The movement of the thermal responsive element 38 creates a corresponding movement with second switch means 57 so as to open or close the blown breaker indicator circuit 33, depending upon the embodiment. In the first embodiment shown in FIG. 3, the light means 50 will be initially off with the first switch means 25 closed, thereby defining a completed load circuit 8. Subsequently, the light means 50 will be activated or on when the breaker 9 has been tripped, or more specifically, when first switch means 25 is triggered to its circuit interrupting relationship with load circuit 8 as shown in FIG. 4. More specifically, as the thermal responsive member 38 bends into its activated position 47, second switch means 57 is pulled into circuit completing relationship with the blown breaker indicator circuit 33. Ideally, as shown in the preferred embodiment second switch means 57 comprises a curvilinear contact wire 58 disposed in spaced apart relationship to an elbow shaped prong 59. This elbow shaped prong 59 is an extension of 24. Upon the trip arm 24 being released by the thermal responsive member 38, the curvilinear wire 58 electrically engages the elbow shaped wire prong 60, as shown in FIG. 4. In the second embodiment of the present invention depicted in FIG. 1, the light means 50 will be initially on or activated with first switch means 25 disposed in circuit completing relationship to the load circuit 8. Subsequently, light means 50 will be off or deactivated when first switch means 25 is disposed in circuit interrupting relationship wLth the load circuit 8 as shown in FIG. 2. In other words, the light means 50 will be deactivated or ■off when an overload to the load circuit 8 occurs. This particular breaker design has practical utilization when a plurality of breakers 9 are incorporated into a single distribution panel. Therefore, there would be a row of light means 50 displayed from a plurality of circuit breaker 9, so that the deactivation of at least one of the light means 50 would become apparent to an observer. Generally, this embodiment differs structurally from the other embodiment in' that as thermal responsive member 38 bends to its activated position 47, the second switch means 57 is pulled forward so as to be disposed in circuit interrupting relationship to the blown breaker indicator circuit 33. Ideally second switch means 57 has its curvilinear wire 58 disposed in electrical engagement with its elbow shaped wire prong 60 when the trip arm is not released, as shown inJ-IG. 1. Upon the trip arm 24 being released by the thermal responsive member 38, the curvilinear wire 58 is in spaced-apart relationship to the wire prong 60 as shown in FIG. 2. The simplified schematic of the circuitry involved in both embodiments of the present invention is presented in FIG. 7. From the simplified schematic, it can be seen that unlike some of the prior art devices, the blown breaker indicator circuit 33 is not in parallel with first switch means 25. More specifically, by electrically interconnecting the blown breaker indicator circuit to a neutral or ground, the load, identified and represented by reference number 49, is free of any current flow when the first switch means 25 is open. This meets certain industrial requirements that. there be no current flow through the load circuit 8, no matter how small, when the breaker 9 has been tripped or blown. Prior schemes to provide a light means 50 that would be activated when the circuit breaker 9 was blown led to circuit designs having a current flow through load 49. Although such current flow was small, it is unacceptable in meeting the regulatory requirements of such circuit breakers. Although the preferred embodiment is shown with a mechanical tripping means 31, the present invention can be incorporated with other conventional breakers, such as the magnetic type described in the parent application of this application, serial no. 847,007 filed October 31, 1977 and issued as U. S. Patent No. 4,056,816. Such a magnetic circuit breaker (not shown) having a magnetic coil and armature would comprise the tripping means 31 of the present invention. More specifically, when there was an overload, in a well known matter the armature would pull the lever 22 to move its contact 20 away from the terminal contact 16. To summarize the operation of the embodiments of the present invention, the handle 13 operates first switch means 25 which includes lever 22 to make or break the load circuit 8 through contact 16 and movable contact 22 in the normal manner. At the same time, the overload of load circuit 8 causes trip arm 24 to change the state of second switch means 57, or more specifically, to either open or close second switch means 57. When second switch means 57 is opened or closed, the light means 50 is deactivated or activated respectively. In either case, the change of the light means 50 from its normal on-off state will provide a blown breaker signal indicating that the circuit breaker 9 has been blown. Although particular embodiments of the invention have been shown and described in full here, there is no intention to thereby limit the invention to the details of such embodiments. On the contrary, the intention is to cover all modifications, alternatives, embodiments, usages and equivalents•of the subject invention as fall within the spirit and scope of the invention, specification and the appended claims . VII. INDUSTRIAL APPLICABILITY It is apparent from the previous paragraphs that an improve- ment of this type for circuit breakers is quite desirable, and in some cases, even necessary. Frequently, the circuit breakers are located in cellars or in other dark places inside the buildings where they are installed. If the electric power is cut-off, the user will have to secure independent lighting means to figure out which circuit breakers blew out. Furthermore, inherent in the mechanism of these breakers is the disadvantage of a very small travel of the switch handle when a circuit breaker is blown and this small travel is difficult to detect, especially when there are a few dozens of these devices in a bank. The introduction of a safe lighted indicator is therefore a valuable improvement in this technology.- .' | CLAIMSWhat is claimed is, 1. A circui't breaker comprising: a) a load circuit having a power receiving first terminal, first switch means for electrically opening said load circuit, tripping means for activating said first switch means to open said load circuit in response to an overload condition of said load circuit; b) a neutral third terminal electrically insulated from said circuit; c) a blown breaker indicator circuit including light means operable to provide a blown breaker signal and second switch means electrically connected in series with said light means, and said blown breaker indicator circuit having one end thereof electrically connected to said power receiving first terminal and the other end thereof being connected to said neutral third terminal; d) overload detector means for activating said tripping means and for changing the on-off state of said second switch means in response to an overload condition of said load circuit. 2. The circuit breaker of claim 1, wherein said second switch means is a normally closed switch responding to an overload condition of said load circuit. 3. The circuit breaker of claim 1, wherein said second switch means is a normally open switch responding to an overload condition of said load circuit. 4. The circuit breaker of claim 2, wherein said overload detector means comprise a thermal responsive element disposed in heat receiving relationship to said load circuit and said thermal responsive element being mechanically coupled to said second switch means through said tripping means whereby movement of said thermal responsive element in response to an overload condition opens said second switch means. 5. The circuit breaker of claim 3, wherein said overload detector means comprise a thermal responsive element disposed in heat receiving relationship to said load circuit and said thermal responsive element being mechanically coupled to said second switch means through said tripping means whereby movement of said thermal responsive element in response to an overload condition closes said second switch means. 6. The circuit breaker of claim 4, wherein said first switch means includes a lever adapted for electrical disengagement from said power receiving first terminal when triggered by said tripping means and wherein said tripping means includes a trip arm releasably latched to said thermal responsive element whereby said trip arm is released by said thermal responsive element in response to an overload and said trip arm being connected to said second switch means whereby movement of said trip arm upon being released opens said second switch means. 7. The circuit breaker of claim 5, wherein said first switch means includes a lever adapted for electrical disengagement from said power receiving first terminal when triggered by said tripping means and wherein said tripping means includes a trip arm releasably latched to said thermal responsive element whereby said trip arm is released by said thermal responsive element in response to an overload and said trip arm being connected to said second switch means whereby movement of said trip arm upon being released closes said second switch means. 8. The circuit breaker of claim 1 wherein said light means comprises a light emitting diode. y^ ^' y ,O.V.Pi X _ . ^Ϊ O~ ' 9. The circuit breaker of Claim 1, wherein said blown breaker indicator circuit including a resistor disposed in series with said light means. 10. In the combination of a circuit breaker with a power distri- bution system having a neutral and at least one phase line electricall coupling a load with a power supply, said circuit breaker comprising a load circuit forming a portion of said phase line, tripping means for activating said first switch means to open said load circuit in response to an overload condition of said load circuit, the improve ment comprising: a) a blown breaker indicator circuit with one end thereof electric ally interconnected to the phase line of the power distribution system at a position intermediate to the power supply and the first .switch means. b) said blown breaker indicator circuit having the other end thereof electrically interconnected to the neutral. c) said blown breaker indicator circuit including light means operable to provide a blown breaker signal. d) second switch means electrically interposed in series with said light means. e) overload detector means for changing the on-off state of said second switch means in response to an overload condition of said load circuit. 11. In the combination of Claim 10, wherein said second switch means disposed in electrically interrupting relationship to said blown breaker indicator circuit in response to the overload condition of said load circuit. 12. In the combination of Claim 10, wherein said second switch means disposed in circuit completing relationship to said blown breaker indicator circuit in response to the overload condition of said load circuit. 13. In the combination of Claim 11, wherein said overload detector means comprising a thermal responsive element disposed in heat receiving relationship to said load circuit, and said thermal responsive element mechanically coupled to said second switch means whereby movement of said thermal responsive element in response to the overload condition opens said second switch means. 14. In the combination of Claim 12, wherein said overload detector means comprising a thermal responsive element disposed in heat receiving relationship to said load circuit, and wherein said thermal responsive element mechanically coupled to said second switch means whereby movement of said thermal responsive element in response to the overload condition closes said second switch means. 15. - In the combination of Claim 10, wherein said first switch means including a lever adapted for electrical disengagement from said phase line when triggered by said tripping means. 16. In the combination of Claim 10, wherein said light means comprising a light emitting diode. 17. In the combination of Claim 10, wherein said blown breaker indicator circuit including a resistor disposed in series with said light means. 18. In the combination of Claim 13, wherein said first switch means including a lever adapted for electrical disengagement from said power receiving first terminal when triggered by said tripping means, and wherein tripping means having a trip arm releasably latched by said thermal responsive element, and wherein said trip arm being released by said thermal responsive element in response to the over- load, and wherein said trip arm being attached to said second switch means whereby movement of said trip arm upon being released opens said second switch means. 19. In the combination of Claim 14, wherein said first switch means including a lever adapted for electrical disengagement from said power receiving first terminal when triggered by said tripping means, and wherein said tripping means being a trip arm releasably latched by said thermal responsive element, and wherein said trip arm being released by said thermal responsive element in response to the over- load, and wherein said trip arm being attached to said second switch means whereby movement of said trip arm upon being released closes said second switch means. | GUIM R | GUIM R |
WO-1979000542-A1 | 1,979,000,542 | WO | A1 | XX | 19,790,809 | 1,979 | 20,090,507 | new | B67D5 | null | B67D5 | B67D 5/371 | A LIQUID DISPENSING DEVICE | A liquid dispensing device in the form of a so-called pistol valve for use with a petrol pump comprises a valve housing (1) having an inlet (2) connected to the pump and an outlet (3); a valve (5) for controlling the flow of liquid from the inlet to the outlet; a discharge pipe (4) connected to said outlet; and a manually operable operating mechanism for controlling movement of said valve, which operating mechanism comprises adjustable means (19) which can be moved between an engagement position and a free position. In order to avoid the risk of unexpected flow of petrol when the pump is activated the movement of the adjustable means (19) between said free position and said engagement position is arranged to take place in dependence upon the pressure of the petrol at the inlet (2), and passage means (29, 30) are arranged for equalizing the overpressure at the inlet (2) when the pump is deactivated when the valve (5) is open or if an attempt is made to open the valve when the pump is deactivated and said pressure is sufficient to move the adjustable means (19). | A liquid dispensing deviceThe present invention relates to a liquid dispensing device, and particularly to a device having the form of a so-called pistol nozzle or pistol valve, such nozzles or valves normally being used in association with petrol pumps at vehicle filling stations.Such pistol valves comprise a valve housing having an inlet and an outlet, a valve for controlling the flow of liquid from the inlet to the outlet, a discharge pipe connected to the outlet, and a manually operable oper- ating mechanism for controlling movement .of the valve, said operating mechanism including adjustable means which can be adjusted or moved between an active or engagement position and an inactive or free position. The operating mechanism normally has the form of two plungers which are a.xially r.oveable in the valve housing and one of which is arranged within the other. In the rest position, the outer plunger forces the valve into sealing abutment with a valve seating under the action of a relatively heavy spring. Each of the plungers is provided with a respective recess which lie opposite each other in said rest position. The inner plunger is moved axially by operating an outer operating handle. The outer plunger can be caused to accompany the inner plunger during said axial displacement thereof owing to the fact that in said rest position two rollers carried by a holder are urged downv/ardly through the recess in the outer plunger and into the recess in the inner plunger. Thus, in this po¬ sition the rollers couple the two plungers together in a manner such that the outer plunger will accompany the axial movements of the inner plunger when the operating handle is activated. Such an axial displacement of the outer plunger allows the valve to be subsequently opened by an overpressure at the inlet.In previously known pistol valves of this type, the holder carrying said rollers is normally spring biased towards its engagement position with said inner plunger. Thus, the handle need only.be moved- to the neutral po¬ sition in order to be able to open the valve, meaning that the recesses of the plungers are located opposite each other and that said rollers will be pressed into said recesses by means of said spring. Subsequent de¬ pression of the handle will cause the valve to open as soon as the requisite pressure prevails at the inlet. The main function of the rollers is to permit the valve to close as soon as the level of liquid in the tank has reached a certain position on the discharge pipe of the pistol valve. To this end, the holder carry¬ ing said rollers is attached to a diaphragm which is arranged to curve upwardly to remove the rollers from the said engagement position with the inner plunger, when an underpressure is obtained in a chamber arranged above said diaphragm, said chamber communicating with an opening arranged at said position on the discharge pipe. If the handle is still held depressed, the inner plunger will remain in its axially displaced position while the outer plunger will be returned by its associ¬ ated spring, thereby causing the valve to seal against its valve seating.Pistol valves of. this type- thereby prevent overfill- ing of the tank, by automatically interrupting the flow of liquid thereto, and hence in manually serviced filling stations these pistol valves are normally provided with latching means by means of which the handle can be held depressed to permit filling of the tank to continue whilst the attendant carries out other servicing de¬ tails on the vehicle. In the case of filling stations which are not serviced by skilled personnel and in which' supervision of the pumps is of a relatively poor stan¬ dard, the provision of means for latching the handle in the filling position is not permitted, since careless- ness or acts of illwill can result in large quantities of petrol flowing out immediately a pump is actuated. For example, this can occur when the operating handle is depressed and latched in its depressed position by some person or other, subsequent to the pump being deactivat¬ ed after a filling operation. This latching of the handle in its depressed position will cause the tension acting on the valve through the outer plunger to be relieved, and hence the valve will open as soon as the pump is started up.This problem becomes more serious in the case of so- called cash petrol dispensers in which a filling opera¬ tion is normally not terminated as a result of the pe¬ trol tank being filled, but as a result of the disper.se- ment of a quantity of petrol corresponding to the amount of cash paid to the pum . VJhen the handle of such a pump can be latched in its inpressed position, it is rela¬ tively easy for the motorist to forget to return the handle to its neutral position before placing the pistol valve back in its recess in the pump, since the handle need never be released in order to close the valve.In order to avoid these problems it has been suggest¬ ed, that the pistol valve is constructed in a manner such that the valve is closed when the pressure of the .liquid in the supply line falls beneath a given minimum value. This is achieved v/ith a liquid dispensing device according to the invention by the fact that movement of said means which are adjustable between an engagement position and a free position, said means in the above example having the form of rollers, is arranged to take place independence upon the pressure of the liquid at the inlet. Thus, the arrangement is such that the rollers cannot be pressed down into the recess in the inner plunger unless an overpressure prevails at the in- let, and such that the rollers return immediately to the inactive or free position as soon as the pressure at the inlet ceases. Thus, this means that the aforementioned rol¬ lers will return to the inoperative position when the required amount of petrol has been supplied to the pe¬ trol tank, and that they cannot be pressed down into the position of engagement with the inner plunger if the overpressure does not remain at the inlet or a new over¬ pressure has built up after the pump has been deactivat¬ ed.In prior art pressure controlled pistol valves, how- ever, subsequent to the valve having been closed, for example by a) the automatic deactivation 'of the pump, b) releasing the handle, or c) by reason of the fact that the incoming flow of petrol has fallen to a mini¬ mum value, a pressure of such magnitude may remain or may be re-built up in the supply line, that when utili¬ zing a re-setting mechanism of the aforedescribed type, the handle and valve can be latched in the inpressed position although the pump has been deactivated. Thus, the aforementioned risk of an unexpected flow of petrol from the filling nozzle when the pump is activated re¬ mains.Another serious disadvantage with known pistol valves is that the pressure in the supply line activates the valve mechanism via a membrane or diaphragm. When the pistol valve is to be used for dispensing petrol, the valve mechanism becomes excessively insensitive, resulting in an unreliable function. This is due to those materials which can be used for diaphragms which are to •come into contact with petrol. A main object of the present invention is to provide a liquid-dispensing device in which the aforementioned disadvantages and accident risks are eliminated.In accordance with the present invention the solution to the aforementioned problems lies in the fact that there shall not remain or be built-up at the inlet an overpressure of such magnitude as to enable the valve to be latched in the open position when the pump is deactivated.In accordance with the present invention the problems are solved by providing means for equalizing the over- pressure at said inlet when the pump is shut-off with the valve open, or if an attempt is made to open the' valve when the pump is deactivated and said pressure is sufficient to move the aforementioned adjustable means of the valve mechanism. In order to obtain a highly responsive and positive functioning when moving said adjustable means, it is preferred that the pressure of the liquid at said inlet is arranged to act on a piston connected with said ad¬ justable means. Among other things, this will eliminate the problems rεaulting from the defficiencies of the conceivable materials from which the aforementioned diaphragm can be made.In the case of cash petrol dispensers the capacity of the pump is limited resulting in a decreasing flow of petrol towards the end of a filling operation as the cash is used up. Since the device according to the in¬ vention, however, is based on the use of an overpressure at the inlet of the pistol valve, the pistol valve when used in cash petrol dispensers must be so constructed that it maintains a given pressure at said inlet. This can be achieved by constructing the valve in a manner such that the opening area of the valve is adapted to the incoming flow of petrol. Thus, the valve can be arranged to be opened by the pressure at the inlet against the action of a spring which determines said given pressure. Conveniently, the valve arrangement is constructed in a manner such that when the last men¬ tioned spring tends to fully close the valve when said incoming flew ceases, there is obtained a small venti- lating passage for equalizing the pressure at said inlet. Other characterizing features of the invention are disclosed in the attached claims.The invention will now be described more clearly with reference to the accompanying drawings. Figure 1 is an axial sectional view of a pistol valve according to the invention ready to carry out a filling operation.Figures 2-4 illustrate in larger scale other posi¬ tions of the operating mechanism. Figure 5 illustrates the valve in a fully open posi¬ tion.Figure 6 illustrates the valve in a ventilating po¬ sition.Figure 7 illustrates an alternative embodiment for equalizing the overpressure at the inlet in conjunction with closing the valve.Figure 8 is an axial sectional view of an alternative embodiment of a pistol valve according to the invention.The pistol valve illustrated in figure 1 comprises a valve housing 1 having an inlet 2 and an outlet 3. The inlet 2 is connected with a hose (not shown) from a petrol pump, while the outlet 3 is connected to a dis¬ charge pipe 4. The valve housing 1 includes a valve body 5 which seals against a valve seating 6 and which is provided with a valve spindle 7. The spindle extends through a guide 8 and is provided at its rear end with a return spring 9, which operates between a stationary washer 10 and a displaceable washer 11.It is assumed that the petrol pump is activated in the illustrated position, the inlet 2 being filled with petrol under pressure. The valve is held closed, however, by the fact that an axially displaceable cylindrical plunger 12 urges the valve body 5 against the valve seating 6 under the action of a spring 13, which coun- teracts the pressure at the inlet 2. An inner plunger 14 is arranged for axial movement in the cylindrical plunger 12. The inner plunger 14 can be displaced by pulling in the handle 15, as indicated in dash lines, and is provided with a return spring 37.The plungers 12 and 14 can be coupled together in a manner such that the outer plunger 12 is caused to ac¬ company the movement of the inner plunger 14. To this end, said plungers are each provided with a respective recess 16 and 17 in which two rollers 19 carried by a holder 18 can be introduced. The holder 18 is suspended from a diaphragm 20 which carries on its opposite side one part 21 of a telescopic claw or clutch mechanism 21, 22. The reference 23 identifies a spring which at¬ tempts to hold the telescopic mechanism in its outwardly extended state, while the reference 24 inditifies a heavier spring which attempts, via the claw arrangement 21, 22 to lift both the diaphragm 20 and the holder 18 with the rollers IS and, in addition, a piston 25.Formed between the diaphragm 20 and the piston 25 is a closed chamber which is used in a conventional manner to close the valve 5 when the level of petrol in the tank has reached a given position on the discharge pipe 4. To this end, the chamber is arranged to communi¬ cate with a channel 26 having a mouth which opens at the outside of the discharge pipe 4 adjacent the end thereof, and with a corresponding channel 27 having a mouth which opens into the valve seating 6. As petrol flows through the valve opening, there is created at this last mention¬ ed mouth an ejector effect which draws air through the channel 26, the chamber obtained between the diaphragm 20 and the piston 25, and the channel 27. The effect of this automatic protection against overfilling is as follows.With the rollers 19 occupying the position illustrat¬ ed in figure 1, the valve 5 can be opened by depressing the handle 15. The inner plunger 14 will be moved to the left in the figure and the outer plunger 12 will accom- m> - ''• --- i pany the movement of the inner plunger 14 as a result of the coupling of said plungers by the rollers 19 and be moved to the left whilst compressing the spring 13. The load on the valve 5 is hereby released, whereupon the pressure at the inlet 2 is able to open the valve. Petrol will then flcv; through the valve and out through the discharge pipe 4, whereupon a certain suction effect is obtained through the channels 26 and 27 and interme¬ diate chamber, as hereinbefore mentioned. When the level of petrol in the tank reaches the mouth of the channel 26 located adjacent the forward end of the discharge pipe, it is momentarily closed, thereby causing, as a re- suit of said ejector action, an underpressure to be ob¬ tained in the chamber above the diaphragm 20. The dia- phrag will thus be caused to curve upwardly whilst com¬ pressing the telescopic claw arrangement 21, 22. This causes the holder 18 to be lifted and the rollers 19 to be moved out of their position of engagement with the inner plunger 14. The outer plunger 12 will then be re- turned immediately, to close the valve 5, under the ac¬ tion of spring 13. The rollers 19 will also be entrained with said closing movement and cannot be pressed down in¬ to the recess of the inner plunger until the handle has been released. In order, in accordance with the invention, to ensure that the pistol valve will not occupy its opened position when the petrol pump is deactivated, which would result in petrol being dispensed as soon as the pump is acti¬ vated, the movement of the rollers 19 between their en- gagement position and free position shall take place in dependence upon the pressure at the inlet 2, in addition to the aforedescribed closing function. To this end a channel 28 is arranged between the inlet and the chamber above the piston 25. Thus, the piston v/ill constantly be activated by a force which is directly proportional to the pressure at the inlet 2. Thus, as a result of the spring 24 the rollers 19 cannot be pressed down into engagement with the inner plunger 14 unless an overpress¬ ure prevails on the upper side of the piston 25. This ensures that the valve cannot be opened by depressing the handle 15 when no pressure prevails at the inlet 2. Similarly, this means that the rollers 19 are lifted up out of engagement v/ith the inner plunger 14 as soon as the pressure at the inlet 2 ceases, since the spring 24 will then return the piston 25 to. its upper position. In order for petrol to be supplied through the pistol nozzle, the valve arrangement must be in the position illustrated in figure 1. Thus, the petrol pump shall be activated so that a pressure exists at the inlet 2, and the handle 15 must be located in its neutral posi- tion, which means that the recesses 16 and 17 of respec¬ tive plungers 12 and 14 are located opposite each other. The' ressure at the inlet 2 will then cause the holder 18, through the action of piston 25, to urge the rollers 19 into engagement v/ith the inner plunger 14. When the handle 15 is then depressed, the inner plunger will be displaced carrying with it the outer plunger 12, which releases the valve 5 which can then be opened by the pressure at the inlet.Figure 2 illustrates the state obtained when no over- pressure exists at the inlet 2. The spring 24 will then hold the piston 25 in its upper position, in which po¬ sition the piston holds the diaphragm 20 and the holder 18 with rollers 19 in a lifted position, via the claw arrangement 21, 22. 'When the handle 15 is depressed in this posistion, the inner plunger 14 will be moved to the left, in the normal manner. The outer plunger 12 v/ill not, however, accompany the movement of the inner plunger, and the valve cannot be opened.Figure 3 illustrates the state obtained when the handle 15 is already depressed when the petrol pump is activated. As was the previous case, the ing on the piston 25 will urge the piston down but since the inner plunger 14 has been moved forward by the depression of the handle, the recesses of the plungers will not be located opposite one and other. The rollers 19 can thus not be pressed into engagemnt with the inner plunger 14. Instead, movement of the piston 25 will cause the telescopic claw arrangement 20, 21 to be com¬ pressed.' Thus, petrol cannot be dispensed until the handle 15 is released and re-depressed, causing the rollers to be pressed down into the recess 17 of the inner plunger 14.A position corresponding to that shown in figure 3 is also shown in figure 4 , this position having been obtained as a result of the pump being automatically deactivated by a full tank. This is illustrated by the fact that the diaphragm 20 has been ' arched upwardly by the underpressure in the chamber between the dia¬ phragm and the piston 25. This upward arching of the diaphragm has resulted in that the holder 18, v/ith the rollers 19, have been drawn up out of engagement with the inner plunger 14 whilst compressing the telescopic claw arrangement 20, 21. The outer plunger 12 has then returned under the action of the spring 13 and closed the valve 5. Thus, it is also necessary in this case to first release the handle and then re-depress the same in order to dispense petrol from the pump.In order to permit the pistol valve according to the invention to be used with cash petrol dispensers, in which the flow varies during a filling operation in a manner such as to be relatively small towards the end of said operation, or to be used v/ith other pumps in which the flow varies, the valve arrangement is con¬ structed in a manner such that a given minimum pressure constantly exists at the inlet during a dispensing operation. This given pressure shall correspond to the pressure required to urge the piston 25 downwardly. ^ ■ ' ' This can be achieved, for example, in the manner illu¬ strated in figures 5-7.Figure 5 illustrates the valve in its fully opened position, v/here contact exists v/ith the end of the outer plunger 12. Opening of the valve takes place against the action of the spring 9, and as a result of the pressure at the inlet 2. When the incoming flow decreases, the press¬ ure on the valve 5 v/ili also decrease, v/hich causes the return spring 9 to reduce the area of the valve opening in a manner such that a given minimum pressure, dependent upon the spring, will constantly exist at the inlet.In all of the aforedescribed embodiments there is ob¬ tained an automatic closing of the valve when the tank is full or when the incoming flow of petrol ceases. Further, the valve is closed when the handle 15 is re¬ leased. When the flow of petrol is interrupted as a re¬ sult of a full tank or because the handle has been re¬ leased, the valve will be closed whilst the pump is still activated. This means that a full pressure will be built up in the hose and will remain whilst the pump is de¬ activated. Since this pressure acts on the piston 25, the valve can be opened and latched by depressing the handle 15. In the case, for. example, of a cash petrol dispenser the valve will tend to close, in a correspond- ing manner before the pressure at the inlet has become so low that the rollers 19 are drawn up out of engage¬ ment with the inner plunger 14. This is due to the fact that the return spring 9 is dimensioned in a manner such that the input pressure is maintained at a value suffi- ciently high to displace the piston 25. A corresponding effect can also be obtained when the hose passing to the pistol valve is filled v/ith petrol under low pressure. In this case, however, the quantity of petrol in the hose may be heated by the sun so that the pressure increases to a value v/hich causes the piston 25 to be displaced. Thus, this will also enable the valve to be latched in an open position.The aforementioned problems are solved in accordance with the present invention by arranging a closeable ven¬ tilating passage from the inlet, through which undesir- able overpressure can be equalized. This can be effected, for example, in the manner illustrated in figures 5 and 6. In the embodiment illustrated in figures 5 and 6, the spring 9 is unable to provide complete closure of the valve 5, but a narrow opening gap will remain until the outer plunger 12 urges the valve 5 into sealing abutment with the valve seating 6. This is achieved by arranging on the valve spindle 7 a shoulder 29 against v/hich the cveable washer 11 will be urged when the spring 9 at¬ tempts to close the valve. The shoulder shall be located at a distance from the end of the valve spindle 7 such that complete closure of the valve 5 cannot be obtained as a result of the action of the spring. Subsequent to interrupting the incoming flow of petrol, the remaining overpressure at the inlet 2 can be equalized through the gap which remains. Subsequent to this equalization of the remaining overpressure, the piston 25 will return and draw up the rollers 19 out of engagement v/ith the inner plunger 14. Thus, the valve cannot be reopened un¬ til the pump has been reactivated. If the pistol valve is closed by automatic disengage¬ ment or as a result of the handle 15 being released v/hilst the pump is still activated, an overpressure will be enclosed in the hose between the pump and the valve 5. This pressure will be sufficient to urge the piston 25 downwards thus permitting the valve to open. In the embodiment of figures 5 and 6, however, cessation of the abutment of the outer plunger 12 v/ith the spindle 7, as a result of depressing the handle 15, causes the aforementioned overpressure to ooen the valve 5 in a manner such as to form the previously mentioned gap between the valve 5 and the valve seating 6 for ing the overpressure at the inlet 2. This equalization of the pressure takes place very quickly, v/hereafter the piston 25 is again urged upwardly by the spring 24. The piston then withdraws the rollers 19 out of engage- ment with the inner plunger 14 , v/hereupon the valve is again closed. No overpressure prevails, however, at the inlet 2.As will be evident from the aforegoing, v/ith the em¬ bodiment illustrated in figures 5 and 6, the enclosure of an overpressure is prevented when the valve 5 closes slowly, cr an enclosed overpressure is quickly equalized when an attempt is made to open the valve.Another method of equalizing the pressure is illu¬ strated i figure 7. In this embodiment, the valve spindle 7 is provided v/ith a through passing channel 30, through which the overpressure at the inlet can be equal¬ ized subsequent to interrupting the incoming flow of petrol. This channel is subsequently sealed in conjunc¬ tion with the return of the outer plunger 12, by means of a rubber body 31 mounted on the end of the outer plunger.The requisite equalization of the overpressure at the inlet can also be realised in other ways, the only re¬ quirement being that said equalization shall take ^place or be possible at all positions, in which the outer plunger 12 does not urge the valve 5 into sealing abut¬ ment with the valve seating 6. Thus, opening and closing of the ventilating channel can be controlled by the move¬ ment of the plunger 12 in the manner desired. Figure 8 illustrates schematically an alternative embodiment of the arrangement according to the invention, said arrangement being based on the same principle that the opening and closing of the valve 5 is dependent unon the pressure prevailing at the inlet 2. As v/ith the earl- ier embodiments, a diaphragm 20 is attached to the holder 18 for defining a chamber above the diaphragm which can be used to automatically deactivate the pump in depen¬ dence upon the level of the liquid in the tank. In this embodiment, however, the holder 18, in the illustrated position, rests on an impact rod 32 which is connected with a piston 33. The piston 33 is biased tov/ards its upper position by means of a spring 34. A pressure chan¬ nel 35 from the inlet of the pistol valve opens into the chamber above the piston 33. This means that when an over¬ pressure prevails at the inlet 2, the piston 33 will be pressed downwardly, v/hich enables the holder 18 with the rollers 19 to be pressed down into engagement with the inner plunger 14 by a spring 36, provided that the recesses in the plungers 12 and 14 are located opposite one and ether. Thus, the function of the embodiment illustrated in figure 8 is exactly the same as the func¬ tion of the previously described arrangement.The invention can also be modified in other respects within the scope of the claims and within the basic prin¬ ciple of the invention, meaning that the opening and closing functions of the valve shall take place in de¬ pendence upon the pressure at the inlet and that a venti¬ lation channel for equalizing an overpressure at the in¬ let shall be obtained. Thus, the holder, for example, v/ith said rollers can be replaced by any optional type of release arrangement, for example a pivotable hook or the like. Neither is the device according to the inven¬ tion limited to use when filling the tank of a vehicle v/ith fuel, but can also be used for disoensing any liquid v/ith or without the use of an automatic protection against overfilling.In all the aforedescribed embodiments the inlet press¬ ure acts on a piston, v/hich provides good response and reliability. With the previously used diaphragms, there is always the risk that the diaphragms v/ill disintegrate v/hen they are made of a thickness which will provide for good response required. Consequently, it is necessary for the diaphragms of prior art valves to be made thick¬ er, v/hich makes them very insensitive to variations in pressure, particularly at low temperatures.Since all the disadvantages mentioned in the introduc¬ tion are eliminated with a device constructed in accordanc v/ith the invention, arrangements for latching the handle can also be applied in pistol valves for self servicing pumps and for pumps used in connection v/ith cash petrol dispensers. | Claims :1. A liquid dispensing device, preferably in the form of a so-called pistol valve, comprising a valve housing(1) having an inlet (2) connected to a pump or the like and an outlet (3) ; a valve (5) for controlling the flow of liquid from the inlet to the outlet; a discharge pipe (4) connected to said outlet; and a manually operable operating mechanism for controlling movement of said valve, said operating mechanism including adjustable means (19) v/hich can be moved between an engagement po- sition and a free position, characterized 'in that the movement of said adjustable means (19) between said free position and said engagement position is arranged to take place in dependence upon the pressure cf the liquid at said inlet (2) , and that means (29; 30) are arranged for equalizing the overpressure at said inlet(2) v/hen the pump is deactivated when the valve (5) is open or if an attempt is made to open the valve v/hen the pump is deactivated and said pressure is sufficient to move said adjustable means (19) . 2. A device according to claim 1, characterized in that the pressure of the liquid at said inlet (2) is arranged to act on a piston (35) connected to said adjustable means (19) .3. A device according to claims 1 or 2 , characterized in that said means for equalizing said overpressure at said inlet (2) includes at least one closeable ventilat¬ ing passage (30) .4. A device according to any on of claims 1-3, in v/hich said adjustable means includes a moveably arranged hol- der (18) carrying rollers (19) , characterized in that said holder (18) is adapted to exert a force on the rollers (19) , upon the occurrence of an overpressure of a given magnitude at said inlet (2) , v/hich force attempts to move said rollers to the engagement posi- tion . 5. A device according to claim 4, characterized in that it comprises a spring (24; 34) adapted to return the rollers (19) to the free position when the pressure at said inlet (2) falls below said value. 6. A device according to any one of claims 1-5, charac¬ terized in that said valve (5) , in the open position, is adapted to adjust the opening area in dependence upon the incoming flow of liquid, thereby to maintain a given pressure at the inlet (2) when the pump is acti- vated.7. A device according to claim 6, characterized in that the valve (5) is adapted to be opened by the pressure at the inlet (2) against the action of a spring (9) v/hich determines said given pressure. S. A device according to claim 7, characterized in that the valve arrangement is so constructed that v/hen the last mentioned spring (9) tends to completely close the valve because the flow of incoming liquid has ceased there is obtained a narrow ventilating passage for equalizing the pressure at said inlet (2) .■ | TRYGG L | TRYGG L |
WO-1979000556-A1 | 1,979,000,556 | WO | A1 | EN | 19,790,823 | 1,979 | 20,090,507 | new | A61K31 | null | null | A61K 31/615 | COMPOSITION CONTAINING SALICYLSALICYLIC ACID AND ACETAMINOPHEN | A safe and effective analgesic composition comprises 100 to 1000 mg of salicylsalicylic acid per 100 to 650 mg of acetaminophen. | COMPOSITION CONTAINING SALICYLSALICYLIC ACID AND ACETAMINOPHENBACKGROUND OF THE INVENTION1. Field of the InventionThis invention relates to a pharmaceutical composition having useful analgesic, antipyretic, antirheumatic and anti-inflammatory properties. This composition may also be compounded, as aspirin and acetaminophen are, with other non-prescription antihistamines, antitussives, sedatives, analeptics, etc., as well as with prescription drugs such as narcotics, barbituates, etc.2. Description of the Prior ArtThere do not appear to be any references in the prior art to the combination of salicylsalicylic acid (hereinafter SSA) and acetaminophen (hereinafter APAP) . However, there are some disclosures of aspirin (acetylsalicylic acid, hereinafter ASA) with APAP.'For example Cotty et al, U.S. Patent No. 4,049,803 discloses that 10 grains of ASA when combined with 5 to 15 grains of APAP, yields increased blood levels of unhydrolyzed ASA shortly and for extended periods after oral ingestion.Fujimura et al, U.S. Patent No. 3,284,298 discloses that a Vitamin B,-active substance fortifies or strengthens the analgesic activity of a number of compounds and compositions. Among the analgesics listed are APAP and SSA.Berger, U.S. Patent No. 2,872,370 discloses a hypnotic composition containing acetophenetidin and salicylamide and suggests the substitution of APAP for acetophenetidiiOMPI However, the substitution of a variety of salicylic acid compounds and derivatives, including ASA, for the salicylamide component is classified as ineffective.The Abstract of Japanese Patent No. 18,232/66 to Nippon Kayaku Company on October 19, 1966 discloses that a eutectic mixture of acetylsalicylic acid and N-APAP is prepared by heating and melting together the ASA and N-APAP, and that a very suitable eutectic is formed with 53% ASA and 37% N-APAP, and increasing concentration in the blood.Robertson, U.S. Patent No. 3,431,293 discloses the production of para-N-acetylaminophenol acylsalicylates by several processes including the simple esterification of the appropriate acyl salicylic acid and N-acetyl-p- aminophenol. Only acetylsalicylic acid and its derivativ are disclosed but other lower aliphatic acid groups might be substituted for the acetyl moiety.Of interest also is Emele, U.S. Patent Numbers 3,063,897 and 3,068,147 which pertain to analgesic compositions containing alkoxybenzamide with a mixture of salicylamide and APAP.Cherkas , U.S. Patent No. 3,439,089 is of interest in that it relates to medicated hard candies which may include, alternatively, APAP, salicylamides, or ASA.British Patent No. 1,019,146 issued February 2, 1966 is of interest for its disclosure of a timed release analgesic tablet. Among several analgesic drugs described as being usable in such tablets were APAP and SSA. Mixtures of several drugs are described as being possible for the practice of that invention, but no combination of SSA and APAP is specifically suggested. Examples III and V in the British patent related to the/ B f manufacture of tablets of acetaminophen and salicylsalicylic acid respectively.The following sections from Chemical Abstracts may be relevant - 73: 75268J 80: 87539f and 81: T54453r.SUMMARY OF THE INVENTIONThe compositions of this invention comprise from 100 to 1000 mg of SSA per 100 to 625 mg of APAP (the combination hereinafter to be abbreviated as SSA-APAP) . The preferred dosage contains approximately 500 mg SSA and 325 mg APAP.Like ASA, SSA-APAP is an acetylated salicylate. But SSA-APAP's salicylate factor, SSA, is (1) longer-acting than ASA, (2) a more effective antirheu atic and anti- inflammatory agent than ASA, and (3) gas rically a minimally irritative factor which causes no occult bleeding above placebo values, while ASA has been shown to cause signficantly more irritation, erosion and bleeding in the gastric mucosa. SSA-APAP's acetyl carrying factor, APAP, is also effectively non-irritative and non-bleeding gastrically, while APAP's analgesic action, proven eguipotent to ASA's, is further potentiated by SSA's additional, longer acting analgesic action. APAP's lack of overdosage warning signs is lessened by the presence of SSA which manifests early, more easily reversible, overdosage signals, such as tinnitus. Thus SSA-APAP is safer and more effective than either ASA, APAP alone, or SSA alone.DETAILED DESCRIPTION OF THE INVENTIONSalicylsalicylic acid (SSA) is also known as salsalate, salysal, diplosal, salicylsalicylate, and salicylosalicylic acid. Chemically it is named in the Merck Index (9th Edition, 1976) referred to as, benzoic acid, 2-hydroxy, 2-carboxyphenyl ester. SSA was introduced by Boehringer and Soehne in Germany in 1908 and is mentioned by U.S. Patent No. 922,955, issued on May 25, 1909. Under the name Salysal it was listed in the AMA Council on Pharmacy and Chemistry's New and Non-Official Remedies (NNR) from 1937 through 1948. It is presently understood to be sold as an ingredient in four commercial preparations. Two comprise unmixed SSA and are sold to the ethical market only. The remaining two formulations are mixtures with ASA and are sold over- the-counter. Compared to the universally used salicylate ASA, SSA is relatively very little-used. Currently the Merck Index (9th ed., 1976) lists SSA as having the actions and uses of an analgesic, antipyretic, and antirheumatic . A special review of OTC internal analgesics completed in 1977 by the FDA's Internal Analgesics Panel (IAP) placed SSA in both its Category I recommended for labeling as an analgesic (Federal Registe Vol. 42, No. 131, 7-8-77, Book 2, p. 35443), an antipyret (p. 35452) and, under a physician's direction, as an anti rheumatic and anti-inflammatory (p. 35468) - and in its Category III: drugs it recommends be further tested.(p. 35350).Overall, medical research shows SSA lower than ASA and APAP in analgesic pain relief but superior to ASA and APAP in antirheumatic, anti-inflammatory action and in safety. SSA showed 1/3 the analgesic effect of ASA in tests using the phenylquinone method on mice (Alberg & Larsson, Acta Pharmacol, et Toxicol., 1970, No. 28). The IAP rated SSA's analgesia at 2/3 ASA's (p. 35443). However, P. K. Smith in an unpublished paper in 1952 reported tests showing SSA delivers equal salicylate to the blood from a 30% lower dose than ASA. Alberg and Larsson (above) got over 50% higher anti-inflammatory effect from SSA as compared to ASA in inhibitory effect tests on S-sulphate incorporation in calf rib cartilage.CHART I The inhibitory effects of salicylates on 35S-sulphate incorporation in calf rib cartilage ____Experiment Per cent ir lhib ion of 35S incorporation ±S.E.M. No . ASA (n) SSA (ii) SA __)_ 1 47 . 0 * 4 . 2 ( 5 ) 63.2 * 0.8 (5) 31.3 ± 1.8 (4) 2 40 . 0 * 5 . 7 ( 4 ) 66.2 * 1.8 (4) 39.8 ± 3.3 (5) 3 69 . 3 * 4 . 2 ( 4 ) 71.6 * 0.7 (5) 37.3 * 1.5 (5)4 48 .7 * 2. 3 (5 ) 73.1 * 0.2 (5) . 41.6 * 3.5 (5)5 39 . 8 * 4 . 6 ( 5) 68.8 * 1.1 (5) 34.4 * 1.4 (5)6 20 . 4 * 9 . 3 ( 5 ) 76.4 * 1.4 (5) 27.1 * 1.5 (5)mean * S.E.M. 44.7 * 3.2 (28) 70.0 ± 0.9 (29) 35.4 * 1.3 (29)The inhibitory effects of ASA, SSA and SA at 6 mM concentration expressed as per cent of mean values for the control groups.Nordqvist, et al (Nord. Med., 74, 1965) found SSA stayed- in the blood far beyond ASA's 4.7 hr. half-life. Bayles and Tenckhoff (Scientific Ex., Am. Acad. G.P., 1959) showed ASA was unable to maintain overnight effectiveness against the morning ache and stiffness of rheumatism and arthritis. Rubin (Am. J. Med. Sci. , July, 1968) , using a preparation containing 485 mg SSA/160 mg ASA, developed overnight effectiveness against osteoarthritis and the morning blood concentration of salicylate continued to build over several days. CHART IISERUM SALICYLATE LEVELS IN 17 PATIENTS WITH OSTEOARTHRITIS AFTER ORAL ADMINISTRATION OF A PREPARATION CONTAINING SALICYLSALICYLIC ACID AND ACETYLSALICYLIC ACID FOUR TIMES A DAY FOR EIGHT DAYSSerum Salicylate (mg./lOO l.)Zero 2 4 6 8 24 8th DaPatient Age Sex Vfeight Hour Hours Hours Hours Hours Hours 8am 2A.A. 66 F 117 0 1.0 6.0 1.0 6.5 7.0 15.0 1D.A. 54 F 130 0 4.5 8.0 9.5 9.5 8.5 12.5 1A.B. 75 M - 178 0 0.5 0.5 2.0 1.5 7.0 22.5 2D.B. 56 F 115 0 5.0 4.0 2.5 11.0 23.5 31.0 1S.B. 72 F 186 0 1.5 1.0 2.0 3.5 10.5 8.0 1T.B. 81 F 157 0 2.0 6.0 8.0 7.0 3.5 14.0 1T.G. 71 F 178 0 3.0 3.5 6.5 8.0 12.0 7.0 1I.H. 72 F 154 0 3.0 3.5 ' 8.5 10.0 10.0 2.0E.I. 70 F 191 0.3 3.0 3.3 6.5 8.5 29.0 1J.J. 77 F 111 0 4.0 3.5 7.0 11.0 10.5S.K. 73 F 125 1.0 2.5 3.0 8.0 9.5 1.5 16.0 2L.K. 61 F 109 0 3.0 2.5 1.5 9.0 19.5 42.0K.M. 80 F 138 0 1.0 4.0 5.0 2.5 6.5 4.5S.R. 72 M 150 0 0.5 1.5 2.0 3.5 9.5 4.0R.S. 80 F 131 0 3.5 5.5 8.0 ' 9.5 16.0 0.5 2A.S. 51 F 140 0 5.5 3.5 3.0 3.5 11.5 3.0 1M.S. 71 F 121 0 2.0 3.5 5.5 4.0 3.5 12.5 1Mean: 69 147 2.9 3.7 5.3 7.1 10.2 14.5 1Denson and Thompson (J. Med. Soc. of New Jersey , Vol. 57, 1960) , testing with a very similar preparation, (500 mg SS 150 mg ASA) , noted much less gastric distress than with AS alone as well as increased antirheumatic and anti-inflamma tory overnight effect.Leonards (J. Lab. & Clin. Med., Dec, 1968), using atomic tracing of occult blood loss, showed SSA did not produce-BUROM■ A. WIP w any bleeding above the control value determined by placebo, while ASA's loss was 4.8 ml/day compared to the placebo's 0.6 ml/day.CHART IIIAverage total blood loss, milliliters per day*Tablet CTablets Tablet A Tablet B (S.S.A. ,+ Tablet DSubject Weight per day (A.S.A. ,+ (lactose 486 mg. ; (S.S.A. ,+ ' (No.) 840 mg.) placebo) A.S.A. , 602 mg.) 162 mg.)R.K. 175 5 4.0 0.5 0.9 0.6R.N. 175 5 13.7 1.2 2.0 1.0A.T. 159 4 3.2 1.5 1.7 1.6M.J. 184 5 1.9 0.8 1.6 0.6P.P. 150 4 3.0 0.5 0.6 0.3J.M. 230 5 1.6 0.4 0.6 0.3F.M. 205 5 17.4 0.5 2.1 1.0M.B. 140 4 2.2 0.3 1.0 0.7B.E. 120 4 1.1 0.1 0.5 0.3A.O. 185 5 1.2 0.7 0.6 0.4J.H. 165 5 3.7 0.8 1.3 0.9R.J. 160 5 N.T-§ 0.2 N.T.§ 0.2*Averages ( ±standard error), 4.8 (±5.2), 0.6 (±0.4), 1.2 (±0.5), and 0.7 (±0.4) for A, B, C, and D, respectively. Comparisons:B vs. A, P 0.05; B vs. C, P 0.01; B vs. D, P 0.10; C vs. D,P 0.01.+A.S.A. denotes acetylsalicylic acid.+S.S.A. denotes salicylsalicylic acid.§Not tested.Aberg and Larsson (see above) also reported examination of the gastric mucosa of guinea pigs with SSA and ASA showed SSA caused no significantly increased. . .irritation , while after ASA the mucosa became hyperaemic and [the ASA] caused numerous erosions. D. Edmar (Acta Radiologica, Diag. , Vol. 11, 1971) examined human stomach mucosa with anOMPI - Olympus GT-Va gastrocamera following comparative doses of ASA and SSA with SSA again showing no effects above place while ASA showed multiple small gastric erosions in all.. subjects (p. 63) . The IAP noted SSA causes less asthma reaction than ASA (p. 35443). Litchfield (Arch. Pediat. , 55, 1938) reports SSA causes less allergy, and milder salicylism onset than ASA. The NNR (1939, p. 379) stated that SSA is no more toxic generally than ASA. SSA's clinical toxic dose is reported in the 5.5 to 6.6 gram range (Ha zlik, Actions and Uses of the Salicylates... 1927, p. 165), while ASA's is 5 to 6 grams (Goodman and Gllman, p. 338). ASA's fatal dose range is 10 to 30 mg (Goodman and Gilman, The Pharmaceutical Board of Therapeutics , 1975 edition, p. 336). SSA's can be expected to be in the same range.The second ingredient of this combination, acetaminophen, aside from being abbreviated APAP, is sometimes referred to as paracetamol. It is a metabolite of phenacetin and acetanilid, and is chemically referred to as n-acetyl- para-aminophenol, formulated C-.HqN02:The AMA Drug Evaluation Guide, 1977 (p. 346) states APAP is: ...an analgesic and antipyretic, its efficacy is equal to that of aspirin and it has the same uses (ie, treatment of headache, mild to moderate myalgia, arthralgia, fever) . Acetaminophen lacks the anti- inflammatory effect of the salicylates, but it is probably the analgesic-antipyretic of choice as an alternative to aspirin, particularly in patients allergic to aspirin or with a history of peptic ulcer. Unlike aspirin, acetaminophen does not antagonize the effects of uricosuric agents...Acetaminophen producesfa little or no methemoglobine ia and has not caused hemolytic anemia. It does not cause gastrointestinal bleeding. Although large doses have been reported to potentiate the action of oral anticoagulants, small doses have no effect on prothrombin time. It is not known whether prolonged use of acetaminophen can cause the type of renal injury associated with abuse of analgesic mixtures containing phenacetin. Hepatic necrosis and death have been observed following overdosage; hepatic damage is likely if an adult has taken a single dose of more than 10 g. The IAP (p. 53335-6) notes: one of the first symptoms of salicylate intoxification, or overdose, is tinnitus or 'ringing in the ears' ...Unfortunately, acetaminophen has no similar sign of toxicity or 'safety valve' to alert the consumer. Vane Prostaglandin Synthetase Inhibitors , (Raven Press, 1974) has shown both ASA and APAP have prostaglandin synthetase inhibition (PSI) actions underlying their very similar analgesic and antipyretic effects (p. 9-10) , and he reports another study (p. 233) showing that their shared acetyl factor plays a role in PSI.Summary of SSA-APAP's Actions, Uses, and Safety Collating all the above information on SSA and APAP, it is now possible to form a summary of how the SSA-APAP combination will be superior in several effects to ASA, APAP, or SSA alone, and to previous combinations of APAP and ASA, and of ASA and SSA. The new combination will be:(1) a more effective analgesic than ASA, APAP, or SSA alone since, while APAP alone is an equipotent analgesic . to ASA, SSA's additional (if weaker) analgesia will improve APAP's analgesia beyond APAP's own and ASA's, in three ways. First, SSA's strong anti-inflammatory action(Aberg-Larsson, Rubin, Denson, etc.) will eliminate any dispute about inflammation weakness as a drawback to APAP's analgesia. Second, both SSA's analgesic and anti- inflammatory actions last significantly longer than ASA's or APAP's, (Nordqvist, Rubin, etc.) so the time course o APAP's potentiated analgesia is extended. Third, SSA can deliver these salicylate analgesia effects from a 30% lower dosage than ASA, (P. K. Smith) .(2) an equipotent antipyretic to ASA, since both APAP and SSA are effective antipyretics (IAP, Merck) . APAP's very similar analgesic and antipyretic action compared to ASA may stem from their sha ed acetyl factors role in prostaglandin inhibition (Vane) .(3) a more effective anti-inflammatory and anti¬ rheumatic agent than ASA or APAP alone in two ways. Firs SSA is longer lasting than ASA at any dosage level, (Nordqvist) , and at antirheumatic dose levels can build up effective overnight action against morning stiffness within 24 hours (Rubin, Denson, etc.). Second, at any dosage levels, it can deliver 30 to 50% more anti- inflammatory action than ASA (P. K. Smith, Aberg-Larsson)(4) safer than either ASA or APAP. It will be effective gastrically non-bleeding and non-irritative since both SS (Leonards, Aberg-Larsson, Edmar) and APAP (AMA Drug Eval. are non-bleeding and non-irritative above placebo values. Both SSA and APAP cause less asthma (IAP) and allergy (Litchfield) . APAP's no -symptoms overdose danger will b lessened by SSA's salicylism tinnitus safety valve effe (IAP) . SSA has similar toxicity, salicylism, and fatal dose levels to ASA's (Hanzlik, NNR) , but the salicylism onset has been reported as milder than ASA's (Litchfield) Previous APAP-salicylate combinations, in the form of APAP-ASA, have been widely used over the years with excellent safety. Both APAP and SSA have been used separately over many years with an excellent record of safety. Both are FDA approved. -li¬ lt may sometime be advantageous to incorporate with this basic combination other pharmaceutically active ingredients. By way of illustrating these other pharmaceutically active ingredients, the following may be mentioned: other analgesics such as propoxyphene, codeine phosphate, or the like; analeptics such as caffeine, amphetamine or the like; antihistamines such as methapyrilene (or its hydro¬ chloride) , chlorpheniramine maleate or the like; anti- tussives or decongestants such as phenylpropanolamine (or the hydrochloride) , phenyleprine (or the hydrochloride) , or the like; sedatives such as bromural, phenobarbital, chlorpromozine, or the like; muscle relaxants such as mephenesin, chlorzoxazone, or the like; and antispasmodics or local anesthetics such as ethyl amionobenzoate, atropine sulfate, or the like. Additionally, potentiating ingredients may also be added, such as B.. active substances, such as in Fujimara, et al, U.S. Patent No. 3,284,298. However, in the preferred embodiment of this invention, the pharma¬ ceutically active material will consist essentially of the SSA-APAP dosage mixture.DOSAGE LEVELSDosage levels for salicylsalicylate alone typically are between 325 mg to 1000 mg. (Federal Register, p. 35443) . Toxic levels for salicylsalicylate begin somewhere between 5.5 and 6.6 grams per day for an adult (Hanzlik, p. 165). The NNR (1939 p. 379) has stated SSA and ASA are toxically similar. ASA's fatal dose is between 10 and 30 grams per day per adult (Goodman and Gilman, p. 338). SSA's is probably in the same range.The average dosage for APAP is in the 325 to 600 mg range. (Goodman and Gilman, p. 347) . A recommended maximum dosage level would be in the range of 2.6 to 4 grams per day per adult (AMA Drug Evaluation Guide, 1977, p. 346, and Goodman and Gilman above). Liver damage may- Λ REA UOMPI occur after a single dose of 10 to 15 grams, and a dose of 25 grams is usually fatal (Goodman and Gilman, p. 345- 346) . In the SSA-APAP combination a dosage level of 325 mg of APAP is sufficient, especially in the presence of SSA's additional analgesia, antipyretic and anti¬ rheumatic actions. Accordingly, an individual capsule or tablet would contain the preferred dosage of the combinat 500 mg of SSA per 325 mg of APAP. A recommended effectiv OTC maximum daily amount of 8-10 tablets will bring total daily consumption to 2.6-3.25 grams of APAP, and 4-5 gram SSA, well within accepted limits. Slightly higher dosage up to full therapeutic doses could also be given under- a physician's advice and supervision for antirheumatic effectiveness.OA A-_ WI | CLAIMS :1. An analgesic composition, which comprises, as active ingredients, from 100 to 1,000 mg of salicylsalicylic acid per 100 mg to 650 mg of acetaminophen.2. The composition of Claim 1 comprising approximately500 mg of salicylsalicylic acid and 325 mg of acetaminophen.3. A process of making an analgesic composition comprising combining from 100 to 1,000 mg of salicylsalicylic acid with from 100 to 650 mg of acetaminophen.4. The process of Claim 3, in which approximately 500 mg of salicylsalicylic acid are combined with 325 of acetaminophe .OMPI■< ° | ZOBIAN E | ZOBIAN E |
WO-1979000559-A1 | 1,979,000,559 | WO | A1 | EN | 19,790,823 | 1,979 | 20,090,507 | new | E01F13 | null | E01C11, E01F9, E01F15 | E01C 11/22B2, E01F 15/08, E01F 9/011F4, E01F 9/087 | IMPROVEMENTS IN LIMIT MARKING UNITS | Improvements in limit marking units of the kind comprising at least two holes (1h or 2f) for connecting and/or anchoring members (5) serving for interconnecting units (1 and/or 2) and/or for anchoring a unit (1 or 2) or units (1 and/or 2) to a base (6). For the purpose, in a simple way to provide a simple and low-cost limit marking unit having very good strength characteristics, the improvements according to the present invention are characterised by at least one reinforcement member (7) which extends from one hole (1h or 2f) for a connecting and/or anchoring member to another and surrounds these holes (1h or 2f). | Improvements in limit marking units.The present invention relates to improvements in limit marking units of the kind having holes for connecting and/or anchoring elements serving for interconnecting units or for anchoring a unit or units to a base.For limit marking units of the kind referred to in the opening paragraph a simple construction together with a very good mechanical stregth is aimed at, both for the single unit and for a number of interconnected units. This has not in the past been attained to the required extent.The object of the present invention was to eliminate this draw¬ back and to provide by simple means a simple and low-cost limit marking unit having a very good mechanical strength. This object, according to the invention, is mainly fulfilled by the improvement that each unit comprises at least one reinforcement member which ex¬ tends from one hole for a connecting and/or anchoring element to another and surrounds these holes.Owing to its disposition, the reinforcement member constitutes a very forceful reinforcement for the separate unit, even if the latter in itself should consist of a comparatively fragile material. The reinforcement member, in addition, forms a link in a chain of interconnected links which can be anchored and which chain will form automatically upon interconnecting a plurality of units. After inter¬ connection, the units cannot get separated when subjected to normally occurring actions, and the units cannot either get tilted if subjec¬ ted to normally occurring strains, since they support each other in an advantageous way and, in addition, may be anchored to the base.The invention and its advantages will be more closely described hereinafter with reference to the accompanying drawings, in which: Fig. 1 in a side-view illustrates a traffic limit marking unit according to the invention;Fig. 2 is a plan view of the traffic limit marking unit; Fig. 3 is a front view of the traffic limit marking unit; Fig. 4 in a side view illustrates two different interconnected traffic limit marking units according to the invention; andFig. 5 illustrates a number of inventive traffic limit marking units interconnected into a limit marking barrier which is provided with marking and separation poles.* κETϊrO PI tb WIIPPOO . The traffic limit marking units 1, 2 illustrated preferably con sist of a casting compound for instance of concrete material. The units 1, 2 are elongated in shape, for instance, and comprise, as seen in side view, a central portion la, 2a of uniform height and the top surface lb, 2b of which is substantially plane. The unit 1 has an end portion lc which is tapering in height in the direction away from the central portion, i.e. its top surface Id is sloping towards its outer end. The unit 1 has a second end portion le which at its top projects from the central portion la and forms a bottom face If to which another unit 1 can be connected with its top surfa Id. The unit 2-, on the contrary, has two uniform end portions 2c decreasing in height from the central portion 2a, i.e. their top surfaces 2d are sloping downward towards the end.Each unit 1, 2 is provided with a plurality of holes for instan three through-hoLes or partially through-going holes lg, 2e for receiving marking poles 3, separating poles 4, a combination of such poles or poles (not shown) of any other type. The end portions lc, le and 2c are provided with through-holes lh, 2f for connecting and/or anchoring elements 5 for interconnecting units 1 and/or 2 and/or for anchoring units 1 and/or 2 to a base 6.In order to provide an extremely simple reinforcement of each unit 1 and 2, which reinforcement enables protection of associated connecting and/or anchoring elements 5 and poles 3 and/or 4, and which reinforcement, in addition, enables the formation of a force- ful chain, the links of which are rigidly interconnected when units 1 and/or 2 are interconnected, at least one reinforcement member 7 is so shaped and arranged as to, as seen from above, surround an area containing all holes lh and lg and 2f and 2e, respectively.In order to attain the best reinforcement-chain-link effect wit a thin reinforcement member 7, the latter could suitably be endless in shape. The effect of strains acting through member 5 or poles 3, 4 in the unit 1, 2 or through unit 1 , 2 on member 5 are effectively reduced by the fact that the reinforcement member 7 follows portion of the periphery of each hole lh, 2f for the extension of the conne tion and/or anchoring members 5 in the peripheral portion or imme¬ diately adjacent the latter, and extends past the hole or holes lg, 2e for the marking and/or delimitation pole or poles 3, 4 so as to pass tangentiolly to this or these holes lg, 2e or immediately adja cent thereto. As a consequence of this arrangement, the reinforce^ ment member 7 will carry said strains very effectively, thus redu¬ cing the danger of breaking the cast material.In order to give the reinforcement member 7 a good stability by eliminating unnecessary bows, and without any need of increasing its dimensions, it may, as seen in side view, extend substantially parallel with the top surface lb, 2b of the central portion la, 2a and deviate downward at its end portions lc, 2c with decreasing height, extending substantially in parallel to the top surface Id, 2d of the end portion lc, 2c to the hole lh, 2f for the connecting and/or anchoring element 5. In constructing the unit 1, a portion of the reinforcement-element-portion extending in parallel with the top surface lb of the central portion la may extend into a projecting end portion le of the traffic separation unit 1, said end portion le being provided with a hole lh for the connection and/or anchoring element 5.To the end of enabling the reinforcement member 7 to carry exter¬ nal loads in the best way possible, it may - as seen from aside - pass through the holes lh, 2f for the connecting and anchoring ele¬ ments 5 about halfway between the end portions of the holes lh, 2f and the holes lg, 2e for the marking and/or limit poles 3, 4 adjacent to the upper end portions of these holes lg, 2f.The reinforcement member 7 will be particularly strong if it has its two longer sides 7a, 7b extending in parallel relation, and if one or more or all the holes comprise eyelets (not shown), these eyelets are suitably rigidly anchored to the reinforcement member 7 in order to increase the strength of the unit.The invention should not be considered as restricted to the embodiments here described and illustrated in the drawings. Thus, the reinforcement member 7 may be penetrated at a point without such penetration, in certain cases, constituting any serious disadvantages, the reinforcement member 7 may be disposed completely or in part out¬ side the body of the unit, more than one reinforcement member 7 may be present, and the reinforcement member 7 may follow the peripheries of one or more holes to a larger extent than as shown in the drawings. The holes 3, 4 may carry road or traffic signs, function as fence paling, marking poles or they can carry other kinds of elements for traffic guiding purposes.The connecting and anchoring member 5 may carry a sleeve (not shown) of elastic material next to its head. This may be compressibOMPI and should serve, inter alia, as a gripping member for a pair of tongs for extracting the member 5. The latter can be made short in order solely to serve as a connection member, or long in order to serve as a connecting and anchoring element. The holes lg, 2e for the poles 3, 4 may be wider at their uppe than at their lower ends in order to allow a certain amount of mov ment of the poles 3, 4 which can be passed through the units and b secured in place by a locking device (for instance a padlock) dis¬ posed beneath the unit. Poles locked in this way may carry parking meters. It may be advantageous in certain cases to provide the hol lg, 2e with a -bottom element which closes the bottom end of the hole completely or in part. This bottom element should be thin eno to enable the same to be broken by means of a pole 3, 4 when neces sary. It may be advantageous in certain cases to dispose sleeves o elastic material within one, several or all the holes so as to giv a resilient support for the poles 3, 4 and/or members 5. The last- -mentioned arrangement, however, has not been shown since it has no direct relation to the inventive principles. | Claims.1. Improvements in limit marking units of the kind comprising at least two holes (lh or 2f) for connecting and/or anchoring elements (5) serving for interconnecting units (1 and/or 2) or for anchoring a unit (1 or 2) to a base (6), and c h a r a c t e r i s e d by at least one reinforcement member (7) which extends from one hole (lh or 2f) for connecting and/or anchoring element to another and surrounds these holes (lh and 2f).2. The improvements of claim 1 and c h a r a c t e r i s e d i n that the reinforcement member (7) is endless in shape.3. The improvements of claim 1 or 2, where the limit marking unit has holes (lg or 2e) for receiving marking and/or limit indicating poles (3 and/or 4) and further c h a r a c t e r i s e d i n that the reinforcement member (7) surrounds the area containing these holes (lg or 2e).4. The improvements of claim 3, c h a r a c t e r i s e d i n that the reinforcement member (7) follows4 portions of the periphery of each hole (lh, 2f) for the connecting and/or anchoring members (5), extending in the peripheral portion or immediately adjacent the latter and extends past the hole or holes (lg, 2e) for the mark¬ ing and/or limit marking pole or poles (3, 4) in tangential relation to this hole or these holes (lg, 2e) or passing immediately adja¬ cent thereto.5. The improvements of any preceding claim, where the limit marking unit (1, 2) is elongated in shape with a substantially uniformly high central portion (la, 2a) as seen in side view, and at least one end portion (lc, 2c) having a height which slopes downward away from the central portion (la, 2a) and has holes (lh, 2f) for said connecting and/or anchoring member (5), and further c h a r a c t e r i s e d n that, as seen in side view, the reinforcement member (7) extends substantially parallel with the top surface (lb, 2b) of the central portion (la, 2a) and deflects downward at the end portion (lc, 2c) with decreasing height, extending substantially parallel with the top surface (Id, 2d) of the end portion (lc, 2c) to the hole (lh, 2f) for the connecting and/or anchoring member (5)..6. The improvements of claim 5, further c h a r a c t e r i s e d i n that a part of the reinforcement-member portion extending in parallel with the top surface (lb) of the central portion (la) extendsOMPI into α projecting end portion (le) of the traffic limit marking uni (1) which end portion (le) is provided with a hole (lh) for the connecting and/or anchoring member (5).7. The improvements of claims 3 or 4 in which the holes (lh, 2f) for the connecting and/or anchoring members (5) extend completely through the traffic limit marking unit (1, 2) and the hole or holes (lg, 2e) for the marking and/or limitation poles (3, 4) extend com¬ pletely or substantially completely through the traffic limit marki unit (1, 2) further c h a r a*c t e r i s e d i n that, as seen in side view, the reinforcement member (7) passes by the holes ( h, 2f) for the connecting and/or anchoring members (5) at a point abou halfway between the end portions of the holes (lh, 2f) .and the hole (lg, 2e) for the marking and/or limitation poles (3, 4) in the vici nity of the upper end portions of these holes (lg, 2f). 8. The improvements of any preceding claim, where the traffic limi marking unit (l, 2) is elongated, further c h a r a c t e r i s e i n that said reinforcement member (7), as seen in a top-plan view has two substantially parallel, longitudinally extending sides (7a( 7b). 9. The improvements of any preceding claim, in which at least one of the holes ( h or 2f) for the connection and/or anchoring member (5) and/or holes (lg or 2e) for marking and/or limit marking poles (3 and/or 4) are each provided with an eyelet, c h a r a c t e r i s e d i n that said eyelet is rigidly connected to the reinforce ment member (7).O | EDEBRAND K | EDEBRAND K |
WO-1979000563-A1 | 1,979,000,563 | WO | A1 | EN | 19,790,823 | 1,979 | 20,090,507 | new | E01C23 | null | E01C23, E02F5, E21C27 | E01C 23/085, E01C 23/12C, E02F 5/32H, E21C 27/46 | PAVEMENT PLANING METHOD AND APPARATUS | Asphalt or concrete pavement is removed from a road bed by an elongated cutter blade (94) that extends in a downward and forward direction along a cutting plane to a cutting edge. The cutting plane forms an acute angle of between 450 and 550 with the surface of the pavement. The cutter blade is intermittently driven with a force parallel to the cutting plane in the forward direction while the cutting edge penetrates the pavement to drive the cutter blade incrementally in a forward direction and plane on the pavement in a chisel-like manner. A source of vibrations (56, 56') is connected to one end of plural spaced apart resonant beams (54, 54'). At the other end, the beams drive the cutter blade. The source produces a reciprocating force that is transmitted to the blade by the beams each of which has an output that reciprocates about a neutral position responsive to the force of the source. A continuous unidirectional force is applied to the source by a tool carrier (44). The blade advances intermittently along a work path through the pavement responsive to the continuous unidirectional force and the reciprocating force. A gap is held between the neutral output position of the beams and the blade when the blade is unable to advance through the pavement responsive to the continuous unidirectional force and the reciprocating force. Specifically, the force of the source is sufficiently large relative to the unidirectional force to overcome the latter, and to drive the tool holder back away from the blade when the blade is unable to advance along the work path, thereby establishing a protective gap. Cessation of resonance is prevented when the blade encounters an immovable object by establishing the protective gap in the described manner. | PAVEMENT PLANING METHOD AND APPARATUSBackground of the InventionThis invention relates to road working equipment and, . more particularly, to a method and apparatus for removing pavement from a road bed. When resurfacing a road, it is often desirable to remove the existing pavement in order to maintain the original grade and/or recycle the pavement material in the case of asphalt. There are a number of known procedures for removing asphalt pavement, all of which require an expenditure of a great deal of time, money, and/or effort.One procedure is to soften the asphalt pavement with a radiant heater or flame burner, and then clean off the softened asphalt in layers with the mold board of a road grader. The thickness of each layer removed in this manner is limited by the depth of the asphalt that can be softened by the radiant heater or flame burner, which is very small.Another procedure that has been used without much success is to remove the asphalt pavement with a plurality of diamond cutting wheels arranged on a common rotating shaft. The experience has been that these cutting wheels are expensive and the operation is slow.A third procedure is to mill off the pavement in layers with a rotating drum on which carbide tips or teeth are mounted. In order to make a deep cut in the pavement, a great deal of downward force needs to be exerted on the drum, which resul in too many fine particles if the asphalt is to be recycledStill another procedure is to use sonic energy to cut into pavement. As described in Bodine Patent 3,232,669, a sonic vibration generator is coupled to the upper end of an essentially vertical beam or bar having pavement-engaging teeth or serrations formed at its lower end. The vibration generator supplies energy to the beam at its resonant fre¬ quency, and the vibrating teeth at the lower end of the bea cut into the pavement. Summary of the Invention One aspect of the invention is a method for removing . asphalt or concrete pavement from a road bed. An elongated cutter blade that extends in a downward and forward directi along a cutting plane to a cutting edge is held in contact with the pavement such that the cutting plane forms an acut angle with the surface of the pavement.. The cutter blade engages the pavement such that the cutting edge penetrates the pavement. The cutter blade is intermittently driven wi a force parallel to the cutting plane in the forward direc¬ tion while the cutting edge penetrates the pavement to driv the cutter blade incrementally in a forward direction and plane off the pavement in a chisel-like manner. Another aspect of the invention is pavement planing apparatus comprising a transversely elongated cutter blade mounted on a support frame to permit reciprocation approxi¬ mately in a cutting plane. The cutter blade is disposed at an acute angle between 45° and 55° to the surface of a pave ment, and extends in a downward and forward direction along the cutting plane to a cutting edge that lies in the cuttin plane. Plural spaced apart force transmitting beams having an input and an output are mounted on the support frame, a source of vibrations is connected to the input of the force transmitting beams, and the output thereof strikes the cutt _0MPI blade to apply a unidirectional force thereto parallel to the cutting plane in a forward direction. A vehicle continuously transports the support frame in the forward direction while the unidirectional force is being applied to the cutter blade. The cutter blade with the described apparatus engages and planes off pavement in a chisel-like manner as the apparatus is transported in the forward direction.A feature of the foregoing apparatus is a support frame comprising plural spaced apart upright support beams, plural spaced apart forwardly projecting support beams, and plural struts, all equal in number to the force transmitting beams. The top of the upright support beams is attached to the back of the respective forwardly projecting support beams. One end of the struts is attached to the front of the respective forwardly projecting support beams and the other end of the struts is attached to the bottom of the respective upright support beams. The force transmitting beams are mounted on the support frame so they are approximately parallel to the respective struts, with the input near the front of the respective forwardly projecting support beams and the output near the bottom of the respective upright support beams. The cutter blade lies in front of the output of the force transmitting beam approximately under the upright support beams. Preferably, the upright support beams have a larger mass per unit length than the forwardly projecting support beams and the struts. As a result, the center of gravity of the support frame is located nearly directly over the cutter blade so its weight counteracts most effectively the reactive forces exerted on the cutter blade by the material being cut.According to another feature of the invention, sonic generator produces a reciprocating force that is transmitted to a tool by a resonant or nonresonant force transmitting member having an output that reciprocates about a neutral position responsive to the force of the sonic generator. A continuous unidirectional force is applied to the force transmitting member. The tool advances intermittently along a work path through a medium responsive to the continuous unidirectional force and the reciprocating force. According to the invention, a gap is held between the neutral output position of the force transmitting member and the tool when the tool is unable to advance through the medium responsive to the continuous unidirectional force and the reciprocating force. The gap protects the tool driving apparatus from destruction.In the preferred embodiment, the sonic generator and the force transmitting member are supported by a tool holder or carrier to which the continuous unidirectional force is- applied. The reciprocating force produced by the sonic generator is substantially larger than the continuous uni¬ directional force applied to the tool holder. Specifically, the force of the sonic generator is sufficiently large relative to the unidirectional force to overcome the latter and to drive the tool holder back away from the tool when the tool is unable to advance along the work path, thereby establishing the protective gap.In one aspect of the invention, which is applicable when the force transmitting member is resonant, cessation of resonance is prevented when the tool encounters an immovable object during application of the continuous unidirectional force and the force of the sonic generator. Preferably, although in the broadest form of the invention not necessaril this is done in the manner described above._ O PI Brief Description of the DrawingsThe features of a specific embodiment of the best mode contemplated of carrying out the invention are illustrated in the drawings, in which: FIG. 1 is a side elevational view of tool driving apparatus embodying the present invention and especially arranged to cut or shear hard material such as asphalt or concrete;FIG. 2 is a top plan view of the front of the apparatus of FIG. 1;FIG. 3 'is a fragmentary enlarged side view of the material cutting assembly of the apparatus with portions broken away to show interior details;FIG. 4 is a fragmentary cross-sectional view taken along line 4-4 of FIG. 3;FIGS. 5A-5C are diagrammatic views of the tool and its drive mechanism in different stages of operation;FIG. 6 is a graph showing the relationship of time and displacement of the tool and drive mechanism in the various operational stages shown in FIGS. 5A-5C;FIG. 7 is a front elevation view of part of the apparatus of FIG. 1;FIG. 8 is a fragmentary cross-sectional view taken along line 8-8 of FIG. 3, omitting the structure between the resonant beams;'FIG. 9 is a side elevation view of the cutting assembly support frame of the apparatus of FIG. 1;FIG. 10 is a front elevation view of the support frame of FIG. 9; and FIG. 11 is a top plan view of the support frame of FIG. 9. Detailed Description of the Specific EmbodimentIt is the general objective of the present invention to provide apparatus for effectively applying driving force to a tool, such as a cutter blade, for rapidly sheari or cutting hard material such as a layer of concrete, aspha or other material from a roadway or similar surface, or to various other tools specific to a particular operation.Specifically, the tool can take the form of a cutter blade having an elongated cutting edge arranged to engage concrete or other material to be removed at a controlled angle and at- a controlled depth, and having a transverse disposition so that, upon energization, a swath of predeter width can be simultaneously removed. The cutter blade is mounted from a powered and steered mobile frame for recipro eating motion, which mounting preferably constitutes a pivo support for the cutter blade so that it moves arcuately fir in a forward cutting direction and then rearwardly. The po of pivotal support is in advance of the cutting edge in the direction of cutting so that such pivotal motion is directed angularly downward into the material which is to be cut or severed, and at an angle which will vary dependent on the hardness and other mechanical properties of the material, and which can be adjusted to optimize the operation.Force impulses are delivered cyclically to the pivotall supported cutter blade by reciprocating drive means, which on its forward stroke engages and drives the cutter blade into the material and thence withdraws preparatory to a subsequent driving stroke, forming a gap between the cutter blade and the drive means. Forward motion of a mobile supporting frame generates a tractive force which tends to close the gap in a fashion such that the reciprocating drive means is brought into contact with the cutter blade after the former's speed (and momentum) approaches a maximum in the forward or cutting direction. Thus, the driv means is in driving contact with the cutter blade itself for less than 180° of any given cycle. The drive means takes the form of a resonant force transmitting member powered by a sonic generator or oscillator incorporating the general principles embodied in the unit shown and described in the aforementioned patent. However, the resonant member constitutes a generally upright beam mounted by a resilient tire at its upper node position to accommodate pseudo-nodes generated during operation. An additional rigid member engages the beam at its lower node position to support and maintain the desired beam disposition. The sonic generator is connected to the resonant beam at its upper end and preferably includes multiple eccentric weights mounted in spaced relation with a multiplicity of bearings on a common shaft so that the requisite force may be generated while minimizing the shaft diameter, and the peripheral speed and wear of the bearings because of the distribution of the bearing loads. The lower end of the beam lies adjacent the cutter blade to deliver the force impulses in substantial alignment with the cutting direction.The input force generated by the sonic generator is greater than the described tractive force resultant from the forward motion of the powered mobile supporting frame, and as a consequence, there is no possibility for clamping of the beam end against the cutter blade (and the engaged material), which would stop the resonant actuation and permit the vibratory action of the sonic generator to be applied in a harmful fashion to itself and the supporting frame members.Obviously, the same force imbalance principle can be applied to other tools such as mentioned, with the same critical and advantageous effect. In each case, however, it is important that the sonic generator provide an input force greater than that of a continuing tractive effect or its equivalent force tending to close the gap.With initial reference to FIGS. 1 and 2, a material cutting assembly generally indicated at 10 is mounted at the front of a mobile carrier 11 which includes forward and rearward frame sections 12, 14, each supported by two rubber-tired wheels 16, 18, the two frame sections being connected by a vertical pivot pin 20 which enables articulation of the frame sections for purposes of steering. Material cutting assembly 10 is specifically designed to cut asphalt or concrete pavement as found on streets, roads, and highways.A steering wheel 22 is mounted forwardly of a driver's seat 24 on the front section 12 of the frame and is arranged to -energize, upon turning, a hydraulic ram 26 pivotally joining the frame sections 12, 14 so as to effect articulation thereof and consequent steering. A hydraulic pump 30 is mounted on the rear section 14 of the frame, and driven by an internal combustion engine 32. Fluid from a hydraulic reservoir 28 is driven by pump 30 through suitable hydraulic conduits (not shown) to hydraulic ram 26.The engine 32 also drives a second hydraulic pump 34 which is hydraulically connected to hydraulic motors 35 to drive the wheels 16 on the front frame section 12 and the wheels 18 on the rear frame section 14, thus to provide motive power for the entire mobile carrier 11 in a generally conventional fashion. As will be understood, the motive power delivered to the wheels will urge the front- mounted cutting assembly 10 against material being cut with a certain tractive force which, for cutting a six-foot swath of concrete or asphalt, should vary for example between 5,000 and 60,000 pounds, depending upon the material resistance and vehicle speed. Assuming the weight of the vehicle and its load, i.e., material cutting assembly 10 and mobile carrier 11, is 75,000 pounds, the maximum tractive force, i.e., motive power delivered to the wheels, must be less than the weight of the vehicle and its load, e.g., about 60,000 pounds, to prevent slippage of wheels 16 and 18. As is well known in the art, the maximum tractive force of the vehicle depends upon the friction between the wheels and the surface on which it moves.Material cutting assembly 10 is symmetrical about a center plane in the direction of movement, i.e., parallel to the plane of FIG. 1. Many of the elements on the right side of the center plane, as viewed from the front, i.e., the left in FIG. 1, which are identified by unprimed reference numerals, have counterparts on the left side of the center plane, which are identified by the same reference numerals primed.In order to mount the mentioned material cutting assembly 10, a pair of laterally-spaced parallelogram units 36, 36' extend forwardly from the forward frame section 12. More particularly, the parallelogram units 36, 36' include parallel upstanding legs 38, 38' pivotally connected at their lower extremities to the central portion of a fixed transverse shaft 40 on the front frame section 12 and pivotally joined at their upper extremities to the rear ends of forwardly projecting legs 42, 42' . These forwardly projecting legs 42, 42' are pivotally joined at laterally- spaced positions (see FIG. 2) to a generally triangular cutting assembly support frame 44. As shown in FIGS. 9 through 11, cutting assembly frame 44 comprises spaced apart, upright support beams 46, 46', spaced apart, forwardly projecting support beams 47, 47', struts 45, 45', and cross beams 49, 51, and 53. Downwardly and forwardly angled stop mounts 57, 57', are formed near the bottom of upright support beams 46, 46'. At its ends, cross beam 51 is attached, for example by welding, to the top of support beams 46, 46', and the back of support beams 47, 47'. At the front of support beams 47, 47' are formed vertically flared bracket mounts 59, 59'. Cross beam 53 is connected between flared bracket mounts 59, 59' and is attached thereto, for example, by welding. An upwardly and forwardly extending platform support beam 61 is attached, for example by welding, to the middle of the cross beam 53. A platform 65 having mounting blocks 89 is attached to the upper end of support beam 61, for example, by welding. Struts 45, 45' are connected between beams 47, 47' near the front, and beams 46, 46' near the bot and are attached thereto, for example, by welding. Cross beam 49 is connected between support beams 46, 46' near the bottom and is attached thereto, for example, by welding. Pairs of rectangular brackets 75, 75' are attached, for example, by welding to the sides of flared bracket mounts 59, 59'. Support beams 46, 46' and cross beams 49 and 51 are made of solid steel so their mass per unit length is as large as possible. Support beams 47, 47', including brac mounts 59, 59', struts 45, 45', and cross beam 53 are hollow so their mass per unit length is as small as possible Consequently, the resultant center of gravity of cutting assembly frame 44 is rearwardly located near support beams 46, 46'. Support beams 46, 46' form the forward upright legs of the parallelogram units 36, 36*. Lower and outwardl curving legs 48, 48' are pivotally connected at their opposi extremities to the lower ends of the support beams 46, 46' and the previously described shaft 40, thus completing the two parallelogram units 36, 36'. Brackets 80, 80' are attached to crossbeam 51, for example, by welding. Forwardl projecting legs 42, 42' are connected to brackets 80, 80' by pivoting links 84, 84' (FIG. 1). Pairs of brackets 85, 85' are attached to upright support beams 46, 46', for example, by welding. Outwardly-curving legs 48, 48' are connected to bracket pairs 85, 85' by pivot pins 87, 87'. A powered hydraulic ram 50 is pivotally secured between the forward frame section 12 and the rear upright legs 38, 38' of the parallelogram units 36, 36' to enable powered variation of the parallelogram disposition and accordingly the angular disposition of the cutting assembly 10. Additional powered hydraulic rams 52, 52' pivotally joined to the top of the frame section 12 and the lower generally horizontal legs 48, 48' of the parallelogram units 36, 36' enable substantially vertical adjustment of the cutting assembly.The cutting assembly frame 44 supports a pair of5 resonant beams 54, 54' m the form of angularly upright parallel resonant beams composed of solid steel or other elastic material. Resonant beams 54, 54' are approximately parallel to struts 45, 45'. A sonic generator in the form of a pair of synchronized orbiting mass oscillators 56, 56'10 is secured by bolts or the like to the upper extremity of each resonant beam and generally incorporates the principles of an orbiting mass oscillator of the type shown in either United States Patent No. 2,960,314 or United States Patent No. 3,217,551. (The disclosures-*-5 of these patents are incorporated fully herein by reference.) Orbiting mass oscillators 56, 56' are driven by a suitable hydraulic motor 58, that is energized through suitable hydraulic conduits (not shown) from a third hydraulic pump 60 driven by the previously described engine 32. In20 order to maximize the resonant power yet provide an extensive useful life, each orbiting mass oscillator 56, 56', as best shown in FIGS. 3 and 4, includes a shaft 62 driven by the hydraulic motor 58 and supported at several axially spaced positions by bearings 64 in a generator housing25 66. A plurality of eccentric weights 68 and 79 are carried by the shaft 62 adjacent to the bearings 64 so that their load on the shaft and the bearing loads are distributed. Preferably, the eccentric mass of the centrally located weight 68 is twice as large as peripherally located weights 0 79; thus, the load on each of bearings 64 is approximately the same. The shaft can be relatively small because of such load distribution, and the exterior diameter and thus peripheral speed of the bearings can be minimized for a given power level. Rather than bolting the sonic generator 5 to the beams as shown, the sonic generator housing and the beams could be cast as a single unit in a one-piece construction.A drive shaft 67 is coupled by pairs of tandemly connected universal joints 69, 69' to shafts 62, 62'. Drive shaft 67 is supported by bearings 63, 63' mounted in the sidewalls of a protective housing 73, through which drive shaft 67 passes. Power transmission means 71 such as a belt, chain, or gear train inside housing 73 couples hydraulic motor 58 to drive shaft 67. Lubricating oil is sprayed in housing 73 by means (not shown) onto power transmission means 71 and bearings 63, 63'. Seals (not show outside of bearings 63, 63' prevent the oil spray from leavin housing 73. Protective housing 73 is secured to mounting blocks 89 (FIGS. 9 through 11). Motor 58 is attached, for example by bolting, to the outside of housing 73. Fly wheels 72, 72' are mounted on shaft 67 outside housing 73 for the purpose of isolating motor 58 and power trans¬ mission means 71 from transient forces exerted by oscillators 56, 56'. Housing 73 is stationary so drive shaft 67 only rotates. Resonant beams 54, 54' reciprocate. Tandemly connected pairs of universal joints 69, 69' permit shafts 62, 62' to reciprocate with beams 54, 54' as they are rotatably driven by drive shaft 67.Energization of the exemplary embodiment illustrated provides a total peak energizing input force to the two resonant beams 54, 54' of 125,000 pounds in the form of sequential sonic oscillations at a frequency of approximately 100 cycles per second, i.e., at or near the resonant frequenc of resonant beams 54, 54'. Thus, the total peak force provide by oscillators 56, 56' is larger than the weight of the vehic and its load. These force oscillations, delivered to the upper end of the beam, cause resonant vibration thereof through appropriate dimensional design of such beam at that frequency so that a corresponding cyclical reciprocal vibration at the lower end of the beam is derived, as shown 1 by the arrow A in FIG. 3, preferably with a total peak-to- peak displacement of approximately one inch. Pairs of weights 55, 55' are attached, for example by bolting, to the front and back of resonant beams 54, 54' at the° lower end to increase the momentum thereof. Each resonant beam 54, 54' is designed and so driven that two vibration nodes are formed thereon inwardly from its opposite extremities, and its ends are free to vibrate, i.e., reciprocate, and in fact do vibrate. In summary, resonant1° beams 54, 54' are driven to form standing wave vibrations in their fundamental free-form mode. Each beam is carried from the cutting assembly frame 44 at its upper node position. However, the connection is resilient to allow for node variations (pseudo-nodes) during actual operation.15 Specifically, as illustrated in FIGS. 3 and 4, pairs of rectangular brackets 75, 75' are attached, for example by welding, to the sides of flared bracket mounts 59, 59'. Pairs of annular resilient members 74, 74' in the form of pneumatic rubber tires are located inside20 pairs of cylindrical housings 77, 77'. Housing pairs 77, 77' are held on opposite sides of resonant beams 54, 54' by pairs of connecting arms 70, 70' attached, for example by bolting, to bracket pairs 75, 75'. Pairs of annular resilient members 74, 74' are mounted on pairs of central 5 hubs 78, 78'. Shafts 86, 86' are press fitted into bores 88, 88' in resonant beams 54, 54' at their upper node positions. Hub pairs 78, 78' are mounted for rotation on the ends of shafts 86, 86' by pairs of bearings 82, 82'. Thus, resonant beams 54, 54' are supported by shafts30 86, 86' and are pivotable about their axes by virtue of bearing pairs 82, 82'. In the manner of a spring, the described pneumatic tires, which serve as upper node supports for resonant beams 54, 54', accommodate the longitudinal changes in the node position (pseudo-nodes)35 resulting from loading of the resonant beams, when the cutter blade described below is in engagement with a material to be cut, sheared, or planed, and the internal tire pressure can be changed as required to control the spring constant. As shown in FIGS. 3 and 8, at the lower node position, resonant beams 54, 54' are encompassed by rigid metal stop members 90, 90' at their rear, resilient rubber pads 91, 91' at their front, and pairs of resilient rubber pads 92, 92' at their sides. Pad pairs 92, 92' and pads 91, 91' comprise pieces of rubber vulcanized on metal mounting plates.' Members 90, 90', pads 91, 91', and pad pairs92, 92' are secured to the lower end of cutting .assembly frame 44. Specifically, stop members 90, 90' are attached, for example by bolting, to mounts 57, 57'. Pairs of bracket 100, 100' are attached to opposite sides of support beams 46, 46', for example by bolting. Cross supports 93, 93' are connected between bracket pairs 100, 100', for example by bolting. Mounts 57, 57', bracket pairs 100, 100', and cross supports 93, 93' define rectangular openings through which the lower portions of resonant beams 54, 54' pass. Pads 91, 91' are secure to cross supports93, 93', for example by bolting, and pad pairs 92,92' are secured to the inside of bracket pairs 100, 100', for example by bolting. Pad pairs 92, 92' at the sides of resonant beams 54, 54' are spaced slightly therefrom and serve to guide the resonant beams as they pivot about their upper node support and reduce noise and wear. When resonant beams 54, 54' are at rest, they lie on and are supported by pads 91, 91'. When resonant beams 54, 54' are resonating during operation of the apparatus, their lower node is driven up against stop members 90, 90' by the reaction of the material being worked upon as shown in FIGS. 3 and 8, and remain in abutment with stop members 90, 90' during operation of the apparatus. Thus, stop members 90, 90' serve as rigid lower node supports for resonant beams 54, 54'. Stop members 90, 90 and pads 91, 91' are spaced sufficiently far apart to enable resonant beams 54, 54' to be shimmed to synchronize their transfer of force to the work tool. Specifically, shims 76, 76' are inserted between stop members 90, 90' and stop mounts 57, 57' so the lower extremities of resonant beams 54, 54' in their neutral position are both spaced precisely the same distance from the lever arms and cutter blade described below. Consequently, since oscillators 56, 56' run in phase and resonant beams 54, 54' reciprocate in phase, the lower extremities of resonant beams 54, 54' strike the cutter blade at the same time, i.e., in synchron¬ ism. As represented in FIG. 8 by the different thicknesses of shims 76, 76', stop members 90, 90' will in general have to be shimmed to a different degree to achieve the described synchronism, because of manufacturing tolerances. This is accomplished by the following procedure: first, one of the stop members is shimmed; second, the cutter blade is lowered into contact with the road surface; third, mobile carrier 11 is driven forward to rotate resonant beams 54, 54' about their upper node supports, until one of the resonant beams contacts its stop member at the lower node support; and fourth, the other stop member is shimmed until the other resonant beam contacts it. For more details about shimming stop members 90, 90' to synchronize resonant beams 54, 54', reference is made to my copending application Serial No. 916,112, filed June 16, 1978.As shown in FIGS. 3 and 7 the material cutting assembly 10 includes a work tool which takes the form of an angularly- directed and transversely-extending cutter blade 94 held in a blade base 95. Cutter blade 94 and blade base 95 extend along the full width of the apparatus between beams 54, 54'. In other words, cutter blade 94 is transversely elongated and is disposed at an acute angle to the surfaceOMPI |\ of pavement to be cut, extending in a downward and forward direction along a cutting plane to a cutting edge that lies in the cutting plane. Cutter blade 94 is clamped to blade base 95 by a retaining bar 81 that is attached to blade base 95 by bolts 83. Lever arms 96, 96', are pivoted about substantially horizontal pivot pins 9*8, 98' on bracket pairs 100, 100'. Lever arms 96, 96' are attached for example by welding to the ends of blade base 95 near resonant beams 54, 54'. It is to be particularly observed, as clearly shown in FIG. 3, that the cutting edge of the cutter blade 94, when in material engagement, lies to the rear of the pivot pins 98, 98' so that any movement of the cutter blade 94 in a forward direction or to the left will be accompanied by a substantial downward force component and thus will result in penetration into the material being cut, without deflection of cutter blade 94 away from material engagement. Furthermore, because the pivotal support provides for a slight arcuate motion of the cutter blade 94, a slight additional separation of the layer of cut material from that lying therebelow will result. Thus, the cutter blade assembly comprising cutter blade 94, blade base 95, retaining bar 81, and lever arms 96, 96' is pivotably supported by brackets 100, 100' so it is adjacent to the lower extremity of the resonant beams 54, 54'. When the beams reciprocate, they drive the cutter blade assembly in a forward and downward direction or to the left, as shown in FIG. 3, and thereafter withdraw from contact with the cutter blade assembly in its cyclical displacement in the opposite or rearward direction. Thus, only unidirectional driving impulses are delivered to the cutter blade assembly in its forward direction, and in alignment with its cutting direction, so the cutter blade 94 advances with a chisel-like action.As depicted in FIG. 7, a conveyor 97 in the middle of the front of assembly 10 above blade base 95 carries materia broken up by cutter blade 94 away from the assembly, as for example in a windrow or pile between wheels or to a dump truck moving with the assembly. For the sake of clarity, the driving and supporting means for conveyor 97 are not shown. Diverters 99, 99', which extend across the front of assembly 10 above blade base 95 on either side of conveyor 97, are attached to brackets 100, 100'. Diverters 99, 99' are positioned to direct all the broken up material to conveyor 97. When frame 44 is lifted from its operating position for the purpose of transporting assembly 10 to a new location, by rams 52, 52', or by other lifting means, blade base 95 pivots against diverters 99, 99', or other stop means, so cutter blade 94 is raised and thus does not scrape along the ground during transportation. Cutter blade 94 comprises a work tool that moves along the road surface, which comprises the work path. Cutting assembly frame 44 functions as a tool holder or carrier. Continuous unidirectional force is applied thereto by mobile carrier 11 in a direction parallel to the work path. Oscil- lators 56, 56' generate a reciprocating force, at least one component of which acts parallel to the work path. Each resonant beam 54, 54' comprises a force transmitting member, its upper extremity comprising an input to which the recipro¬ cating oscillator force is applied, and its lower extremity comprising an output from which the reciprocating force is transferred to the tool. The tool advances intermittently along the work path responsive to the continuous unidirec¬ tional force applied by mobile carrier 11 and the recipro¬ cating force applied by oscillators 56 and 56'. Obviously, when the cutter blade 94 engages the material, reactive forces will be directed thereagainst, both in horizontal and vertical directions, and will be dependent upon the character of the material. An angle between 45° and 55° relative to the surface of the material has been found optimum for cutting pavement to maintain the-BUREΛtfOMPI ultimate cutting in a plane parallel to the material surface in the direction of machine travel. In general, the harder the material the larger the angle. Thus, for ordinary asphalt the angle has been found to be between 48° and 52°, for soft asphalt the angle has been found to be be¬ tween 45° and 48°, and for concrete the angle has been found to be between 52° and 55°. The parallelogram units 36, 36' can be shifted by appropriate energization of the angular adjustment ram 50 to optimize the cutting action on the ° material encountered. Similarly, the cutting depth of cutte blade 94, below the grade, i.e., surface of the pavement, can be automatically or manually controlled by appropriate energization of the vertical adjustment rams 52, 52'. The previously described design of cutting assembly frame 44, 5 which locates its center of gravity close to upright support beams 46, 46', i.e., nearly directly over cutter blade 94, permits the weight of cutting assembly frame 44 to counteract most effectively the reactive forces exerted on cutter blade 94 by the material being cut. This minimizes ° the forces and moments exerted on parallelogram units 36, 36' by cutting assembly frame 44 and discourages cutter blade 94 from moving out of engagement with the material being cut. When the beams 54, 54' withdraw from contact with the cutter blade 94 during resonant vibration a momentary 5 gap is formed which will remain until a repeated forward motion of the beams 54, 54'. To maximize the cutting force, it has been found that contact of the beams with the cutter blade preferably is made in the region where maximum forward velocity (and momentum) of the beams is approached in the forward (cutting) direction. Since the cutter blade 94 is in engagement with material to be cut, the adjacent beam is urged forwardly relative thereto, thus to close the momentary gap at the appropriate time of the resonant cycle. This action, which is important to the effective cutting of concrete, asphalt, and other hard materials, can be explained more readily by reference to FIGS. 5A-5C wherein the various operational dispositions of the cutter blade 94 and the resonant beams 54, 54' are diagrammatically illustrated in somewhat exaggerated form for purposes of explanation.In the time-displacement graph of FIG. 6, the abscissa N represents the neutral position of beams 54, 54', sinu¬ soidal waveform S represents the reciprocating displacement of the beam outputs about their neutral position as a func¬ tion of time, and the dashed line represents the position of the tool, i.e., cutter blade 94, relative to frame 44 as a function of time. For maximum force transfer, it is desirable for the beams to strike the tool when the beam outputs are traveling at maximum forward velocity, i.e. , at the neutral position of the beam outputs. The neutral position of the beam outputs is their position when at rest, i.e., not resonating or being deflected, while the beam is in operating position, i.e. , pivoted into abutment with stop member 90. During operation, as beams 54, 54' resonate, when the beam outputs are at their neutral position, which is represented by point A in FIG. 6, a small momentary gap typically exists between beams 54, 54*, and the back surface of lever arms 96, 96', as illustrated in FIG. 5A. As the beam outputs move slightly forward from their neutral position toward the tool, they simultaneously strike the tool and drive it forward to perform the desired work, i.e., cutting through the concrete or asphalt road surface. The beam outputs remain in contact with the tool, as illustrated in FIG. 5B, until the beam outputs reach the forward extremity, i.e., peak, of their reciprocating excursion, which is represented by point B in FIG. 6. This is approximately slightly less than 90° of the beam reciprocation cycle. As the beam outputs begin to move in a rearward direction on their reciprocating excursion, a momentary gap is formed•BUREAITO Pf between the beam outputs and the tool, which is represented by the distance between lines D and S in FIG. 6. The continuous forward movement of frame 44 with mobile carrier 11, while the tool is held stationary by engagement with the road surface, reduces the distance between the tool and the neutral position of the beam outputs, which is represented in FIG. 6 by the slope of line D toward line N. When the beam outputs are moving in a rearward direction beams 54, 54' are spaced from lever arms 96, 96' as illustra ° in FIG. 5C. The momentary gap between the tool and the beam outputs is maximum at a point of their reciprocating excursion slightly before the rear extremity, which is represented by point C in FIG. 6. In summary, during each cycle of reciprocation of beams 54, 54', the beam 5 outputs contact the tool during a short interval approaching 90° of the beam cycle, which is represented in FIG. 6 by the distance along waveform S between points X and Y. During the remainder of each cycle, the beam outputs are out of contact with the tool, which is represented 0 in FIG. 6 by the distance along line D between points B and X. As previously indicated, the most efficient transfer of force from the beam outputs to the tool occurs with a contact interval approaching 90° of the beam cycle. To achieve this contact interval, the speed of mobile 5 carrier 11 is adjusted accordingly to the stroke of the beam outputs, i.e. , their peak to peak amplitude. The larger the stroke, the faster the speed of mobile carrier 11.Cessation of resonance is prevented when the tool encounters an immovable object or unyielding material during the forward movement of mobile carrier 11. Spec¬ ifically, a protective gap is established between the neutral position of the beam outputs and the tool when the tool is unable to advance along the work path responsive to the impulses transferred to it by beams 54, 54'. BU EAOMPI y, WIPO (This is to be distinguished from the momentary gap described above, which continuously opens and closes during normal operation through yielding material.) In the embodiment disclosed in this specification, the peak sonic force generated by oscillators 56, 56' is substan¬ tially greater than the maximum tractive force generated by mobile carrier 11, i.e., the weight of the vehicle and its load. Specifically, the sonic force is sufficiently large relative to the tractive force to enable the sonic force to overcome the tractive force and to drive the entire machine, including material cutting assembly 10 and mobile carrier 11, backwards away from the tool when the tool is unable to advance along the work path. In my U.S. application Serial No. , , filed on 26 December 1978 (attorney docket case 12300), the disclosure of which is incorporated herein fully by reference, the protective gap is established in a different manner, namely, by a tool stop which prevents the beam output in its neutral position from contacting the tool when it encounters an immovable object. In either way, by thus establishing a protective gap between the beam output in its neutral position and the tool when it encounters an immovable object, cessation of resonance is prevented. It has been discovered that without such a protective gap, when the tool encounters an immovable object the beam output becomes clamped between the tool and the tool holder, thus terminating resonance and preventing transfer of the oscillator force to the tool. This is a common source of damage to the parts of the tool driving apparatus such as the resonant beam, the oscillator, or portions of the tool carrier. Thus, the gap protects the tool driving apparatus from destruction by an immovable object. The term immovable object as used in this specification is relative, not absolute; it is an object that hinders the advance of the machine sufficiently that, in the absence of the protective gap, the vehicle would drive the force transmitting member against the tool and would thus prevent the force transmitting member from transmitting the oscillations to the tool, with the result that the apparatus would destroy itself. In the case of a resonant force transmitting member or beam as described herein, when the output of the beams is clamped against the tool, the end of the beam is no longer free and becomes a node. The nodes thus shift and the entire mode of vibration changes, the largest vibrations now occurring at the node supports, which destroys the node supports and/or the oscillator and beams.Although the invention is illustrated in a machine for cutting concrete or asphalt road surfaces, it could be incorporated into any number of material working machines such as a coal planar, timber shearer, a bulldozer, a front end loader, a rock ripper, or a shovel bucket. In each case, an appropriate tool is employed. In the case of a shovel bucket, the continuous unidirectional force would be the closing force, i.e., line pull, of the bucket, which is con¬ tinuous over the intervals of time in which the bucket is closing and is interrupted while the bucket is carrying its load from place to place. In general, the invention is applicable to any type of material working function wherein a tool is advanced through the material to perform the desired work. The invention can be practiced with other types of force transmitting members including resonant beams of other configurations, such as the angular configuration shown in my U.S. application Serial No. , , filed on 26 December 1978 (Attorney Docket Case 12300), or nonresonant members vibrating in a forced mode. In any case, the gap prevents the oscillator force from being transferred self-destructively back through the force transmitting member. Although it is preferable to practice the invention in apparatus employing sonic rectification fURO.,< IP as that term is used in Bodine Patent 3,367,716, the invention is also applicable to apparatus in which the tool is attached to the force transmitting member, e.g., the resonant beams, as in Bodine Patent 3,232,669. The described embodiment of the invention is only considered to be preferred and illustrative of the inventive concept; the scope of the invention is not to be restricted to such embodiment. Various and numerous other arragements may be devised by one skilled in the art without departing from the spirit and scope of this invention. For example, the invention can be practiced with other types of force transmitting members, including resonant beams of other configurations, such as the angular configuration shown in my U.S. application, Serial No. , filed 26 December 1978 (Attorney Docket Case 12300), or non-resonant members. Further, the described support frame could be used with other types of apparatus, such as, for example, an earth or rock ripper.___OMΠ | - WHAT IS CLAIMED IS :1. A pavement planer comprising: a transversely elongated cutter blade disposed at an acute angle between 45° and 55° to the surface of a pavement, the cutter blade extending in a downward and forward direction along a cutting plane to a cutting edge that lies in the cutting plane; a support frame; means for mounting the cutter blade on the support frame to permit reciprocation approximately in the cutting plane; means mounted on the support frame for inter¬ mittently applying a unidirectional force to the cutter blade at plural spaced apart regions parallel to the cutting plane in the forward direction; and means for continuously transporting the frame in the forward direction while applying the unidirectional force to advance the cutter blade incrementally in the forward direction when the cutter blade engages a pavement.-BU AUOMPI.. ι ι< 2. The pavement planer of claim 1, in which the support frame comprises plural spaced apart upright first support beams each having a top and a bottom, plural spaced apart forwardly projecting second support beams each having a front and a back, the second support beams being equal in number to the first support beams, the back of the second support beams being attached to the top of the respective first support beams to form plural first junctions, plural struts equal in number to the first support beams, the struts having a first end attached to the front of the respective second support beams to form plural second junctions and a second end attached to the bottom of the respective first support beams to form plural third junctions; the unidirectional force applying means comprises plural force transmitting beams equal in number to the first support beams, the force trans¬ mitting beams being mounted on the support frame so they are approximately parallel to the respective struts with an input near the front of the second support beam and an output near the bottom of the first support beam, and a source of vibrations connected to the input of the force transmitting beams to drive the output of the force transmitting beams into vibration about a neutral position, the output of the force transmitting beams lying behind the cutter blade approximately in the cutting plane; and the cutter blade lies approximately under the plural first support beams.Λ . W1PO 3. The pavement planer of claim 2, in which the first support beams have a larger mass per unit length than the second support beams and the struts.4. The pavement planer of claim 3, in which the first support beams are two in number and the support frame additionally comprises a first cross beam connected between the first junctions, a second cross beam connected between the second junctions, and a third cross beam connected between the .third junctions, the first and third cross b beams having a larger mass per unit length than the second cross beam.5. The pavement planer of claim 4, in which the source produces oscillations at or near the resonant frequency of the force transmitting beams to produce therein an upper node and a lower node.6. The pavement planer of claim 5, in which the uni¬ directional force applying means additionally comprises mean for pivotably mounting the force transmitting beams at the upper node on the support frame, and plural stops attached to the support frame behind the respective force transmittin members at the lower node. 7. The pavement planer of claim 6, in which the gap between the cutter blade and the neutral position of the output of each of the plural force transmitting beams is precisely the same so the plural force transmitting beams apply unidirectional force to the cutter blade in synchronism.8. The pavement planer of claim 6, in which the stops are shimmed so the gap between the cutter blade and the neutral position of the output of each of the plural force transmitting members is precisely the same so the plural force transmitting beams apply unidirectional force to the cutter blade in synchronism.9. The pavement planer of claim 9, in which the means for pivotally mounting the force transmitting beams includes means for accommodating changes in the position of the upper node.10. The pavement planer of claim 9, in which the accommodating means for each force transmitting beam comprises bearing means attached to the beam, closed annular elastic bearing support housing means surrounding the bearing means, a fluid in the housing means, and means for attaching the housing means to the support frame.11. The pavement planer of claim 1, in which the mounting means includes means for adjusting the acute angle of the cutter blade. 12. The pavement planer of claim 1, in which the mounting means includes means for adjusting the elevation of the cutter blade.13. The pavement planer of claim 1, in which the mounting means comprises means for pivotably mounting the cutter blade to rotate about a support axis parallel to the cutting plane and the cutting edge, such that the cutting edge lies in front of the support axis.14. The pavement planer of claim 1, in which the transporting means applies to the frame a tractive force having a maximum value, and the unidirectional force applyi means applies to the cutter blade a unidirectional force that is sufficiently larger than the maximum value of the tractive force to drive the frame back, thereby establishing a gap between the neutral position of the output of each force transmitting beam and the cutter blade.15. The pavement planer of claim 1, in which the transporting means comprises a wheeled, motorized vehicle that applies a force up to a maximum value to the frame, the unidirectional force applying means applying to the cutter blade a force larger than the combined weight of the vehicle and its load. 16. The pavement planer of claim 1, in which the unidirectional force applying means comprises: plural, elongated, force transmitting beams, each having a longitudinal axis, an input at one end, and an output at the other end, the beams being mounted on the support frame so their longitudinal axis is transverse to the cutting plane and their output lies behind the cutter blade approximately in the cutting plane; and a source of vibrations connected to the input of the beams to drive the output thereof into vibration about a neutral position.17. The pavement planer of claim 16, in which the source of vibrations has a frequency at or near the resonant frequency of the beams to drive the beams into resonant vibration.18. The pavement planer of claim 17, additionally comprising means for preventing cessation of resonance when the cutter blade encounters an immovable object while the frame is being transported.19. The pavement planer of claim 1, in which the entire unidirectional force is parallel to the cutting plane. 20. A method of removing pavement on a road bed comprising the steps of: holding in contact with the pavement an elongated cutter blade that extends in a downward and forward direction along a cutting plane to a cutting edge such that the cutting plane forms an acute angle with the surface of the pavement; engaging the pavement with the cutter blade such that the cutting edge penetrates the pavement; and intermittently driving the cutter blade with a force parallel to the cutting plane in the forward direction while the cutting plane in the forward direction while the cutting edge penetrates the pavement to drive the cutter blade incrementally in the forward direction and in a chisel like manner plane off the pavement.21. The method of claim 20, in which the acute angle is between 45° and 55°.22. The method of claim 21, in which the pavement is concrete and the acute angle is between 52° and 55°.23. The method of claim 21, in which the pavement is soft asphalt, and the acute angle is between 45° and 48'24. The method of claim 21, in which the pavement is ordinary asphalt, and the acute angle is between 48° and 52' 25. The method of claim 20, in which the holding step comprises pivotally supporting the cutter blade for reciprocation approximately in the cutting plane.26. The method of claim 25, in which the driving step comprises supporting an elongated force transmitting beam having a longitudinal axis transverse to the cutting plane, so that one end of the beam lies behind the cutter blade, applying to the other end of the beam an oscillating force at or near the resonant frequency of the beam to cause the one end of the beam to strike the cutter blade, and applying to the beam as a whole a unidirectional force to continuously move the beam in the forward direction.27. The method of claim 26, in which the other end of the beam comprises an output that oscillates about a neutral position and the oscillating force is sufficiently larger than the maximum value of the unidirectional force to overcome the unidirectional force and to drive the tool holder back, thereby establishing a gap between the neutral position of the output and the cutter blade when the cutter blade is unable to advance responsive to the unidirectional force and the oscillating force. 28. The method of claim 25, in which the driving step comprises supporting a pair of substantially identical elongated force transmitting beams having longitudinal axes transverse to the cutting plane in spaced-apart relationship so that one end of each beam lies behind the cutter blade, coupling a sonic generator to the other end of each beam, the sonic generator producing vibrations at or near the resonant frequency of the beams, and continuously moving the beam in the forward direction.29. The method of claim 28, in which the one end of each beam vibrates about a neutral position, and the gap between the neutral position of each beam and the cutter blade is precisely the same, so that the beams strike the cutter blade in synchronism. 30. Apparatus for performing work on a median, the apparatus having a support frame; means for continuously transporting the support frame in a forward direction; an elongated force transmitting member mounted on the support frame at an acute angle so the top of the member lies forward of the bottom of the member; a vibration generator connected to the top of the member to cause vibrations at the bottom of the member; and a tool facing in the forward direction coupled to the bottom of the member, wherein the improvement comprises: a support frame having an upright support beam with a top and a bottom; a forwardly-projecting support beam having a front and a back, the back of the forwardly-projecting support beam being attached to the top of the upright support beam to form a junction; and a strut having a first end attached to the front of the forwardly-projecting support beam and a.second end attached to the bottom of the upright support- beam such that the strut is approximately parallel to the force transmitting member, the upright support beam having a larger mass per unit length than the forwardly projecting support beam and the strut, the bottom of the support beam and the tool lying near the upright support beam. 31. Material cutting apparatus which comprises: a cutter mounted for reciprocating motion in its cutting direction; a reciprocal drive means adjacent said cutter and arranged to apply sequential cutting force impulses to said cutter in a forward direction; a mobile carrier for said cutter and said drive means to advance the same and apply a tractive force to said cutter in the forward direction; and means for energizing said drive means with force greater than the maximum tractive force of said mobile carri32. Material cutting apparatus according to claim 31, wherein said drive means includes a resonant beam, one end of which lies adjacent said cutter, and a sonic generator connected to the opposite end of said resonant beam to effect vibration thereof.33. Material cutting apparatus according to claim 32, wherein said sonic generator includes a shaft, a plurality of eccentric weights thereon, and a plurality of bearings supporting said shaft at axial intervals.-BURO , ->, W1P 34. Tool driving apparatus which comprises: a resonant member; a sonic generator connected to said resonant • member for applying an input force thereto; a tool supported adjacent said resonant member for movement relative thereto and for periodic contact therewith when said resonant member is energized by said sonic generator to provide periodic force impulses to said tool in a forward direction and leaving a gap between said tool and said resonant member intermediate the period of contact; and means constantly urging said resonant member towards said tool with a maximum force less than the input force applied to said resonant member but tending to close said gap whereby, regardless of the engaged material, the resonant member will remain in resonant vibration.35. A material working machine having a tool holder, a tool adapted to move relative to the tool holder along a work path, a resonant member supported by the tool holder, the resonant member having an output coupled to the tool and an input, means attached to the tool holder for applying an oscillatory, resonance causing force to the input of the resonant member for a given period of time, and means for applying a unidirectional force to the tool holder for the given period of time to advance the tool intermittently along the work path as the resonant member resonates, wherein the improvement comprises means for preventing cessation of resonance when the tool encounters an immovable object during the given period of time. 36. The machine of claim 35, in which the tool is movably attached to the tool holder and unattached to the resonant member and the resonant member has a neutral position about which it oscillates, and the preventing means comprises means for maintaining a gap between the neutral position of the resonant member and the tool when the tool is unable to advance along the work path responsive to the unidirectional force applying means.37. The machine of claim 36, in which the maintaining means comprises means for driving the tool holder back when the tool is unable to advance along the work path responsiv to the unidirectional force applying means.38. The machine of claim 36, additionally comprising means for movably attaching the tool to the tool holder so the output of the resonant member only applies the oscillatory force to the tool while the resonant member is oscillating on one side of its neutral position.39. The machine of claim 35, in which the resonant member has one or more nodes where the resonant member is attached to the tool holder.40. The machine of claim 35, in which the resonant member has first and second nodes between the input and the output where the resonant member is attached to the tool holder. 41. Apparatus for performing work on a medium comprising : a tool having a work path along which it is designed to move to engage the medium; a sonic oscillator producing a reciprocating force at least a component of which is parallel to the work path; means for transmitting the reciprocating force from the oscillator to the tool, the transmitting means having an output that reciprocates responsive to the oscillator; - and means for applying to the output of the transmitting means a unidirectional force to advance the tool intermittently along the work path responsive to the unidirectional force and the reciprocating force, the unidirectional force being sufficiently small relative to the reciprocating force to enable the output of the transmitting means to continue to reciprocate when the tool is unable to advance.42. The apparatus of claim 41, in which the trans¬ mitting means comprises a beam resonant at or near the frequency of the reciprocating force. 43. Apparatus for performing work on a medium comprising: a tool having a work path along which it is designed to move to engage the medium; a sonic oscillator producing a reciprocating force having at least a component parallel to the work path; means for transmitting the reciprocating force from the oscillator to the tool, the transmitting means having an output that reciprocates about a neutral position responsive to the oscillator; means for applying to the output of the trans¬ mitting means a continuous unidirectional force to advance the tool intermittently along the work path responsive to the unidirectional force and the reciprocating force; and means for holding a gap between the neutral position of the output and the tool when the tool is unable to advance responsive to the unidirectional force and the reciprocating force.44. The apparatus of claim 43, in which the transmittin means comprises a resonating beam. 45. Apparatus for performing work on a medium comprising: a tool having a work path along which it is designed to move to engage the medium; a sonic oscillator producing a reciprocating force having at least a component parallel to the work path; means for transmitting the reciprocating force from the oscillator to the tool, the transmitting means having an output that reciprocates about a neutral position responsive to the oscillator; and means for applying to the output of the trans¬ mitting means a continuous unidirectional force to advance the tool intermittently along the work path responsive to the unidirectional force and the reciprocating force, the • reciprocating force being sufficiently larger than the maximum value of the unidirectional force to overcome the unidirectional force and to drive the transmitting means back, thereby establishing a gap between the neutral position of the output and the tool when the tool is unable to advance responsive to the unidirectional force and the reciprocating force.46. The apparatus of claim 45, in which the applying means comprises a wheeled, motorized vehicle and the reciprocating force is larger than the vehicle and its load.47. The apparatus of claim 41, additionally comprising a tool carrier, means for mounting the tool on the tool carrier to move back and forth, and means for mounting the transmitting means on the tool carrier so the output of the transmitting means intermittently strikes the tool as it reciprocates. 48. The apparatus of claim 43, additionally comprisin a tool holder, means for mounting the tool on the tool hold for reciprocal motion, and means for mounting the transmitt means on the tool holder so the output of the transmitting means strikes the tool on one side of the neutral position withdraws from the tool on the other side of the neutral position.49. The apparatus of claim 45, additionally comprising a tool holder, means for movably attaching the tool to the tool holder for reciprocal motion, and means for attaching the transmitting means to the tool holder so the output of the transmitting means intermittently strikes the tool as it reciprocates from the neutral position in one direction.50. A method for driving a tool that is mounted on a tool holder for reciprocal motion through a force trans- mitting beam mounted on the tool holder with an input and an output that reciprocates about a neutral position to intermittently strike the tool on one side of the neutral position, the method comprising the steps of: applying to the tool holder a continuous unidirectional force of a given maximum value to advance the tool holder; and applying to the input of the beam a reciprocating force that is sufficiently larger than the maximum value of the unidirectional force to overcome the unidirectional forc and to drive the tool holder back, thereby establishing a ga between the neutral position of the output and the tool when the tool is unable to advance responsive to the unidirection force and the reciprocating force. 51. A method for driving a tool that is mounted on a tool holder for reciprocal motion through a force trans¬ mitting beam mounted on the tool holder with an input and an output that reciprocates about a neutral position to intermittently strike the tool on one side of the neutral position, the method comprising the steps of: applying to the tool holder a continuous unidirectional force of a given maximum value to advance the tool holder; applying to the input of the beam a reciprocating force to drive the tool; and holding a gap between the neutral position of the output and the tool when the tool is unable to advance responsive to the unidirectional force and the reciprocating force. | GURRIES CO | GURRIES R |
WO-1979000567-A1 | 1,979,000,567 | WO | A1 | EN | 19,790,823 | 1,979 | 20,090,507 | new | E04C3 | null | A63H33, E04B1, E04H1 | A63H 33/00H, E04B 1/12, E04H 1/12 | BUILDING ELEMENTS ESPECIALLY FOR CONSTRUCTION OF PLAYHOUSES FOR CHILDREN THAT CAN BE DISMOUNTED,BUT ALSO FOR OTHER PROVISIONAL BUILDINGS OR SCHREENINGS | Building elements especially for construction of children's playhouses that can be dismounted, but also for other provisional constructions and screenings. Building element of flexible polyurethan foam formed with cuts as logs, and which can be covered with washable textile, serves for building constructions which can be dismounted e.g. playhouses. In connection with children's play, it is an unquestionable advantage to use flexible and light materials both safety wise and handling wise. | Building elements especially for construction of play¬ houses for children that can be dismounted, but also for other provisional buildings or screenings.The invention in question concerns building elements especially for construction of children's playhouses that can be dismounted, but also for other provisional build¬ ings or screenings where the only demand to the strength of the building or screening is that it should be self- supportable.From the Danish patent paper No. 108. 0 a playhouse with such dimensions is known that children can stay inside and play, consisting of sidev/alls hinged together in the form of a collapsible ring provided with doors and windows and roof plates made of stiff, plateshaped material. The roof plates in this house are hinged together with the opposite sidewalls in the ring so that these cannot fall down, when the opposite sidewalls are pulled from each¬ other during the extraction of the house.Such houses are very suitable for small children to play in, but do not satisfy their needs to build a house or a cave themselves.To cover these needs it has been suggested to build play¬ houses of wooden plates, which are fastened together. Small children, meaning children of the kindergarten age, can easily learn to fit such plates together, but partly the plates have to be smooth and have rounded corners and edges, partly the plates cannot be bigger than that the children can handle them safely without risking to over¬ strain themselves and without risking to hit eachother with them during the construction, and partly it is difficult for the children to build them in such a height that they can stand up inside. By the invention in question it is intended to indicate building elements, which to a higher degree than previous¬ ly suggested elements satisfy small children's needs to build playhouses themselves, in which they can both lie down, sit up and stand up, with the feeling that they are in a really selfbuilt room or house.Thus the invention concerns building elements of the in the introduction claim 1 indicated kind, and which are characteristic in that they consist of plates of flexible polyurethan foam which at the ends are formed as logs. Preferably according to the invention polyurethan foam with open cells should be used, as this material gives more flexibility, but nevertheless is suf iciently stiff for the purpose.It has been proved that constructions of building elements according to the invention, besides being suitable for playhouses, also are very suitable for construction of screenings, f.inst. in places where repairs of machinery or buildings by means of noisy implements have to take place.For the building elements - according to the invention - flexible polyurethan foam is preferably used as the use of this material results in the elements being easy to mount even though the building elements have to be placed on a base, the side lines of which are not absolutely rectilinear, and besides effects that no sound bridge between the single elements is formed, neither in the cor¬ ner joints nor where the elements meet edge to edge.When the elements are designed for playhouses, they can be covered with a washable textile. Another possibility is a cover made of a foil of artificial material, and this possibility is used when the elements are used f.inst. as sound silencing construction around a machinery repair so that oil and dirt can be wiped off easily.Various versions of building elements according to the in¬ vention are shown on the drawing.Fig. 1 shows a bottom- or topelement for two opposite sides in a rectangular construction.Fig. 2 a side elementFig. 3 an element v/hich is part of a side andFig. a house end elementThe element 1 shown in fig. 1 is a rectangular, prismatic polyurethan foam plate v/ith the height h and the length 1, and which at one of the long edges is formed with two cuts 2 and 3 and with a length equal to the thickness of theOMPI IPO plate t and which has been cut halfway into the plate with the distance t from the endedge of the plate.The element shown in fig. 2 has a height 2h and is at both long edges formed with cuts 2' , 2 and y , 3 which have the same dimensions as the cuts 2 and 3« I has the same length and thickness as element 1.The element 5 shown in fig. 3 has the same height as element 4, but a length which is only about 1/3 of its length. It is at each long edge at one end of the ele¬ ment formed with two cuts 2' , 2 with the same dimen¬ sions as the cut 2 in element 1,With these elements a house can be built f.inst. by first putting 2 elements 1 parallel to the uncut long edge on a leve'l base and in the distance l- t from eachother, then the two elements are connected with two elements k, fasten¬ ing the two elements by means of the cuts.Over one of the elements 1 an element 5 is fastened on e_:ch side, while element L. is used for the construction of the other sides. The construction is continued in this way with elements placed in layers, using for the last layer two elements 1 and two elements 4 so that the walls of the construction are of the same height. The construc¬ tion can be terminated by elements placed flat down so that the result is a square roofed construction with an entrance between the elements 5.Instead of a flat roof it is possible by means of the ele¬ ment shown in fig. . v/hich is formed as element 1 with a fixed triangular piece, to build a roof by placing the elements k and/or 1 to form the oblique sides of the roof.An appropriate size of the elements 1 and is a length of appr. 1.5 and a thickness of appr. 7 cm and a height of 18 and 3β cm respectively. V/ith these dimensions the weight of one element is about 1 kg and can thus easily be handled by a kindergarten child.For special purposes the elements can be formed in other lengths. It is, however, a condition for the stability of the constructions that are made that the cuts are no clo¬ ser to the end edges of the element than the thickness of the plate.OMPI WIPO | P A T E N T C L A I M1. Building elements for construction of buildings or screenings by means of plane plate elements which can be dismounted and which each at least at one end has at least one cut designed for fastening to a corresponding cut in a transverse plate element, c h a r a c t e r i z e d by the fact that each plate element consists of flexible polyurethan foam.2. Building element according to claim 1, c h a r a c ¬ t e r i z e d by the fact that each element has at least two cuts, the distance of v/hich from the end edge of the plate is equal to the thickness of the polyurethan foam plate.3. Building element according to claim 1, c h a r a c ¬ t e r i z e d by the fact that the flexible polyurethan foam is covered with washable textile or foil of artifici¬ al material.O P IP | HANSEN B | HANSEN B |
WO-1979000573-A1 | 1,979,000,573 | WO | A1 | EN | 19,790,823 | 1,979 | 20,090,507 | new | F15B15 | null | F15B15 | F15B 15/28B | CONTROLLING FLUID ACTUATED PISTON AND CYLINDER DEVICES | A fluid actuably piston and cylinder device arranged to act as an electrical switch so that the device can be controlled or monitored comprising a piston (2) and piston rod (3) which is electrically insulated from the cylinder (1) while the piston is spaced from the ends of the cylinder and which is electrically connected to at least a portion of the cylinder when the piston is at an end position in the cylinder, the electrical connections associated with the piston and with the said portion of the cylinder enabling an electrical voltage to be applied across the piston and cylinder. | CONTROLLING FLUID ACTUATED PISTON AND CYLINDER DEVICESTECHNICAL FIELDThe invention relates to fluid actuated piston and cylinder devices. More particularly, but not exclusively, the invention relates to the control of compressed air actuat.ed piston and cylinder devices.BACKGROUND ARTIt is known to control such devices pneumatically by means of control valves. ounted at each end of the cylinder. Such an arrangement doubles or trebles the number of fluid lines associated with the device and an.'automatic machine employing several such devices therefore requires a large and unwealdy number of such lines.More importantly devising the circuitry necessary for correct sequential control of the various operations of the piston and cylinder devices of the automatic machine, using fluid actuated switches operating in cascade , involves many hours of skilled labour. This problem is particularly acute where one-off automatic machines are involved since for each different machine a unique circuit will need to be devised.This problem can be mitigated by controlling all of the piston and cylinder devices of the machine by means of any one of a number of known multi-channel, electrical or pneumatic programmers. Such an arrangement requires however the use of piston and cylinder devices provided with means for sensing when the piston is in an end position in the cylinder. It is known to provide piston and cylinder devices with micro-switches or micro-valves for this purpose but such devices are too expensive for many applications.DISCLOSURE OF INVENTION We have now discovered that it is possible to make a fluid actuated piston and cylinder device operate as an electrical switch without the necessity of separate micro- switches.According to the invention there is provided a fluid actuable piston and cylinder device comprising a piston and piston rod which is electrically insulated from the cylinder while the piston is spaced from the ends of the cylinder, and which is electrically connected to at least a portion of the cylinder when the piston is in an end position in the cylinder, and electrical connections associated with the piston and with the said portion of the cylinder enabling an electrical voltage to be applied across the piston and cylinder.Preferably the cylinder is electrically connected to the associated machine frame which is maintained at a known (e.g. earth) potential while the piston is connected to a voltage source. For this latter purpose an electrical contact may be provided on the cylinder body, but insulated therefrom, for sliding contact with the piston rod. Alternatively the piston may be connected to the voltage source via a flexible (preferably insulated) lead connected to the piston rod at its end remote from the piston. Such arrangements will of course require the piston and rod to be electrically interconnected, but this is usually the case in practice. One convenient way of electrically insulating the piston and rod from the cylinder is by employing conventional plastics seals.However, in most cylinder devices the nose bearing which supports the piston rod is electrically connected to the cylinder. It is necessary for the purpose of thisBVREOMPI invention that this nose bearing is insulated from the cylinder body e.g. by being mounted in a plastics bush. It will usually be necessary in addition to insulate the piston rod from the part of the machine to which it is connected and further it may be desirable to enclose the piston rod, e.g. in a flexible gaiter, to avoid unintentional earthing of the piston rod.BRIEF DESCRIPTION OF DRAWINGSTypical embodiments of piston and cylinder device are illustrated by way of example in the accompanying drawings in which:-Fig. 1 is a longitudinal section through a piston and cylinder device, andFig. la is a scrap view of part of a piston and cylinder device.BEST MODE OF CARRYING OUT THE INVENTIONIn Figure 1 of the drawings a pneumatic piston and cylinder device comprises a cylinder 1 provided with end caps 12 and 13 respectively and in which a piston 2 is slidingly mounted. The piston is connected to a piston rod 3 which extends outside the cylinder and which is sealed to the cylinder by means of a plastics bush 4 in the end cap 13. The piston 2 and rod 3 are electrically conductive but are insulated from the cylinder 1 and end caps 12 and 13 by the bush 4 and by piston seals 7. The cylinder 1 and end caps 12 and 13 are electrically conductive. A flexible wire 9 which is insulated from the cylinder and end caps is connected to the piston rod so that when the piston is in a limiting position at either end of the cylinder 1 an electrical circuit between the cylinder and the wire 9 is completed. The part of the piston rod protruding from the cylinder is covered by an insulating gaiter 5 to 'prevent unwanted earthing of the piston rod and the free end of the piston rod is connected to a machine part to be actuated by the piston and cylinder device by means of an electrically insulating coupling 6 e.g. of plastics. The end cap 12 of the cylinder is provided with an adjustable stroke limiting device in the form of a screw threaded bolt the bolt being electrically conductive.In Figure la of the drawings there is shown a modified piston and cylinder device generally similar to that described with reference to Figure 1 except that the flexible electrically conductive insulated wire 9 has been replaced by an electrical contact which makes sliding engagement with the piston rod and which comprises an electrically conductive spherical member 10 which is resiliently urged into contact with the piston rod 3 by means of a spring 11 which is preferably mounted in the end cap 13 but electrically insulated therefrom the spherical member 10 being electrically connected to an electrical pickup 9 by means of which the circuit can be completed.Where it is desired to sense separately when the piston is at one or other end of the cylinder this can be achieved by insulating one end of the cylinder from the other, e.g. by providing a plastics seal between the body of the cylinder and one end cap thereof, both parts of the cylinder having electrical connection to the control circui It may be advantageous in this case to maintain the piston at earth potential and to apply the voltage to the cylinder and end cap.INDUSTRIAL APPLICABILITYBy means of the invention, fluid actuated piston and cylinder devices may be controlled by an electrical or pneumatic programmer the steps of which are initiated by signals from the said devices which arise whenever such said devices move from one end position to the opposite end position, it being unnecessary for the programmer to 'know' which of the two end positions has been reached, but merely that a change of position has taken place.The movement of the piston from one end of the cylinder to the other breaks a circuit and then re-makes it. It is this break and remake of a switch (i.e. the piston/cylinder) that can be used directly or indirectly to operate a stepping relay. | CLAIMS1. A fluid actuable piston and cylinder device comprising a piston and piston rod which is electrically insulated from the cylinder while the piston is spaced from the ends of the cylinder, and which is electrically connected to at least a portion of the cylinder when the piston is in an end position in the cylinder, and electrical connections associated with the piston and with the said portion of the cylinder enabling an electrical voltage to be applied across the piston and cylinder.2. A fluid actuable piston and cylinder device according to claim 1, comprising an electrical contact on the cylinder body, but electrically insulated therefrom, for sliding contact with the piston rod.3. A fluid actuable piston and cylinder device according to claim 1, wherein the piston is connected to the voltage source via a flexible lead connected to the piston rod at its end remote from the piston.4. A fluid actuable piston and cylinder device according to any preceding claim, wherein one end of the cylinder is electrically insulated from the other, both parts of the cylinder having electrical connections.5. A fluid actuable piston and cylinder device according to any preceding claim, wherein one end of the cylinder carries an electrically conductive adjustable stop member arranged to contact the piston to limit movement thereof in one direction.6. A fluid actuable piston and cylinder device substantial as hereinbefore described with reference to, and as illustrated in, the accompanying drawings.- 0MPI | CINIGLIO A; ELLEFSEN A; HADFIELD R; ROTAWINDER LTD | CINIGLIO A; ELLEFSEN A; HADFIELD R |
WO-1979000576-A1 | 1,979,000,576 | WO | A1 | XX | 19,790,823 | 1,979 | 20,090,507 | new | B65G67 | B60D7, G08B21 | B60D1, B60T1, B60T3, B65G67, B65G69, F16F7 | B60D 1/38, B65G 69/00B, F16F 7/08 | A DEVICE FOR RELEASABLY SECURING ONE UNIT AGAINST A SECOND UNIT | A device (10) is provided for use in releasably securing one unit (e.g., the rear end of a truck vehicle) against a second unit (e.g., a loading dock (D)). The device (10) comprises an elongated member (11) mounted for controlled endwise movement relative to a locking assembly (17), the latter being adjustably mounted on the loading dock (D). Carried by the elongated member (11) and extending from an end thereof towards the truck is an attaching cable (12) which is adapted to be releasably secured to the truck when the elongated member (11) is disposed in a predetermined relative position with respect to the locking assembly (17). A brake (25) is adjustably mounted within the locking assembly (17) for movement between operative and inoperative positions. When the brake (25) is in an operative position, the exterior of the elongated member (11) is frictionally engaged thereby so that the elongated member (11) can be moved endwise in only one direction away from the truck. When the brake (25) is in an inoperative position, the elongated member (11) can be moved in either endwise direction relative to the locking assembly (17). The brake (25) is biased to normally assume an operative position. Manually actuated lever (32) and finger (30) are carried on the locking assembly (17) for moving the brake (25) from an operative position to an inoperative position. | A DEVICE FOR RELEASABLY SECURING ONE UNIT AGAINST A SECOND UNITBackground of the Invention Positive securement of the rear end of a truck vehicle against a loading dock or the like is essential in avoiding serious problems and mishaps occurring during loading or unloading of a truck vehicle parked at a loading dock. Without proper securement, there is a real potential hazard in the truck vehicle inadvertently moving away from the dock while goods are being loaded on or removed from the truck bed by lift trucks or the like.Heretofore, one effort to avoid such a potential - hazard has been to utilize wheel blocks placed on the roadway beneath the truck and wedged against the front, of the rear tires. Such a practice, however, is undesirable for one or more of the following reasons : a) the blocks may become lost or damaged; b) the roadway surface may be slippery due to spilled oil, rain, snow or ice and thus impair effectively wedging the blocks against the tires; and c) the blocks are awkward to handle and sometimes difficult to remove from a wedged position.Other attempts to obtain proper securement of the truck vehicle to the loading dock have involved the use of elaborate mechanisms which are of costly and complex construe- tion, interfere with access to and from the truck bed, are not readily capable of being utilized with a wide variety of truck vehicle designs , and require an external source of pneumatic and/or hydraulic pressure in order to enable the mechanisms to operate properly. Summary of the Invention Thus, it is an object of the invention to provide a device which is not beset with any of the aforenoted shortcomings associated with prior devices of this general type.It is a further object of the invention to provide a device which is easily installed and maintained and may be utilized in concert with dock leveling equipment and the like. Further and additional objects will appear from the description, accompanying drawings, and appended claims.In accordance with one embodiment of the invention a device of the class described is provided for securing and retaining one unit against a second unit. The device comprises an elongated member mounted for controlled endwise movement relative to a locking assembly which is adjustably mounted on the second unit. Carried by the elongated member and extending from one end thereof towards the one unit is an elongated attaching means. The attaching means is adapted to be releasably connected to the one unit when the elongated member assumes a predetermined position with respect to the locking assembly and the one unit is position against the second unit. The locking assembly includes a friction means which is adjustably mounted for movement between operative and inoperative positions. When the friction means is disposed in an operative position, the exterior of the elongated member is engaged thereby so that the latter is movable endwise in only one direction away from the one unit. When the friction means is disposed in an inoperative position, the elongated element is capable of being moved endwise in opposite directions relative to the locking assembly. The friction means is biased to normally assume an operative position. Mounted on the locking assemb is a manually actuated means which is adapted to move the friction means from an operative position to an inoperative position. Description For a more complete understanding of the invention reference should be made to the drawings wherein:Fig. 1 is a fragmentary perspective view of one form of the improved device.Fig. 2 is similar to Fig. 1 but showing the protec¬ tive hood removed from the device.Fig. 3 is a fragmentary sectional view taken along line 3-3 of Fig. 1. Fig. 4 is a fragmentary sectional view taken along line 4-4 of Fig. 3.Fig. 5 is a fragmentary end elevational view taken along line 5-5 of Fig. 3.Fig. 6 is a fragmentary perspective view of a portion of the device of Fig. 2 and showing the components thereof in exploded relation.Referring now to the drawings and more particularly to Figs. 1 and 2, one form of the improved securing device 10 is shown which is readily adapted for use in releasably securing one unit (e.g. , the rear end of a truck vehicle) not shown, against a second unit ( •£•, a loading dock D) . The loading dock, or platform, normally embodies an elevated horizontal surface Da which forms an extension of the floor of the warehouse or building in which the dock is provided. The dock is normally accessible from a roadway or ramp on which the truck vehicle is parked during loading and unloading thereof. The height of the horizontal surface is approximately the same as the height of the bed of the truck vehicle. Normal height differentials between the dock surface and the truck bed may be readily compensated for by leveling apparatus frequently incorporated in the dock itself and well known in the art.When the truck vehicle is in position for loading and/or unloading, the rear end of the truck bed should be disposed in abutting relation with vertically extending bumpers or the like, not shown, which normally form a part of the dock construction. The device 10 to be hereinafter described is intended to effectively and readily secure the truck vehicle in proper position with respect to the dock bumpers and prevent the vehicle from inadvertently moving away from the dock during the loading and unloading opera- tions.Device 10 includes an elongated tubular member 11, the axis of which is disposed in spaced substantially parallel relation with respect to the horizontal surface Da of the loading dock. Carried by and extending through member 11 is an attaching means 12, which in the illustrated embodiment, is in the form of a flexible heavy duty cable. The cable projects from the forward enlarged end lla_ of member 11; said end being disposed closest to the parked truck vehicle. The distal forward end 12a. of the cable is provided with a hook 13, or some other suitable device, which is adapted to engage and be readily connected to a portion of the rear end of the truck vehicle.The opposite, or rear, end 12b of the cable 12 is provided with a block or stop piece 14 which is fixedly secured thereto and is adapted to abut against an adapter piece 15a_ carried by a telescoping element 15, the latter being disposed adjacent the rear end lib of the elongated member 11, see Fig. 3. The operation of element 15 will be discussed more fully hereinafter. The opening in piece 15a. will allow the cable itself to pass therethrough but not the block 14. To facilitate assembly of the piece 15a. on the element 15 and around the cable extending forwardly of block 14, the piece may be provided with an open end transverse slot 15b through which the cable will pass, see Fig. 5. Spaced longitudinally from block 14 along the cable 12 and affixed thereto are a plurality of spaced, elongated guides 16 which are sized to slidably engage the surface of the center bore B, formed in elongated member 11. Member 11 extends through and is supported by a locking assembly 17 which, in the illustrated embodiment, includes a cylindrically-shaped housing 18, the axis of which coincides substantially with the axis of member 11. Depending from housing 18 is a studlike element 20 which is adapted to engage in a slip-fit relation a sleeve 21, anchored in a recess formed in the dock surface Da_, see Fig. 3. When the element 20 and sleeve 21 are in assembled relation, the housing 18 is free to swivel about the sleeve 21 as an axis but not in a lateral direction with respect thereto; thus , as the cable 12 is drawn up taut and the truck bed is against the dock bumpers , the elongated member 11 and the housing 18 will self-align themselves in a direction towards the point of connection between the cable hook 13 and the truck vehicle. The swivel axis is normally at a right angle with respect to the dock surface Da..As seen in Fig. 3, the upper end 21a of the anchored sleeve 21 projects a slight amount above surface Da_ and slidably contacts a flattened surface area 18a. formed on the underside of the housing 18 and from which the element 20 depends.The housing 18 includes disc-shaped front and rear end plates 22, 23, respectively, and a cylindrically shaped center section 24 interconnecting the end plates. The upperside of the center section 24 is provided with an elongated cutout 24a_ through which extend the upper portions 25a_ of a plurality of friction plates 25 , the latter being adjustably disposed within the housing 18. Each friction plate 25, in the illustrated embodiment, is of a similar rectangular configuration and is provided with a hole 25b formed in the lower portion 25c of the plate and through which the elongated member 11 is adapted to extend. The hole 25b in each instance is sized slightly larger than the circumference of member 11, so that when the plates are disposed perpendicular with respect to the axis of member 11, the latter is free to be manually adjusted endwise in opposite directions (arrows F and R) relative to the housing 18. The perpendicular disposition of the plates is referred to as an inoperative position.When, however, the plates 25 assume a tilted, or askewed, position (referred to as an operative position) relative to the axis of member 11, as seen in Fig. 3, the member 11 is prevented by the plates from being adjusted in an endwise direction (arrow F) towards the truck vehicle because of the frictional engagement between the perimeter of the plate hole 25b and portions of the exterior of membe 11. Notwithstanding the askewed position of the plates 25, the elongated member 11 may be manually moved endwise in a rearward direction (arrow R) away from the truck bed, thus enabling the cable to assume a taut condition after the hoo 13 has lockingly engaged the rear end of the truck vehicle. As observed in Fig. 3, the plates are arranged in face-to- face relation and the lower edges thereof rest upon the interior surface of the lower portion of the housing center section 24 and are confined within an area defined by a forward stop 26 and a rear stop 27, both of which are affixed within the interior of the housing 18. The number of friction plates to be utilized may, if desired, be varie from that shown. In any case, however, when the plates are in operative positions, the greater the force exerted in direction F on cable 12, the greater the friction that will be applied on member 11 by the plates.The size of the cutout 24a_ formed in center secti 24 is such that the plates 25 can be moved without' interfer between operative and inoperative positions. An additional stop 28 is provided within the housing, rearwardly of the plates, and is adapted to be engaged by the rearmost fricti plate when the latter is in its inoperative (perpendicular) position.The plates 25 are biased by a spring 29 to normal assume an operative position, see Fig. 3. The spring 29 is disposed rearwardly of the plates and one end thereof engages the rearmost plate above the hole 25b thereof and the opposite end engages the interior surface of the rear end plate 23. Movement of the plates 25 from their operative position to their inoperative position is effected by a manually actuated finger 30 which is pivotally connected at 31 to a projection 24b formed on the exterior of the housing center section 24. The projection 24b is disposed forwardly of the cutout 24a., see Fig. 2. Manual manipulation of the finger 30 is facilitated by a lever 32. Telescoping element 15, as seen in Fig. 5, is con¬ nected to an upstanding leg 33a_ of an L-shaped bracket 33. Also connected to leg 33a. and spaced above element 15 is a signal switch assembly 34. The second leg 33b of bracket 33 is spaced beneath element 15 and slidably engages an elon- gated tonguelike member 35 which is affixed to and extends rearwardly from housing 17, see Fig. 1.Thus, by reason of bracket 33, the telescoping element 15 and switch assembly 34 are adapted to move endwise in a direction F with respect to the rear end portion llb_ of member 11 in response to predetermined pulling forces exerted on the forward end 12a. of the cable attaching means 12. It will be noted in Figs. 3 and 6 that element 15 is normally in an axially extended position with respect to the rear end portion lib of member 11 by reason of a coil spring 36 enclosed within element 15. Thus, the pulling force exerted upon the attaching means 12 must be of sufficient magnitude to overcome the bias of spring 36 before element 15 , switch assembly 34, and bracket 33 will move longitudinally as a unit along member 11 towards the housing 18. Carried on the front end portion of assembly 34 and depending therefrom is a vertically adjustable actuator 34a. The actuator is in rolling contact with an exterior segment of the member rear end portion llb_. Formed in the exterior segment is an annular groove G in which the depending end of the actuator 34a. is disposed, when the telescoping element 15 assumes its normal extended position with respect to the rear end portion lib of member 11, see Fig. 3. When the actuator end is disposed in groove G, the switch assembly 34 is in a first position of adjustment whereupon a visual, or audio, signaling device, not shown, will assume a predeter¬ mined first condition to be hereinafter described. Extensible electrical leads 37 interconnect the switch assembly 34 with the signaling device.When the predetermined external pulling force is exerted upon the attaching means 12, the element 15 and assembly 34 will move endwise of the member 11 towards housing 18 whereupon the actuator end 34a. will roll out of groove G causing the actuator to be moved upwardly and the switch to assume a second position of adjustment whereupon the signaling device is in a predetermined second condition. Where, for example, the signaling device is a visual type, it may include a pair of lights mounted on the interior of the building and observable by the persons operating the lift trucks, etc., and a third light disposed on the exterior of the building and observable by the driver of the truck vehicle parked at the dock. Thus, with such a signaling device, when the actuator is disposed in groove G, only one light of the pair will be illuminated indicating to the dock personnel that the device is not in proper securing relation with a truck vehicle. Where, however, the actuator has been moved out of groove G, the other light of the pair, as well as the exterior light, will be illuminated indicating a safe condition exists.In order to control the maximum extent to which elongated member 11 may extend forwardly from the locking assembly 17, a collar 38 is fixed to the exterior of member 11 between the housing 18 and the telescoping element 15, see Fig. 3. When the maximum forward position of member 11 has been attained, collar 38 will abut the rear end plate 23 of the housing 18. Coil spring 36 disposed within member 15 will compensate for any change in the amount of force F exerted on the attaching cable 12, due to changes in the relative height of the truck bed with respect to dock surface Da_ during loading or unloading of the truck bed.To control the maximum extent to which element 15 can retract relative to the rear end portion lib of member 11, a spacer sleeve 40 is disposed within the element 15. Sleeve 40 encompasses the biasing spring 36 and maintains the latter in properly aligned relation with respect to the rear end of member 11 and the interior surface of element 15.As seen in Figs. 1 and 2, an inverted U-shaped handle H is pivotally connected to the front end 11a. of elongated member 11. The handle facilitates endwise move¬ ment of the member 11 depending upon the positioning of the friction plates 15. When the hook 13 is being connected to or disconnected from the truck vehicle, the friction plates 15 are moved to their inoperative position by manipulation of lever 32 whereupon the member 11 can be moved to its fully extended (forward) position by the operator manually pulling forwardly (arrow F, Fig. 3) on handle H. When member 11 is in such a position, there is sufficient slack in the cable 12 to allow the hook 13 to be readily attached or detached with respect to the truck vehicle. Once, for example, the hook 13 has been properly attached to the truck vehicle, which had been previously parked against the loading dock, and the lever 32 manipulated so that the friction plates return to their operative position, the slack in the cable 12 is taken up by the operator pulling rearwardly (arrow R, Fig. 3) on the handle H whereby the member 11 will move rearwardly endwise relative to the locking assembly 17. Once the member 11 has been manually moved rearwardly to the fullest extent, the truck vehicle cannot then move away from the loading dock without causing the signaling device to assume an alert or first condition whereupon persons in the vicinity of the truck vehicle and dock know a dangerous situation exists and that no further loading or unloading should take place, or continue, until the dangerous situation has been corrected. - -To protect various components of the securing device 10 from weather, dirt and/or vandalism, a protective hood 41 is provided which has the front end thereof attached by suitable fasteners 42 to the front end plate 22 of housing 18, see Fig. 1. The rear end portion of the hood 41 is supported by a U-shaped strap 43 which is affixed to the rear end of the tonguelike member 35. Suitable fasteners 44 secure the hood to the strap 43.It will be noted in Fig. 1 that the bottom edge of hood 41 is spaced above the exterior of member 11 so as not to obstruct relative endwise movement of the latter. Furthermore the front end wall of the hood is provided with an elongated slot 45 through which lever 32 extends and is free to move relative thereto.Thus, it will be seen that an improved securing device has been provided which is of simple, compact construc¬ tion, and yet is capable of withstanding rugged handling. The device may be readily installed and is capable of being attached to truck vehicles which vary in size and shape over a wide range. Furthermore, the improved device does not require any outside pneumatic, hydraulic or electrical source to retain the device in a locked condition. | AMENDED CLAIMS (received by the International Bureau on 2 July 1979 (02.07.79))1. A device for use in releasably securing one unit against a second unit, said device comprising an elongated member; first means adjustably carried on an en of said elongated member remote from the one unit; an attaching means carried by said -member and having one end thereof extending from a second end of said elongated mem nearest the one unit and being adapted to be releasably connected to the one unit, said attaching means having a second end engaging said first means, the latter being adjustable in one direction relative to said elongated member in response to a predetermined pulling force exert on said attaching means one end; and a locking assembly o which said elongated member is mounted for controlled endwise movement, said locking assembly being adapted to adjustably mounted on the second unit and including frict means movable independently of said elongated member betw operative and inoperative positions, said friction means, when in an operative position, engaging said elongated member and allowing endwise movement thereof only in a direction away from the first unit, and, when in an in¬ operative position, allowing endwise movement in either direction, second means engaging said friction means and biasing said friction means into said operative position, and manually actuated means adjustable independently of s elongated member for moving said friction means from an operative position to an inoperative position.2. The device of claim 1 wherein the friction means includes a plurality of confined platelike elements arranged in substantially face-to-face relation, each element being provided with an opening through which exte an exterior portion of the elongated member; said element assuming an askewed relation with respect to the longitud axis of said elongated member and having perimetric segme of the openings in frictional engagement with the exterio™ of said elongated member, when said friction means is in said operative position.3. The device of claim 2 wherein said locking assembly includes a housing in which at least a portion of each platelike element is confined, said elongated member extending through said housing and being movable relative thereto depending upon the positioning of said friction means; said platelike elements being tiltable as a unit about corresponding edges of the elements as a fulcrum, when said friction means is being moved between operative and inoperative positions.4. The device of claim 1 wherein said first means is adjustable endwise in one direction relative to the end of said elongated member remote from the one unit in response to the said predetermined pulling force exerted on said attaching means one end.5. The device of claim 4 wherein said first means includes a switch means movable relative to said elongated member and having a portion of said switch means actuated by said elongated member in response to said predetermined pulling force for effecting adjustment of a signal means to a predetermined first condition.6. The device of claim 5 wherein the portion of said switch means is in rolling contact with an exterior portion of said elongated member, said exterior portion having a cam-like surface configuration.7. The device of claim 1 wherein the locking assembly is adapted to be swivelly mounted on the second unit; the swivel axis being substantially perpendicular to and intersecting the longitudinal axis of said elongated member . 8. • The device of claim 1 wherein the elongated member is of tubular configuration and the attaching mean has a portion thereof extending therethrough and the seco end of said attaching means is provided with a stop means the latter being impassable with respect to the first mea adjustably mounted on the end of said elongated member remote from the one unit.9. The device of claim 5 wherein said first means, when the predetermined pulling force exerted on th attaching means is released, is biased to assume a pre¬ determined position with respect to the end of said elong member whereby said switch means is adapted to effect adj ment of the signal means to a predetermined second condit10. The device of claim 9 wherein the bias of said first means is effected by a spring disposed inter¬ mediate a portion of said first means and the end of the elongated member remote from the one unit; the biasing fo of said spring varying in response to the amount of in¬ dependent movement of the first means relative to said en of said elongated member. | RITE HITE CORP | HAHN N; NEFF R; WHITE A |
WO-1979000577-A1 | 1,979,000,577 | WO | A1 | XX | 19,790,823 | 1,979 | 20,090,507 | new | A41B11 | null | A41B11, A41B17, A45D26, A61K8, A61Q9 | A41B 11/00, A61K 8/02C, A61K 8/11C, A61Q 9/04, K61K 201/10 | DEPILATORY BEARING FABRIC | A fabric garment (10) which automatically removes unwanted hair (30) while being worn against the skin (16) of the user (15). The garment (10) is coated with a pressure sensitive microencapsulated depilatory agent (20). Pressure exerted by a hair stubble (30) against the fabric (10) causes the microencapsulation to rupture and dispense the depilatory agent in a small localized area around the hair follicle. The depilatory agent dissolves the hair stubble without irritating the user's skin. | DEPILATORY BEARING FABRIC Technical Field This invention relates to a fabric garment to be worn tightly against the skin of a user, which during use, automatically removes unwanted hair. More particularly, the invention relates to hosiery which is coated with a microencapsulated depilatory agent which automatically dispenses the depilatory to only a localized area around the hair follicle thereby dissolving the hair without irritating the user's skin.Background Art Throughout the ages, man has developed various devices and methods for removing unwanted body hair. These prior art devices have ranged from mechanical cutting edges which shave the hair stubble adjacent to the skin such as straight, safety, and electric razors, to modern depilatory agents which are applied directly to the skin to dissolve the hair stubble by a chemical process. Although these methods and devices have proven useful in many applications, there are inherent deficiencies in their use.Since the cutting edge devices contact the hair stubble as they are pulled across the skin of the user, there is a tendency for the hair to bend, causing a failure to shave the hair close to the skin. Additionally, these mechanical devices suffer from the all too frequent cutting of the user's skin as well as the hair stubble.Alternatively, the depilatory agents, although capable of chemically dissolving the hair close to the skin, in many instances cause minor skin irritation to the user or possess an obnoxious sulfide odor which is extremely difficult to mask.Further, a major limitation of both the mechanical edge devices and depilatory agents are that they are time-consuming to use. When using cutting edge devices, pre-shave lotions or lather must first be applied to the skin to soften the hair stubbles and protect the skin from abrasion. Then, subsequent to shaving, these lotions must be rinsed from the skin with water. Similarly, use of the depilatory agents require that a hair dissolving lotion be applied and left in contact with the skin for a period of time and then be removed by washing. In many instances, use of these prior art devices and methods require as much as thirty minutes be expended each day by the user in removing unwanted body hair. Disclosure of InventionThe applicant has discovered a convenient and economic device and method for automatically removing unwanted body hair which substantially eliminates these deficiencies of the prior art. The present invention provides a garment which is coated with a microencapsulated depilatory agent which effectively and automatically removes unwanted body hair when worn by the user. The invention is extremely suitable for use in womens' hosiery which is typically worn tightly against the skin of the user.The invention comprises hosiery which is coated with a pressure sensitive microencapsulated depilatory agent. This microencapsulation facilitates deposition of the liquid depilatory upon the hosiery in a capsule form without wetting or altering the original dry appearance of the fabric, and additionally allows the dispensing of the depilatory to only a localized area adjacent the hair stubble.When the hosiery of the present invention is worn tightly over the skin of the user, the pressure exerted by the hair stubble against the fabric ruptures the microencapsulation, thereby selectively releasing the depilatory agent in the area surrounding the hair stubble. The depilatory agent quickly begins to break down the prote structure of the hair and completely dissolves the hair stubble during normal wearing of the garment.As can be readily seen, the present invention alleviates the time consumption deficiencies of the prior art by providing hosiery which automatically removes unwanted hair while being worn. Additionally, the present invention automatically removes hair close to the skin surface without the possibility of accidental cutting of the skin. Further, due to the localized area of contact between the depilatory and the hair, contact between the depilatory and the user's skin is minimized. This permits prolonged contact duration of the depilatory with the hair stubble, so that a moderate strength depilatory agent can be used which does not possess an unpleasant odor. The microencapsulation, by limiting skin contact with the depilatory (only the hair stubble ruptures the capsules) , permits the user of depilatory chemicals which would be too harsh to apply directly to the skin for prolonged periods.Brief Description of Drawings These and other features of the present invention will become more apparent upon reference to the drawings wherein:Figure 1 is a schematic view of a nylon hose coated with a microencapsulated depilatory and being worn tightly against the skin of the user; Figure 2 is an enlarged pictorial representation of the nylon hose against the skin of the user showing the spacial relationship between the fabric, hair stubble and the microencapsulated depilatory; andFigure 3 is an enlarged cross-sectional view showing a filament of the nylon hose with a microencapsulated depilatory thereon.Best Mode For Carrying Out the Invention Referring to Figure 1, there is shown the microencapsulated depilatory coated hosiery 10 of the present invention being worn around the legs of a user 15. As can be seen, it is advantageous if the fabric, in this case the hosiery 10 , is capable of being tightly worn in direct contact with the user's skin 15, yet be elastic enough to stretch and conform to normal body movement.The hosiery 10 is preferably formed of a looped fabri knit and made from synthetic fibers such as nylon or rayon which are typically used in hosiery manufacturing. Such looped fabric construction is well known in the art and provides hosiery having high elastic and memory properties which easily stretch to accommodate body movement and quickly return to the prestretched configuration of the fabric after such movement. Additionally, the synthetic fibers possess high strength and are easily dyed to allow the hosiery to be manufactured in a variety of cosmeticall pleasing colors. The microencapsulation process utilized in the presen invention is a relatively new technology which has been significantly developed in recent years. Basically, this microencapsulation process comprises the formation of a hard thin shell or film which coats a minute-sized liquid depilatory material, thereby forming a pressure sensitive depilatory capsule. Various microencapsulation processes suitable for use in the present invention are well known in the art and are disclosed in U.S. Patent No. 3,804,775 (gelatin phase change), U.S. Patent No. 3,607,775 (complex coacervation), U.S. Patent No. 2,800,458 (salt coacervatio and U.S. Patent No. 3,565,819 (wax-hydrophilic colloid), the descriptions thereof incorporated herein by reference.These pressure-sensitive depilatory capsules 20 are schematically shown in Figure 3, and include a depilatory, liquid core 18 and a surrounding, typically spherical wall 22. The capsules 20 typically range from a few to several hundred microns in diameter, and are deposited upon the hosiery 10, thereby contacting the hair stubble 30 as well as the user's skin 16 during use. The dispersion of depilatory capsules 20 is preferabl sprayed or coated upon the hosiery 10 immediately after the microencapsulation process is accomplished. At this stage in the process, the outer walls of each capsule are wetted and substantially pliable. This wetted, soft condition allows each capsule to adhere and conform to the shape of the hosiery fabric. Referring to Figure 3, it can be seen that at the interface of the microcapsule 20 and the hose filament 12, the generally spherical shaped wall 22 of the microcapsule deforms into a substantially flat surface 32 which effectively bonds the microcapsule 20 to the hosiery 10. Subsequently, the hosiery 10 with the dispersion of capsules 20 thereon is dried at an elevated temperature and the capsule walls hardened around the fabric, thereby adhering each capsule' to the hosiery 10. Alternatively, depositing of the capsules 20 may be accomplished by initially drying the capsules to form a powder-like substance and then spraying the capsules upon the hosiery 10 with a moderate, water insoluble adhesive.The liquid depilatory agent is contained within the microcapsules 20 must be inert to the microcapsule wall material, and still reduce the disulfide cross-links of body hair, preferably without causing substantial irritation to the user's skin. Solutions having a moderate concentration of calcium thioglycolate or 1,4 dimercapto-2,3 butane diol have been found to be preferable over sulfate or sulhydrate solutions due to their non-obnoxious odor and non-skin irritant properties. Such calcium thioglycolate and dimercapto butane diol depilatories are disclosed in U.S. Patent No. 3,527,559 and U.S. Patent No. 3,865,546, respectively, which are incorporated herein by reference. The automatic hair removing process of the present invention can now be described. Referring to Figure 2, it can be seen that the hosiery 10 is composed of length-wise and cross-wise extending nylon filaments 12 and 14, respectively, which form a looped fabric knit. Depending upon the desired sheerness, these filaments typically measure .003 to .012 of an inch in diameter. The hosiery 10 is coated with a dispersion of icrocapsules 20. A hair stubble 30 which initiates from a hair follicle (not shown) extends outward from the skin surface 16.In use, the hosiery 10 is tightly worn over the user's skin 16 and is in direct contact with the hair stubble 30. Due to the outward protrusion of the hair stubble 30, increased pressure in the area adjacent the hair stubble 30 is exerted upon the outer walls 22 of the depilatory microcapsules 20. This pressure causes the wall 22 to rupture, thereby releasing the depilatory 18 in a localized area at the hair stubble 30. Upon contact with, the hair stubble 30, the depilatory 18 immediately begins to reduce the disulfur cross-links of the hair and completely dissolves the stubble 30 within the normal, course of wearing, for example, a day.It is advantageous to select a microencapsulation material and thickness which ruptures in response to either abrasion by the hair stubble, or the increased pressure at the stubble but hwich will not ordinarily rupture when pressed against the user's skin.As can be easily recognized, due to the hosiery being typically worn throughout the day, the hair removal process can extend over a period of hours, thereby allowing the user of a more moderate strength depilatory which is less irritating to the user's skin. Additionally, since the depilatory is only released in a localized area at the hair stubble, rather than over the entire leg area, these skin irritation effects are further reduced.In the preferred embodiment, the hosiery is designed for single usage and is easily disposed of after wearing. However, with careful handwashing and air drying, multiple usage of the hosiery may be accomplished. | 1. A device for automatically removing hair from the skin of a user including a fabric material worn tightly against the skin of a user, said device characterized by: plural microcapsules attached to said fabric; a depilatory agent contained within said plural microcapsules; and said microcapsules rupturing and releasing said depilatory agent in a localized area surrounding a hair stubble in response to pressure exerted by said hair stubble against said microcapsules.2. The device of Claim 1 further characterized in that said microcapsules each comprise a pressure sensitive thin shell. 3. The device of Claim 1 further characterized in that said depilatory agent chemically reduces the disulphur cross links of said hair stubble upon contact with said hair stubble.4. The device of Claim 1 further characterized in that said depilatory agent removes said hair stubble without irritating the skin of the user.5. The device of Claim 1 wherein said fabric material comprises a stocking worn against the skin of the user. 6. The device of Claim 2 further characterized in that said depilatory agent is inert with respect to said thin shell. | MCGALLIARD J | MCGALLIARD J |
WO-1979000580-A1 | 1,979,000,580 | WO | A1 | XX | 19,790,823 | 1,979 | 20,090,507 | new | G02B5 | null | A61C1, A61C19, F21V8, G02B6, G08B1, G08B21 | G02B 5/16C2, G02B 6/00L4C, G02B 6/26C, G02B 6/26C2, G02B 6/35E8, G02B 6/35S, G02B 6/42C3B, K61C 1/08L, S02B 6/42C6, S02B 6/42H2 | ELECTRICALLY ISOLATED ILLUMINATION CONTROL FOR DENTAL DRILL | Control means for a fiber optic illumination system are disclosed having a light source and a fiber optics bundle (192) with a proximal end positioned adjacent to said light source and a distal end positionable in the immediate region where light is desired, said control means comprising a control unit (194) whose small size enables the control unit to be positioned so as not to interfere with the normal use of other implements being employed in the dental work area ad having signal generating means (123) including switch means (111) for activating said signal generating means to develop a function control signal, sensing means (124) displaced from and electrically isolated from said signal generating means for generating an activating signal upon receipt of said function control signal, and means (125) responsive to said activating signal for energizing said light source. The control means may comprise means for sensing the presence or absence of light, or means sensitive to other electromagnetic waves. | TITLE:Electrically Isolated Illumination Control For DentalDrillTECHNICAL FIELD: This invention relates to fiber optic illumination systems, and particularly to dental fiber optic illumina¬ tion systems.BACKGROUND ART:One of the most widely used and important tools employed by dentists and dental hygienists is the hand-held drill which is typically a hand-held piece specifically designed and having a shape which provides for proper orientation within the mouth of the patient without requiring any awkward or unusual contortions on the part of the operator in order to appropriately position the operating end of the hand-held drill piece for the purpose of drilling, cutting, polishing, buffing, hammering, tamping, and the like. The patient's mouth is a confined area requiring the skilled operator to exercise a high degree of care in the performance of dental procedures. It is quite imperative that the immediate region of concern be adequately lighted so that the operator is confident that he is performing the proper function in the proper location. This capability has been very adequately provided for in the form of an elongated fiber optic bundle having its proximal end positioned immediately adjacent a source of illumination and having its distal end mounted within the body of the drill handpiece and positioned adjacent the output shaft of the drill to flood the area of concern with light of an adequate level to permit the operator to perform the desired procedures in an assured manner.-BUREA UOMPI ' The articulated design of the handpiece, tool and supply tray and even the dental chair enable these members to be easily manipulated and movable with the objectives of both patient comfort and operator efficiency in mind. As a result, it is most advantageou and in many cases even necessary to place the lamp source and power unit provided therefor in some location where it does not interfere with the articulated equipment employed by the operator during the performanc of normal dental procedures. Since the drill handpiece is normally utilized in an intermittent fashion, it is most efficient and economical to be able to turn the lamp source on and off in a simple and straight forward fashion. This basic capability is adequately provided for as taught by U.S. Patent No. 3,758,951, issued September 18, 1973, and assigned to the applicant of the present invention, wherein a small, compact, lightweight unit identified therein as a remote control unit (RCU) is adapted to be positioned in the immediate vicinity of the work area, and which is provided with an on/off switch within easy reach of the operator to enable quick and simple turnoff or turnon of the lamp source, and wherein the small size of the remote control unit enables the unit to be positioned within easy reach of the operator (typically beneath the articulated tray) without in any way interfering with other apparatus in the vicinity or with the access of the operator to such apparatus. The conventional approach for such on/off control means is to provide an electrical circuit including switch means mounted within the remote control unit and coupled across a pair of conductive leads extending between the remote control unit and the illuminating lamp supply source. The switch may be selectively turned on and off in order to respectively energize and deenergize the light source to convey light to the area of concern by way of the fiber optics bundles. Since water is continuously utilized during many of the dental procedures such as, for example, to cool the drill bit and tooth during drilling, as well as to periodically rinse a drilled tooth to facilitate examination to determine the progress of any procedure, it is not only important but frequently required by both local and Federal regulations that the level of electrical energy of any electronic components present in the immediate working area be no greater than 21 volts at virtually zero current to protect both operator and patient from electrical shock or injury. With the apparatus of the above- mentioned issued patent, this is accomplished by providing a step-down transformer within the housing of the supply source to reduce the voltage output derived from a conventional wall receptacle typically rated at 115 volts AC, down to the above-mentioned voltage/current level. Although this technique reduces the output power delivered to the remote control unit, the danger of minor shock is still present. In addition thereto, the weight of the step-down transformer required for the above application, together with its size, makes the supply source unit unduly large and heavy, serving to increase the cost of the equipment and imposing physical restrictions on both the ease of mounting and the locations in, on or upon which the unit may be mounted. DISCLOSURE OF INVENTION: The present invention is characterized by comprising a combination remote control unit and lamp supply source of reduced size and weight as compared with the conventional device described hereinabove, through the use of novel wireless signaling means which simply and yet effectively provides for selective automatic turnon and turnoff of the lamp source while totally eliminating the need for an electrical connection between the main supply unit and the remote control unit. The compact remote control unit may be enclosed within a small housing having bracket means suitable for securing the housing at an easily accessible position on or adjacent to the patient's chair, and typically beneath the tray provided for supporting tools and materials normally used during dental pro¬ cedures. The larger light source and power supply unit may be mounted at a location remote therefrom so as not to interfere with activities undertaken around the chair by the skilled operator. According to one preferred embodiment, there is provided control means for a fiber optic illumina- tion system having a light source and a fiber optics bundle whose proximal end is positioned adjacent to said light source and whose distal end is positionabl in the immediate region where an examination procedure is being performed so as to provide increased acuity in the region to be illuminated, said control means comprising a control unit small enough so as not to interfere with the normal use of other implements being employed in the work area; signal generating means contained within said portable control unit and including manually operable switch means for activating said signal generating means to create a function control signal; sensing means for generating an activating signal upon receipt of said function control signal; and means responsive to said activating signal for energizing said light source whereby no electrical connection whatsoever exists between said portable control unit and said sensing means.According to another preferred embodiment, there is provided control means for a fiber optic illumina- tion system having a light source and a fiber optics bundle with a proximal end positioned adjacent to said light source and a distal end positionable in the immediate region where light is desired, comprising a control unit whose small size enables the control unit to be positioned so as not to interfere with the normal use of other implements being employed in the dental work area and having signal generating means including switch means for activating said signal generating means to develop a function control signal, sensing means displaced from and electrically isolated from said signal generating means for generating an activating signal upon receipt of said function control signal, and means responsive to said activating signal for energizing said light source. According to a further preferred embodiment, there is provided control means for selectively energiz¬ ing a lamp serving as the illumination source for an elongated fiber optics bundle having a first end positioned adjacent to said lamp and a second end mounted at the working end of a dental handpiece, comprising switch means, signal generating means for generating a signal responsive to operation of said switch means, an AC power source, and sensing means responsive to the signal generated by said signal means for coupling said AC power source with said lamp, said signal generating means being totally electrically isolated from both said AC power source and said sensing means to protect the user of said dental handpiece.BRIEF DESCRIPTION OF DRAWINGS:Figure 1 shows a perspective view of a control apparatus designed in accordance with the principles of the present invention. Figure la shows a sectional view of the remote control unit of Figure 1 looking in the direction of arrows la-la.Figure lb shows a sectional view of the remote control unit of Figure 1 looking in the direction of arrows lb-lb. Figure 2 shows a perspective view of another preferred embodiment of the present invention.Figure 3a .shows a top plan view of a portion of another preferred embodiment of a remote control unit embodying the principles of the present invention. Figure 3b shows a sectional view of the remote control unit of Figure 3a looking in the direction of arrows 3b-3b.Figure 3c shows a sectional view of a modification of the remote control unit of Figure 3a looking in the direction of arrows 3b-3b.Figures 3d and 3e shows still further preferred embodiments of the present invention employing battery powered electrical means for utilization in the remote control unit, wherein Figure 3e further employs level control means of the type employed in Figures 3a-3c. Figure 3f shows still another embodiment of the present invention employing wireless carrier techniques.Figure 4 shows a perspective view of still another preferred embodiment of the present invention in which the remote control function is integrated into the dental handpiece.Figure 4a shows a sectional view of the switch portion of the handpiece of Figure 4 looking in the direction of arrows 4a-4a.Figure 4b shows a detailed perspective view of the switch arrangement of Figure 4.Figure 5 shows one typical dental unit for use in treating patients and the manner in which the apparatus of the present invention may be mounted with regard thereto. Figure 6 shows a simplified perspective view of a cradle for supporting a dental handpiece and for automatically activating the main light source. Figure 6a shows a simplified schematic of an electrical circuit which may be employed with the cradle of Figure 6.Figure 7 shows a block diagram of another embodi¬ ment of the control means .Figure 7a shows a detailed block diagram of the phase shift control circuitry shown in simplified form in Figure 7.Figure 7b shows an alternative embodiment of a magnetically coupled isolator which may be used in place of the optically coupled isolator of Figure 7 Figure 8 shows a dental handpiece assembly which may be operated by the control circuitry of Figure 7.Figure 8a shows a pressure sensitive switch which may be used to control turnon and turnoff of the lamp. Figure 9 is a perspective view of a stand alone fiber optics illuminator embodying the principles of the present invention.Figure 10 shows a schematic diagram of another isolator circuit which may be employed to couple the remote switch of Figure 7 to the count of three counter of Figure 7.BEST MODES OF CARRYING OUT THE INVENTION:Turning initially to a consideration of Figure 5, there is shown therein a patient unit 10 comprised of a pedestal 11 upon which chair 12 is mounted in a fashion so as to be both tiltable and swingable upon pedestal 11. A horizontally aligned arm 13 extends outwardly from pedestal 11 and to one side of chair 12. A vertically aligned post 14 is mounted upon the free end of arm 13 and has a swivel arm 15 pivoted thereto so as to swing about pivot point 15a. The free end of arm 15 is pivotally connected to a second arm 16 swingable about pivot point 16a so as to enable tray 17, mounted to the free arm of 16, to be positioned at a location convenient for the operator to place implements and materials utilized during a dental procedure without leaving the patient's side. The housing 18 may be mounted on post 14 and is designed to house a variably intensity light source which is remote from the immediate work area, such mounting being accomplished through suitable mounting brackets or other securement means.A remote control unit 19 is mounted upon tray 17 and is shown as being positioned immediately adjacent to the control panel 20a of a control housing 20 providing easy and immediate access for manipulation of the dials and/or switches associated with control functions normally required in the dental work area. The remote control unit is typically provided with switch means in the form of a manually operable knob 19a for turning the light source on or off and, in some preferred embodiments, for controlling the intensit of light emitted by the light source. In certain preferred embodiments, the remote control unit 19 is coupled to the light source receptacle 18 by a suitable electrical cable or conduit 21 which may be clamped on post 14 and arms 15 and 16 at spaced intervals, for example as shown by the clamping means 22.The light source housed in receptacle 18 is preferably a lamp capable of utilizing conventional 115 volt AC power. Although not shown in Figure 5 for purposes of simplicity, a blower is preferably provided within housing 18 for cooling the lamp.The blower is preferably turned on and off in conjunctio'BΪOM y - I with the lamp. Louvers 18a may be provided along one or more surfaces of the receptacle to aid in such cooling.The lamp conveys light to the dental handpiece by means of a fiber optics bundles, the proximal end of the fiber optics bundle being positioned imme¬ diately adjacent the lamp housed within receptacle 18 and the distal end thereof being fixed to the handpiece so as to be in close proximity to the drill mounted within the handpiece, as is described in detail in the above-mentioned U.S. Patent 3,758,951, and as shown for example in Figure 1 of the patent.In another preferred arrangement, as shown herein in Figure 4, the fiber optics bundle 23 may extend through the body of the handpiece 24 and be divided into first and second branches 23a and 23b, whose distal ends 23a-l and 23b-l are positioned on opposite sides of the handpiece drill 25 so as to flood the region to be drilled with light. Considering Figures 1 through lb, showing remote control unit 19 and a portion of receptacle 18, the apparatus for controlling on and turnoff of the lamp utilizes fiber optics bundles and operates in the following manner: Receptacle 18 is provided with a separate small housing 30 divided into compartments 30a and 30b by barrier wall 31. A first fiber optics bundle 32 has its proximal end 32a secured by bracket 35 to one face of cover plate 33 having an opening 33a. Compartment 30b houses an LED 34 coupled between the positive terminal of a voltage source and ground potential as shown. The distal end of 32b of fiber optice bundle 32 is secured to the top surface of remote control unit 19 by suitable mounting means 36. Although not shown, it should be understood that the fiber optics bundle 32 may be housed within a separate protective sleeve. Thus, light emitted from LED 34 is conducted through fiber optics bundle 32 to remote control unit 19 and through the opening 19c in top surface 19b as shown best in Figure la. Chamber 30a houses a phototransistor 37 having its collector coupled to the positive terminal of a voltage source through resistor Rl and having its emitter coupled to ground through resistor R2. The emitter of 37 is also coupled to the trigger input 38a of a bistable flip-flop 38 through capacitor Cl whose opposite terminal is coupled to trigger input 38a and to ground potential through resistor R3.The cover plate 39 of chamber 30a is provided with an opening 39a. The proximal end of fiber optics bundle 40 is secured to the upper fa'ce of cover plate 39 by mounting means 41. The distal end of 40b of fiber optics bundle 40 secured to one side face 19d of remote control unit 19 by a mounting bracket 43. Side face 19d is provided with an opening 19e.The remote control unit 19 houses a reflective member 44 which reflects light entering into housing 19 from fiber optics bundle 32 toward fiber optics bundle 40 when an unobstructed light path is present. The condition of the light path is controlled by switch means 19a comprised of a slide member 46 having an upwardly extending manually operable projection 46a extending through elongated slot 19f in upper surface 19b. The slide member 46 is slidably guided between two downwardly depending arms 47 and 48, each having inwardly directed flange portions 47a and 48a, respec¬ tively, forming slide grooves Gl and G2 which receive the opposite sides of slide member 46 as shown best in Figure lb. By moving projection 46a in the direction shown by arrow 49, the right-hand portion thereofIsUREO PI -Il¬ extends into the path P, of light emitted from fiber optics bundle 32 so as to prevent light from reaching reflective member 44 so as to be directed toward the distal end of fiber optics bundle 40. By moving the slide arm projection in the opposite direction as shown by arrow 49a, the right-hand end of slide member 46 moves out of the light path P- enabling light from fiber optics bundle 32 to impinge upon the reflective surface of member 44 so as to be directed into the distal end of fiber optics bundle 40 and thereby conveyed by bundle 40 to impinge upon phototransistor 37.The current signal developed by phototransistor37 is applied to the trigger input of the bistable flip-flop 38 causing its output terminals 38b and38c to go high and low respectively. The high output at terminal 38b is utilized to turn on the lamp source in receptacle 13 to provide light of suitable intensity for the dental handpiece 24 as shown, for example, in Figure 4 of the present invention.The switch may be automatically reset by coupling a suitable biasing spring 50 between the right-hand end of slide member 46 an the vertical side wall 19d requiring a subsequent opening of the switch turnoff of the light source. For example, by closure of the switch under the control of spring 50, light no longer reaches phototransistor 37, causing the voltage level at its emitter to drop to reference potential. Bistable flip-flop 38 may be of the type which changes state only on a positive going edge and hence the negative going edge has no effect on its state. By operation of the switch at a later time, the next positive going edge causes flip-flop38 to reverse its stable state whereby outputs 38b and 38c go low and high respectively to turn off the main lamp source. Obviously, any other type of switching means may be provided, it being understood that the nature of the control established through the fiber optics is such as to totally eliminate the need for any electrical leads between the remote control unit 19 and receptacle 18.The arrangement of Figure 2 eliminates the need for two fiber optics bundles and LED 34 by providing a remote control unit 19' which, although having a similar switch arrangement 19a, is provided with an opening 19c in its upper face 19b which is preferably fitted with a transparent lens member 53.The separate chamber housing 30' provided in receptacle 18 is provided with a single chamber 30a housing the phototransistor 37. The opening 39a serves as a means to enable the passage of light from the proximal end 40a of fiber optics bundle 40 to the phototransistor 37. The distal end 40b of fiber optics bundle 40 extends into remote control unit 19' and is preferably positioned beneath an in close proximity to transparent lens 53. The similar switch arm assembly 46 is provided so as to position its right-hand portion between opening 19c and the distal end 40b of fiber optics bundle 40, or to be moved to a position displaced therefrom so as to enable ambient light passing through the transparent lens 53 to reach the distal end of fiber optics bundle 40 an be conveyed through the bundle 40 in opening 39a so that the light impinging upon phototransistor 37 causes generation of a signal for operating bistable flip-flop 38 in a manner similar to that described hereinabove. Since the dental area is normally well lighted, ambient light will be of a level more than sufficient to assure positive operatio of the switching means. Thus, the embodiment of Figure 2 performs the same switching function as the remote control unit of Figure 1 while totally eliminatingOMP one fiber optics bundle and LED 34 as well as its powering means.The embodiments described hereinabove serve to control the selective turnon and turnoff of a remote electrical function. However, numerous applica¬ tions exist wherein it is desirable to not only turn on and turn off the main lamp, but to adjust its light intensity. Figures 3a through 3e teach embodiments for providing this capability. Turning initially to a consideration of Figures 3a and 3b, the top face 19b of the remote control unit is shown as having a circular opening 19c and an arcuate shaped slot 19g concentric with opening 19c. A polarized lens 56 is fitted in opening 19c. A second polarized lens 57 is rotatably mounted between three roller members 58, 59, and 60, arranged at 120 intervals about the axis of rotation A of polarized lens 57. Each of these rollers is provided with a groove. For example, roller 58 is shown as being provided with a groove 58a arranged around its cylin¬ drical periphery to receive and support the marginal edge of polarized lens 57. A thin frame 62 encircles polarized lens 57 and has secured thereto an outwardly extending projection arm 63 whose free end 63a is bent upwardly so as to extend through arcuate shaped slot 19g to serve as the operating arm for the remote control means.By moving the operating arm 63a either clockwise or counterclockwise, lens 57 may be rotated through an angle of 100 or more. This permits relative rotation between polarized lenses 56 and 57 to prevent light rays from the ambient light as represented by arrow L„ from passing through the lenses and entering into the distal end 40b of fiber optics bundle 40. By rotation of lens 57 through a suitable angle from the position where the lenses provide an opaque condition, the amount of ambient light passing there¬ through may be controlled over a range which at one limit provides a substantially opaque condition and at the other limit provides a substantially transparent condition to thereby attenuate the light passing through fiber optics bundle 40 by an adjustable amount which may be utilized to cause a phototransistor to generate a current whose magnitude is a function of the intensity of light so as to control a servo- mechanism or other suitable device (not shown for purposes of simplicity) to convert the intensity of light and magnitude of current into a control value for controlling the intensity of light emitted by the main light source which illuminates the fiber optics bundles serving to illuminate the mouth of the patient, such as, for example, the fiber optics branches 23a-l and 23b-l of the dental handpiece 24 shown in Figure 4 of the present invention. Obviously suitable markings may be provided adjacent arcuate slot 19g for simplifying the adjustment of the operator to obtain the desired light intensity.The embodiment shown in Figures 3a and 3b is designed to take advantage of ambient light. However, this embodiment may be altered in a manner shown in Figure 3c to be utilized with the LED In photo¬ transistor arrangement 34, 37, respectively, of Figure 1. This is accomplished by securing the distal end 32b of fiber optics bundle 32 in an opening (Figure 3c) provided in the upper face 19b of the remote control unit. Thus, light directed from LED 34 (see Figure 1) is conveyed to the upper surface of polarized lens 57. Lens 56 is shown as being mounted in a stationary fashion beneath rotatable lens 57 with its bottom surface adjacent to the distal end 40b of fiber optics bundle 40. In all other respects, the embodiment of 3c functions inO _ A>- w the same manner as the embodiment of Figures 3a and 3b. However, the use of a separate LED assures more accurate control over the level of light being attenuated as compared with the use of ambient light. Figure 3d shows still another alternative embodi¬ ment for the present invention wherein the remote control unit utilizes only one fiber optics bundle 40 having its distal end secured above the opening 19c. An LED 66 is mounted within the remote control unit 19' and is electrically coupled between a reference potential and a potentiometer 67 comp'rised of a rotary switch arm 67a and a resistance element 67b adapted to be slidably engaged by the free end of switch arm 67a. One end of resistance element 67b is coupled to reference potential while the other terminal is coupled to a positive DC source which is preferably a small penlite battery or nickel-cadmium battery. By moving switch arm 67a from the stationary OFF contact 68 to the grounded contact 69, LED 66 remains deenergized. However, moving the rotary switch arm 67a in a clockwise direction between contact 69 and contact 70 reduces the ohmic value of the resistance coupled between LED 66 and the battery', causing the intensity of the light emitted by the LED to continually increase. This operation may be performed by manual manipulation of the control knob 71 which is preferably mounted upon top surface 19b of the remote control unit. Thus, the arrangement of Figure 3d provides a means for controlling both ON/OFF and light intensity by employing an LED mounted within the remote control unit together with a small battery. Since the LED 36 has a very low current drain, the battery need be changed very infrequently, for example, once a year. Also, there is no danger whatsoever of experiencing any shock as a result of the presence of a small low power battery in the remote control unit.Figure 3e shows an embodiment in which the LED arrangement of Figure 3d may be combined with the polarized lens arrangement of Figures 3a and 3b. As shown therein, LED 66 may be coupled to the plus terminal of the DC source through a resistor R5 by a simple closure of switch 72. Thus, light is emitted through the polarized lenses 56 and 57 to enter the distal end 40b of fiber optics bundle 40. Light of a constant brightness is provided, and the intensity of light is regulated by rotating polarized lens 56 relative to lens 57 in the same manner as the control apparatus shown in Figures 3a and 3b. Again, the embodiment of Figure 3e utilizes a small, low power battery within the remote control unit, which battery experiences low current drain due to the low current requirements of the LED 66. Figure 3f shows still another embodiment of the present invention wherein a positive DC source, which is preferably a penlite battery, is selectively coupled to a high frequency generator 76 by means of a normally opened switch 77. Switch 77 is normally biased to the open position by spring means 78. By depressing switch button 77a, movable arm 77b provides a shunt path across stationary contacts 77c and 77d to energize tone generator 76 which generates a constant frequency tone, the tone being transmitted over antenna 79 to a small receiver antenna 80 provided within the receptacle 18. The received signal is stepped down in frequency at 85, is amplified at 81, undergoes filtering by band-pass filter 82, and is again amplified at 83, which circuit further provides wave shaping of the signal to create a trigger signal for operating a bistable flip-flop 84 for turnon of the main lamp source referred to - hereinabove. The tone generator 76 generates a radio frequency wave picked up by a receiver 85 tuned to the proper frequency. Alternatively, the tone generator 76 may generate a signal in the audio range, preferably in excess of 20,000 cycles per second so as to lie above the normal hearing range. The signal may be generated by a constant frequency generator 76 and applied to a piezo-electric crystal element for converting the electrical signal into a sonic frequency. The receiver 80 is preferably a piezo- electric crystal utilized to convert the received audio frequency signal into an electrical signal which is again amplified, filtered and appropriately wave-shaped to control the bistable flip-flop 84, or, for that matter, any other control circuit suitable for turning on and turning off the light source. The main light source may be automatically activated merely by lifting the light carrying hand¬ piece. For example, Figure 6 shows the handpiece 24 (of Figure 4) as being held by a cradle member100 when not in use. The cradle member is bifurcated to receive the body portion 24a in slot 101, while the bifurcated arms 100a and 100b support the larger diameter- head portion 24c. As shown in Figure 6a, the cradle may be pivotally mounted at a point 102 intermediate its ends, a spring 103 having a light spring force tends to urge the cradle clockwise about pivot 102. A microswitch 104 is connected between a voltage source +V and a transmitter 76 (see also Figure 3f).When the handpiece 24 is resting in the cradle 100, the weight of the handpiece overcomes the light spring force of spring 103 and rotates the cradle counterclockwise, causing the right-hand end of the cradle to urge the arm 104a of the microswitch contacts (not shown) in the open position. When the handpiece is lifted from the cradle, the spring 103 urges the cradle clockwise about pivot 102 to move the cradle arm away from the microswitch arm 104a causing the microswitch to couple source +V to transmitter 76 which operates in the same manner as was described in connection with Figure 3f.In place of a pivotally mounted cradle, the microswitch may be activated by insertion of the handpiece into a nesting opening (not shown) which is adapted to receive and support the handpiece 24 when not in use. The microswitch may be activated when the handpiece is inserted and/or removed from the nesting socket.The microswitch may be replaced by a switching technique of the type shown in Figures 4-4b, wherein the cradle may be provided with a projection movable between the adjacent ends of two fiber optics bundles to couple light from a light source to a phototransistor for activating the main light source.As still another alternative embodiment for the present invention, the capability of the remote control unit may be directly built into the dental handpiece as an integral part thereof, or, alterna¬ tively, may be strapped to or otherwise affixed to the handpiece, preferably at a location which does not interfere with the holding and manipulation of the handpiece so as to avoid accidental turnon or turnoff of the light source. Alternatively, the handpiece may comprise only a light source usable alone or with a drill handpiece by being strapped or otherwise secured to the dental drill handpiece. As shown in Figures 4 through 4b, the handpiece is provided with an elongated body portion 24a having a coupler 24b at its lower end for coupling the drive air, water, exhaust and fiber optics bundle 23 extending from their sources to the handpiece24 as is conventional in such prior art apparatus.-BUR In addition thereto, the handpiece of the present invention provides coupling for two additional fiber optics bundles 32 and 40 which extend into the bottom portion of handpiece 24. The lower end of the handpiece body 24a is fitted with a manually operable slide button 90. The surface thereof is roughened or otherwise provided with a plurality of V-grooves 90a to facilitate simple movement of the slide button between an ON and an OFF position. As shown, for example, in Figures 4a and 4b, the interior side of the slide button 90 which extends into body 24a is provided with a pair of L-shaped flanges 91 and 92 which define grooves 95a and 95b adapted to slidably receive the marginal edges of an opening 95 in handpiece body 24a so as to permit the slide button to be reciprocally movable along the handpiece body. A sheetlike projection 97 extends from the interior surface of slide button 90 into the body of the handpiece so as to be movably positioned between the distal ends 40b and 32b of the fiber optics bundles 40 and 32, respectively. Thus, as shown in Figures 4 and 4b, when the slide button is moved to its uppermost (OFF) position, the sheetlike projec¬ tion 97, which is preferably opaque, extends between the distal ends of fiber optics bundles 40 and 32 to prevent light from passing therebetween. By moving slide button from the OFF position and downwardly in the direction shown by arrow 99, the plate-like projection 97 is moved from its position between the distal ends 40b and 32b of the fiber optics bundles 40 and 32 to permit light conveyed toward the distal end of fiber optics bundle 32 (for example, from the LED 34 shown in Figure 1) to enter the distal end 40b of fiber optics bundle 40 so as to be conveyed, for example, to phototransistor 37 shown in Figure 1 so as to enable remote operation of the main light source conveying light to the fiber optics branches 23a and 23b, to be controlled directly from the dental handpiece, thereby totally eliminating the remote control unit. Obviously, if desired, the fiber optics bundle 32 may be eliminated and ambient light may be utilized in the embodiment shown in Figures 4-4b by using the technique described in connection with the embodiment of Figure 2. Also, the alternative arrangements for providing intensity control and/or a localized power source at the dental handpiece may also be incorporated therein (i.e., a penlite battery). However, it is most desirable to maintain the handpiece as trim and uncluttered as is possible so that the preferred arrangement therefor is that shown in Figures 4 through 4b.Turning to a consideration of Figure 7, there is shown therein still another preferred embodiment110 of the present invention which is comprised of a miniature size switch 111, preferably of the normally-open type push-button and which is adapted to be mounted either directly upon or in close proximity to the dental handpiece (see Figure 8). A pair of elongated leads 112 serve to couple the remote switch111 into the activating circuit to provide automatic control of the lamp as will be more fully described.■Considering Figure 8, the aforementioned pair of lead lines 112 is combined in a single bundle with the other conduits which serve as the means for conveying light, pressurized air, water, and so forth to the handpiece. Typically, the handpiece 24 may be coupled with a bundle of conduits such as the water 113, air 114, chip air 115, and exhaust 116 conduits, as well as a fiber optic cable 117 in which is mounted the fiber optics bundle 118. A strain relief cord 119 may also be provided to prevent any of the individual conduits, cables, BU EOMPI lead lines and the like from being stretched or broken.Exhaust conduit 116 may be provided with a pressure transducer or pressure sensitive switch 115 mounted within conduit 116 and coupled to suitable circuit control means by lead lines 120. The pressure transducer or pressure sensitive switch 155 is rendered operative in the presence of air under pressure within the exhaust conduit 116 for the purpose of controlling lamp 131 as will be more fully described. The lead lines 112 may extend to a position just below the handpiece coupling member 24C as shown at 112' or, alternatively, may extend through coupling 24C as shown at 112 and may extend into the handpiece 24 as shown at 112 , enabling the switch 111 to be mounted directly upon handpiece 24. Alternatively, the remote switch 111 may be mounted at or just below the handpiece coupling 24C which is also a convenient location for manipula- tion by the operator.The bundling of the lead lines 112 in the manner shown does not in any way complicate the design of the handpiece or its conduits and further serves to prevent the lead lines for switch 111 from interfer- ing in any way with the physical positioning, movement or functioning of the handpiece and the conduits servicing the handpiece.Turning to a consideration of Figure 7, remote switch 111 is shown as being connected in electrical series with pulse circuit 121 and the light emitting diode element 123 provided within the optically coupled isolator 122.The optically coupled isolator 122 is,, in one preferred embodiment, a small, fully self-contained package comprised of an enclosure having lead lines extending through the body of the enclosure for facilitating its connection in an electrical circuit and housing in its interior a light emitting diode123 and a phototransistor 124. One suitable device of this type is the 4N25 optically coupled isolator which may be obtained from Optron, Inc., and having a light emitting diode 123 of the gallium arsenide infrared type and having a silicon type phototransistor 124.As shown in Figure 7, the light emitting element 123 is connected in the electrical circuit loop including remote switch 111 and pulse circuit 121. Pulse circuit 121 is comprised of parallel connected resistor and capacitor Rl and Cl, respectively. A resistor R2 is connected in series with the parallel connection, while a power source El, which in the present example is a small size 9 volt battery, is utilized as the low voltage power source for the pulse circuit.Momentary closure of remote switch 11 causes & pulse to be instantaneously applied to the light emitting element 123, said pulse instantaneously building to the voltage of source El, and decaying at a rate determined by the value of the circuit components Rl, Cl and R2. The aforementioned generated pulse causes the light emitting diode (LED) 123 to conduct and thereby emit light (in the infrared wave length i the example given) . This light is detected by phototransistor124 whose conductivity increases as a function of the intensity of infrared light impinging thereon.The conductor-emitter electrodes of phototransistor 124 are connected across the terminals of capacitor C2 forming a part of receiver circuit 125. Receiver circuit 125 is further comprised of a transistor Ql which has its collector connected to a positiveDC source +Vcc through resistor R4 while its emitter is connected to ground. A charging resistor R3 connects capacitor C2 to source +Vcc and the common terminal between R3 and C2 is connected to the base electrode of Ql through diode Dl. During the time that photo- transistor 124 is nonconductive, capacitor C2 charges to the level +Vcc causing transistor Ql to conduct so that its collector electrode is substantially at ground potential.When remote switch 11 is closed, causing emitting element 123 to be pulsed with electrical energy, the infrared light emitted from LED 123 substantially increases the conductivity (i.e., substantially reduces the resistivity) of phototransistor 124 to ground. The abrupt reduction in the voltage level at the common terminal between R3 and C2 serves to turn transistor Ql off, causing the voltage level at the collector of Ql to move abruptly toward the supply level +Vcc. This positive going pulse is applied to the trigger input 126a of a counter 126. In the preferred embodiment, counter 126 is provided with two stages and is electrically hand-wired so as to be capable of counting up to a count of 3 and then automatically resetting the counter, thus repetitively producing the binary outputs (00), (01), (10), (00), (01), (10). One typical way of providing the desired circuitry is through the employ¬ ment of an integrated circuit, for example of the type 4027 which is comprised of first and second J-K master/slave flip-flops. One suitable integrated circuit of this type Is the' CD 4027 AD digital inte¬ grated circuit produced by the Solid State Division of RCA.The control signals utilized for purposes of controlling off, on and lamp intensity level are taken from one output of each 126b and 126c of the two stages (i.e., flip-flops) comprising counter 126. In order to operate the fan, a third output 126d of the second stage is utilized. A description of the manner in which the output signals of the counter 126 are employed to control turnon and intensit level of the lamp and turnon and turnoff of the blower is set forth hereinbelow in greater detail.The outputs 126b and 126c are coupled to an on/off and intensity decoder circuit 127. An on/off decoder circuit 128 for the fan is connected to output 126d.Decoder 127 is coupled to a lamp phase shift intensity control circuit 129, while decoder 128 is coupled to a similar type circuit 130 for controlling selective energization of fan 132. Lamp 131 and fan 132 are connected in a circuit loop with AC source 135 and triacs 133 and 134, respectively.The triacs 133 and 134 are three-terminal devices. Two of the terminals (133a and 133b) may be likened to anode and cathode electrode while the third terminal (133c) is a gate electrode. Each triac will conduct when the voltage across its anode-cathode electrodes (133a and 133b) is greater than zero and when pulsed at its gate electrode such that the direction of the pulse applied at the gate electrode and the polarity of voltage across terminals 133a and 133b determines the direction of current flow. As a result, triacs 133 and 134 can be seen to be bidirectional devices with the anode and cathode electrodes 133a and 133b being interchangeable and functioning as cathode and anode electrodes during one half cycle and as anode and cathode electrodes during the next succeeding half cycle of the alternating current signal from source 135. Thus, if the gate electrode 133a is pulsed at the beginning of each half cycle, triac 133 will turn on and remain on throughout that half cycle. However, as soon as the alternating current wave form passes through zero so that the voltage levels at the anode and cathode electrodes are reversed, triac 133 will no longer conduct unless another gate pulse of the proper polarity is applied to gate 133c at the inception of or at some point during the inception of the next half cycle of the AC signal. The gate pulse may occur at any time during each half cycle. If each gate pulse is caused to occur upon the initiation of each half cycle, i.e., as each half cycle passes through zero voltage in the positive going direction, triac 133 may remain on for 1007o of each cycle of AC signal. However, by delaying application of each gate pulse a predeter- mined time after initiation of each half cycle, it is possible to regulate the portion of each half cycle during which triac 133 is turned on.These characteristics are utilized to advantage in the present invention by regulating the turnon time of the triac during each half cycle of the AC signal, in accordance with the count present in counter 126 to either turn off lamp 131, turn on lamp 131 at half intensity, or turn on lamp 131 in full intensity, respectively. The manner in which this is accomplished is by means of the decoder and phase shift intensity control circuitry shown in greater detail in Figure 7a. As shown therein, the on/off and intensity decoder 127 is comprised of operational amplifier 137 having an inverting input coupled to output 126b of counter 126 through diode D2 and having a noninverting input coupled to output 126c of counter 126. The output of operational amplifier 137 is coupled to the non¬ inverting input of the amplifier through resistor R5. The output of the operational amplifier is also coupled to the input of comparator 138 forming a part of the lamp phase shift and intensity control circuit. The circuit 129 further includes a zero crossing detector 139, ramp generator 140, zero current detector 141, control logic circuit 142, chopper circuit 143, output logic state circuit144 and gate pulse stage 145.The zero-crossing detector circuit 139 is coupled to the AC source 135 which serves to power lamp131 as well as fan 132. Each time circuit 139 detects a zero crossing, its output 139a triggers ramp generato 140 to develop a ramp signal at its output 140a. This signal is compared by comparator 138 against the level appearing at the-output of operational amplifier 137. When the ramp signal developed at output 140a reaches the voltage level applied to comparator 138 by operational amplifier 137, control signals are developed at outputs 138a and 138b of comparator 138. The zero-crossing detector also determines the polarity of each gate pulse signal a d is coupled to control logic 142 for this purpose. Zero-current detector circuit 141 is connected in series with AC source 135 and lamp 131 through resistor R7 to monitor the current through lamp 131. When the current through lamp 131 falls to zero, output 141a applies an enabling signal to control logic 142. Control logic circuit 142 which includes gating means (not shown for purpose of simplicity) serves to develop an output pulse. Three conditions occur simultaneously, i.e., when there is no current flowing through lamp 131, when the AC wave form has made a zero crossing, and when the signal level ramp generator 140 has been reset and has increased to the level applied to comparator 138 by operational amplifier 137. The square pulse developed by control logic 142 is applied to chopper circuit 143 through capacitor C6 which converts the square pulse into an impulse signal. The output 138d of comparator coupled to chopper 143 prevents spurious gate pulses from forming before the comparator has switched correctly. The impulse signal appearing at output 143a is applied to output logic stage 144 which develops an output signal so long as a zero-crossing conductor is present. The output signal from the output logic stage 144 undergoes pulse shaping at gate pulse stage 145 to provide a sharp pulse of the proper polarity for application to the gate electrode 133a of triac 133. The manner of operation is such that when counter 126 is at a count of zero, the control level applied to input 138a of comparator 138 through operational amplifier 137 is sufficiently high to prevent the ramp signal from reaching that level during each half cycle so as to keep lamp 131 in the off condition.By closing switch 111, the count in counter 126 is advanced by one count (i.e., to 01) to develop a signal level applied to input 138a of comparator 138 by operational amplifier 137 to turn on triac 133 after a delay subsequent to each zero crossing which is sufficient to illuminate lamp 133 at half intensity. A subsequent momentary closure of switch 111 causes counter 126 to be advanced by one count to a count 10, causing the output level applied by operational amplifier 137 to input 138a of comparator 138 to be reduced below the aforesaid half intensity level, whereby the signal developed by ramp generator 140 builds to the signal level at input 138a at a time still closer to the last occurring zero crossing to cause the gate of the triac to be pulsed at a closer point in time to the beginning of each half cycle to increase the on time of the lamp during each AC half cycle sufficient to cause the lamp to glow at full intensity. By closing remote switch 111 once more, counter126 is automatically reset to a count of zero (00) returning the lamp 131 to the off condition by developing a signal level at input 183a high enough to prevent the ramp signal from reaching the level at input 138a during each AC half cycle.The on/off decoder 128 and the fan on/off control 130 may be comprised of the same type of circuitry as that utilized for the lamp decoder 127 and lamp' pulse shift intensity control 129, except that the fan on/off control and decoder is preferably connected to cause the fan to be operated at its full rated output regardless of the fact that the lamp is on at either full or half intensity. The circuitry which may be employed for the decoder and triac phase shift control is the L120 integrated circuit for triac phase control available from SGS-ATES.The arrangement of Figure 7 may be simplified by replacing the count of 3 counter 126 by a count of 2 counter, i.e., by a bistable flip-flop which is driven to one of its two stable states by closure of switch 111 and which is driven to the other of its two stable states by a subsequent closure of switch 111, wherein these states are utilized for turning off lamp 131 and for turning on 131 to full intensity, respectively.Obviously, the opposite capability may likewise be provided wherein count of 3 counter 126 may be replaced by counter means having a capability of counting to greater than 3 counts in order to provide levels of intensity other than half intensity and full intensity as was set forth hereinabove.As still another alternative to the embodiment described hereinabove, the optically coupled isolator may be replaced by a transducer capable of generating an audio frequency and a receiver element adapted to generate an electrical signal responsive to operation of the transducer element at the frequency of the transducer.Figure 7b shows still another alternative embodi- ment wherein the optically coupled isolator may be replaced by a reed switch assembly 150 comprised of a pair of switch elements 152 encapsulated within an evacuated envelope 153 and adapted to be maintained in the normally open position. The reed switch assembly is further comprised of a winding 151 wound about envelope 153 and electrically connected within the circuit loop including remote switch 111 and pulse circuit 121. Upon momentary closure of switch 111, winding 151 is pulsed to set up a magnetic field which causes momentary closure of reed switch contact elements 152. By connecting these reed switch contact elements across capacitor C2, shown in Figure 7, capacitor C2 may be caused to discharge through the closed reed switch elements to pulse counter 126 in the same manner as previously described with respect to the phototransistor 124 of the optically coupled isolator 122. It should be understood that the embodiment of Figure 7 accomplishes all of the advantages of previously described embodiments of the present invention in that all of the elements shown in Figure 7, with the exception of the remote switch 111 and its lead line 112, may be housed within a single housing represented by dashed line 60. The assembly is provided with a single power cord which may be coupled to a conventional 115 volt AC 60 Hertz power source which is wired to provide the power for driving lamp 131 and fan 132. The aforementioned integrated circuit type L120, further includes the capability of rectification and filtering of the AC signal to provide the DC levels necessary for powering transistor Ql and counter 126, as well as the DC powered circuits of decoder 127 and the shift control circuit 129, which circuits are shown in Figure 7A. In addition, the circuit of Figure 7 totally eliminates the need for an expensive and heavy transformer and for a special purpose lamp, which elements are required in the prior art design of U.S. Patent No. 3,758,951, described hereinabove. The last described embodiment is quite compact, having a housing which occupies a small amount of space. 0Figure 8a shows a pressure actuated switch assembly 155 which is advantageous for use in the present invention. The switch is comprised of enclosure halves 156a and 156b forming enclosure 156, having a hollow interior 157 for mounting resilient blades 5 158, 159 connected to electrical terminals 160, 161, respectively, through conductive pins 162, 163. Screw 156c adjusts the exposure of an aperture 156e in housing to control the pressure sensitivity. 0 Hollow pressure port 156d receives air under pressure through a flexible conduit 165, coupled to drive air conduit 114 (Figure 8) through T-connector 166. Diaphragm 170, which is sandwiched between enclosure halves 156a and 156b, moves upwardly against canti- 5 levered contact 158 to close the switch.When the operator depresses the pressure delivery switch, not shown for purposes of simplicity, air pressure is introduced into drive air conduit 114. The dental handpiece is typically provided with 0 an impeller rotated by the drive air to operate a drill mounted at the working end of the dental handpiece. The drive air conduit 114 extends to one end of the impeller while the exhaust air conduit is placed on the downstream side of the impeller „,. and carries exhaust air away from the dental handpiece to avoid an undesirable pressure drop at the impeller. The pressure activated switch 155 is mounted within the exhaust air conduit 116 and closes when air under pressure is delivered to the dental handpiece24. Switch closure may activate the pulse circuit121 of Figure 7 to selectively energize lamp 131 and fan 132 in the manner previously described.The switch may alternatively take the form of a transducer which generates an electrical signal for activating one of the transmitting devices 123, 0 for example, for controlling lamp 131 and fan 132.Figure 9 shows a fiber optics illuminator which may employ the remote switching capability of the present invention and which is an independent unit, as opposed to being integrated in a dental handpiece. _■ The unit 190 is comprised of an elongated sleeve191 whose lower end is shown broken, but is understood to be positioned adjacent to the lamp source 131, for example, as shown in Figure 7.The sleeve 191 houses a bundle of optical fibers 0 which are separate from one another to allow the sleeve to bend through rather small bending radii to facilitate manipulation and positioning of the unit.The upper end 192 of the bundle is comprised of said optical fibers which have been potted in a transparent epoxy and then polished.Elongated helical spring 193 serves to prevent undue bending of the upper end of the illuminator 190. Q switch 194 having a depressible member 195 is arranged below spring 193. By depressing member 195,, the switch contacts (not shown) are closed. The contacts may be similar to those shown schematically as switch 111 in Figure 7. c Figure 10 shows another electrical isolation technique which may be substituted for the optical isolator 122 shown in Figure 7.The circuitry 200 shown in Figure 10 is comprised of a low voltage 10kHz signal generator 201 coupled to capacitor 202 through the one winding 203a of a transformer 203. The transformer further includes a winding 203b tightly inductively coupled to winding 203a by transformer core 203c. The end terminals of winding 203b are coupled to remote switch 111 through conductive leads 112 which may extend through sleeve 191 of the illuminator 190 shown in Figure 9.The closing of remote switch 111 alters the impedance of winding 203a by providing a direct short circuit condition across winding 203b. The short circuit condition across winding 203b is reflected back to winding 203a, thereby greatly increasing the charging current to capacitors 202 and 204. Diode 205 prevents capacitor 204 from discharging back to either capacitor 202 or the oscillator 201. Thus, capacitor 204 can only discharge through resistor 206 which has a high ohmic value (of the order of 100k ohms) so that capacitor 204 discharges slowly.When capacitor 204 charges to a sufficient level, Ql is turned on to operate the count of 3 counter in the same manner as was previously described with regard to Figure 7.The signal developed by oscillator 201 is insuf¬ ficient to cause any shock or injury to an operator especially due to its low voltage rating, and further avoids the need for a separate battery since oscillator 201 may be powered by rectifying and filtering line voltage down to a level of the order of 5 volts d.c. , or less.INDUSTRIAL APPLICABILITY:The present invention can be used in illumina¬ tion systems for dental drills. In such an environment, the invention provides added safety in that the patient is isolated from possible high-voltage shocks, etc. The invention may also be used, generally, for controlling any fiber optic illumination system. | AMENDED CLAIMS (repeived by the International Bureau on 13 August 1979 (13.08.79))1. Control means for selectively energizing a lamp serving as an illumination source for an elongated fiber optics bundle having a first end positioned adjacent to said lamp and a second end mounted at the working end of a dental handpiece, characterized by signal generating means (123) including switch means (111 or 155) for generating an enabling signal upon an actuation of said switch means, means (127, 129, and 133) for selectively applying AC power to said lamp, and sensing means (124-125) responsive to said enabling signal generated by said signal means and switch means for causing said means for selectively applying to couple AC power to said lamp, said signal generating means being electrically isolated from both said means for selectively applying AC power and said sensing means to protect the user of said dental handpiece, said sensing means including means (126) for latching said means for selectively applying AC power to said lamp in a coupling relationship with said lamp until a subsequent activation of said switch means for disabling said means for selectively coupling.2. Apparatus according to Claim 1 -characterized in that said sensing means and said means for selectively applying comprise: counter means (126) having a plurality of stable states and responsive to each enabling signal to advance the counter means from one stable state to the next, a triac (133) and an AC source (135) coupled in series with said lamp (131), said triac having a gate electrode (133a), means (129) for generating a gate signal responsive to the state of said counter means for controlling the time when the gate signal is applied to said gate electrodeO P■ under conditions where said gate signal is inhibited when said counter is in a first one of said stable states, said gate signal 'is applied to said gate electrode at a first predetermined time after the initiation of each half-cycle of the AC signal when said counter is in a second one of said stable states , and said gate signal is applied to said gate electrode at a second predetermined time after the initiation of each half-cycle of the AC signal , said second predetermined time being greater than said first predetermined time.3. Apparatus according to Claim 1 characterized in that said sensing means and said means for selectively applying comprise: counter means (126) for counting the number of operations of said switch means, anAC source (135) and a triac (131) connected in series with said light source, means (139) for detecting the zero crossings at the AC signal provided by said AC source, ramp signal generating means (140) responsive to each zero crossing for generating a ramp signal, delay control means (127) coupled to said counter means for developing a signal level representative of the count in said counter, comparator means (138) coupled to said delay control means and said ramp signal generating means for generating a signal when the level of said ramp signal reaches the level of the signal developed by said delay control means, and means (143, 144, 145) responsive to the output signal of said comparator means for applying a gate pulse to the electrode of said triac for triggering said triac to conduct at a point in each half-cycle of the AC signal which is a function of the count in said counter means . 4. Apparatus according to Claim 1 characterized in that said dental handpiece includes an air conduit (114) for delivering air under pressure to said dental handpiece having a branch conduit (165) communicating with said air conduit, and said switch means comprising pressure sensitive means (155) arranged in said branch conduit and responsive to the delivery of air under pressure to said dental handpiece through said air conduit to cause a generation of said enabling signal.5. Apparatus according to Claim 4 characterized in that said pressure sensitive means comprises a normally-open pressure sensitive switch (158, 159) acting to assume a closed condition when air under pressure is introduced into said air conduit.6. Apparatus according to Claim 1 characterized in that said signal generating means comprises manually operable switch means (111), oscillator means (201) provided at said illumination source, impedance means (203a) coupling said oscillator means to said sensing means, and means (203b, 203c) inductively coupling said switch means to said impedance means for reducing said impedance when said switch means is operated.7. Apparatus according to Claim 6 wherein said oscillator means is a high-frequency oscillator and further including an iron core transformer (203) and wherein said impedance means is formed by a first winding (203a) of said transformer (203) , and said inductive coupling means is formed by a second winding (203b) of said transformer which is inductively coupled to said first winding. 8. Apparatus according to Claim 1 characterized in that said signal generating means comprises means (76) for generating an electrical signal of a signal frequency in the audio range, transducer means (79) for converting the electrical signal into a sonic wave, said sensing means comprising transducer means (85) responsive to receipt of said sonic wave for converting same into an electrical signal, and filter means for passing electrical signals lying within narrow predetermined frequency range (82) .9. Apparatus according to Claim 1 characterized in that said signal generating means comprises means (76) for generating a radio frequency signal and miniature antenna means (79) for transmitting said radio frequency signal, and said sensing means comprises an antenna (80) for picking up the aforesaid radio frequency signal, filter means (82) for passing only those received signals lying within a narrow pre¬ determined frequency range, and means (84) responsive to those received signals passed by said filter means for generating said activating signal .10. Apparatus according to Claim 1 characterized in that said signal generating means comprises field producing means (151) for generating a magnetic field responsive to operation of said switch means, and said sensing means includes second switch means (152) responsive to said magnetic field for producing said activating signal. STATEMENTUNDERARTICLE19In response to the receipt of the International Searc Report, dated 13 June 1979 and in order to place this applic tion in better form for filing in designated national and regional offices, applicant hereby cancels all of Claims 1-4 (Pages 34-45) and hereby submits replacement Claims 1-10 (replacement Pages 34-37) .Of the replacement Claims 1-10, only Claim 1 is inde¬ pendent and represents a substantially amended form of origi Claim 34. Dependent Claims 2-10 correspond to originally fi Claims 31, 32, 35, 36, 38, 41, 8, 10, and 29, respectively, amended so as to properly depend on replacement Claim 10.IftR O | VICON PRODUCTS CORP; VICON PROD CORP | BINNER P; SCRIVO L; WEINSTEIN L |
WO-1979000604-A1 | 1,979,000,604 | WO | A1 | XX | 19,790,823 | 1,979 | 20,090,507 | new | D01H11 | null | D01H4, D01H11 | D01H 4/24 | AUTOMATIC CLEANING SYSTEM FOR OPEN-END SPINNING APPARATUS | An aero-mechanical open-spinning machine including spinning rotor cleaning means such as a fibrous brush (20) or air jet for continuously agitating any foreign matter on the interior surface of the spinning rotor (13) so that same may exit in the airstream accompanying the open-end spun yarn. | BACKGROUNDThis invention relates to systems for open-end spinning, and particularly to systems for continuously cleaning aero-mechanical open-end spinning apparatus, especially the spinning rotor or turbine thereof.The technique for open-end spinning is a process of separating staple fibers from an input feedbunch and transporting them to a revolving open- end reassembly and twisting point to form a yarn. There are at least three main approaches to open-end spinning: aero-dynamic systems, electro-mechanical systems, and aero-mechanical systems.The aero-dynamic systems , a spiral airflow is . roduced downwardly in a tube into which separated staple fibers are introduced by means of a secondary air inlet. A seed yarn is introduced into the spiral flow, and the separated fibers gather on its tail. The seed yarn is withdrawn from the tube and, as it is withdrawn, the staple fibers gathered on it are twisted by the rotation of the yarn in the airstream. The yarns produced by this method are, however, weak and irregular.In electro-mechanical systems, electrostatic forces generated from high potentials (on the order of 30 kilovolts) transport the separated staple fibers from a drafting system, and hold them in control during the mechanical twisting action impaited by a rotating needle basket.In aero-mechanical systems, the separated staple fibers are delivered along with the air stream into a revolving rotor (often referred to as a spinning rotor or turbine) , forming a fiber ring around the periphery thereof. A seed yarn is introduced into the rotor, and its tail collects the fibers lying around the periphery. The fibers so collected are twisted into the yarn by the rotation of the rotor as the seed yarn is withdrawn. This is a system of open-end spinning which has been commercially exploited. Machines employing this system include that manufactured by Toyoda Automatic Loom Works, Ltd. of Aichi-Ken,. Japan, . known as Model BS, and that manufactured by Schurr, Stahlecker & Grill GmbH, Suessen, West Germany, known as the Suessen Open-End Spintester. Such open end spinning machines have been described in detail in numerous publications and patents.Despite its commercialization, the yarn produced by present aero-mechanical systems is initially produced at a given quality level, but that yarn quality graduall deteriorates as bits of lint and particles of other foreign substances build up on the interior surface of the spinning rotor or turbine. As a result the rotors on present commercial open-end spinning equipment have to be cleaned frequently on a regular schedule.BRIEF SUMMARY OF THE INVENTIONIt is the object of the present invention to provide an open-end spinning system which will contin¬ uously and automatically avoid accumulation of foreign matter inside the spinning rotor or turbine, thereby increasing the quality of the resultant yarn.The foregoing object and others are accom¬ plished in accordance with the present invention by employment in an open-end spinning system of spinning rotor cleaning means, which may comprise a fibrous brush or air jet extending from the material in which the yarn exit or navel of the open-end spinning apparatus is formed, and impinging upon the interior surface of the spinning rotor or turbine, to thereby con¬ tinuously make airborne any particles of lint or other foreign matter entering the rotor or turbine with the yarn fiber feedstock, so that said foreign matter is evacuated from the rotor or turbine in the airstream accompanying the formed yarn exiting through the navel.BRIEF DESCRIPTION OF THE DRAWINGS For a better understanding of the- invention, as well as other objects and further features thereof, reference is made to the following detailed disclosure of preferred embodiments of the invention taken in conjunction with the accompanying drawings thereof, wherein:Fig. 1 is a partially schematic, cross- sectional view of an exemplary prior art open-end spinning machine;Fig. 2 is a partially schematic, plan view of the exit navel area of a machine like that shown in Fig. 1;Fig. 3 is a partially schematic cross- sectional view of an exemplary open-end spinning machine like that shown in Fig. 1, except now including an embodiment of the present invention.Fig. 4 is a partially schematic, plan view of the exit navel area of a machine like that shown in Fig. 3, including an embodiment of the present invention. «Fig. 5 is a partially schematic cross- sectional view of an exemplary open-end spinning machine like that shown in Fig. 1, except now including another embodiment of the present invention.Fig. 6 is a partially schematic plan view of the exit navel area of a machine like that shown in Fig. 5 including said other embodiment of the present invention.DETAILED DESCRIPTION The manufacture of textile yarns by open- end spinning is well known. A typical open-end spinning machine includes a turbine or rotor on the interior surface of which fibers are actually spun into yarn. Sliver is typically carried to that spining rotor or turbine by a feed roller equipped with a pressing nose, and then transferred to a combing roller. Metallic wires in the shape of -saw-teeth are wound around the combing roller, and comb sliver fed to that combing roller. The combed .fibers are then pushed by the toothed combing rotor so' that they leave the combing roller and are transferred on an airstream, shown at 11 i Fig. 1, through a port 12 leading to the inner wall* of the turbine 13. The fibers are collected and spun at the largest interior diameter of the turbine. The resultant yarn is then drawn out through an exit opening 14 in navel 15 and transported to a take-up roller 16 where it is wound into a cheese.__s more clearly shown in Fig. 2, in one embodi¬ ment the port 12 through which the combed fibers enter the interior of the spinning rotor or turbine 13 is in an upstanding shoulder 17 which surrounds or is a part of the regiorf of navel 15. The turbine13 spins in a position adjacent and covering the shoulder 17 and navel 15 as shown in Fig. 1. As illustrated ire Figs. 1 and 2, the turbine rotates clockwise when one views the interior thereof. Hence, as illustrated in/Fig. 2, the combedfibers emerging from port 12 commence their residence within the spinning turbine at a location around the periphery thereof which corresponds to point A, those fibers then following the path 18 in a direction B on the interior of the spinning rotor or turbine, just adjacent shoulder 17, and the resultant yarn 19 is then pulled into' exit opening14 so that the spun fibers leave the periphery of the spinning rotor or turbine at approximately point C as shown in Figure 2. When the direction in which the point where the spun fibers leave the inner wall of the turbine moves in the same direction as that in which the turbine rotates, the condition is called forward-direction spinning. While under certain conditions those two conditions may become opposite to produce backward-direction spinning, OM W1P forward-direction spinning is a more stable situation in which better quality yam is spun. This relationship between the direction of rotation of the rotor or turbine, and the yarn being spun is well known, and is explained in a publication entitled Technical Background of Toyoda Open-End Spinning Machine, by T. Tooka, Director, Toyota Automatic Loom Works, Ltd., Aichi-Ken Japan.However, as explained in that same publication, if the sliver fed to an open-end spinning machine contains foreign matter such as trash, this foreign matter is deposited on the inner wall of the turbine, with the deposits becoming heavier in the course of time. Buildup of such deposits decreases the strength of the resultant yarn, increases the uneveness of the yarn, as well as other yarn defects, and increases the frequency of end breakage during open-end spinning. As explained in that publication, an earlier solution to this problem was the removal of trash from raw fibers, such as cotton, by blowing, with most of the rest of such trash being removed by a card. However, that solution was not completely satisfactory, so a further attempt at solving the problem utilized a purifying roller on a card, to there¬ by crush any leaf fragments remaining in the fibers. into fine particles. Additionally, a tandem card equipped with two sets of purifying rollers was used for further removal of leaf fragments.The present invention provides a new solution to the problem of foreign matter deposits building up on the inner wall of the spinning rotor or turbine and the resultant decreases in yarn quality. As shown in Figure 2, there is a minor sector C-A of the circumference of shoulder 17 or navel 15 about which fibers do not pass during the open-end spinning process. In the advantageous system of the present invention, . this free sector of the spinning apparatus is utilized as the site of means for continuously agitating any foreign matter deposits on the inner wall of the spinning rotor or turbine, and the^ airstream within the rotor or turbine to thereby make such foreign matter airborne, so that it is evacuated from the area within the spinning rotor or turbine in the airstream which accompanies the spun, yarn leaving that area through exit port 14. In various embodiments, this inventive means may comprise a mechanical agitator such as a fibrous brush, or may comprise ah airstream impinging upon the interior surface of the spinning rotor or turbine, or any other suitable means for loosening foreign matter particles deposited thereon. It is important to place the means for removing foreign matter built up upon the inner wall of the turbine in the sector C-A through which fibers being spun do not pass, since the presence of the inventive means should not disturb the fibers being twisted in the spinning rotor or turbine.One specific embodiment of the presently claimed invention is shown in Figures 3 and 4 where a number of bristles have been inserted into a hole so that those bristles contact the largest diaiueter portion of the interior of the spinning rotor or turbine 13 in a manner to remove any foreign matter particles accumulated thereon, and to indeed prevent a substantial accumulation thereof. As shown in Figure 4, the bristles 20 extend in a direction which is obliquely similar to the direction D in which spinning rotor or turbine 13 rotates so that the tips of the bristles 20 have a tendency to agitate any foreign particles from the interior surface of the rotor 13. The bristles themselves may comprise any suitable'materia such as hog bristles, nylon fibers, or others cut to a length so hat they just come into contact with the surface of the rotor or turbine.Still another embodiment of the present invention is shown in Figures 5 and 6 wherein the means for agitating and making airborne any particles of foreign material accumulated on the inner surface of the turbine comprises an air jet emerging from the region of shoulder 17 in a direction obliquely similar to the direction of rotation of rotor or turbine 13. This direction is shown by the path 21 emerging from air jet 22 as shown in Fig. 6. In various embodi¬ ments, the air jet 22 may simply be flush with the surface of shoulder 17, or may extend therefrom. Compressed air emitted through air jet 22 should have sufficient direction and velocity to remove particles of foreign matter which may have accumulated on the interior surface of the turbine, and to prevent further accumulation thereof, but the direction and velocity thereof should not be such as to interfere with the desired yarn spinning operation of the apparatus.The advantageous cleaning system of the present invention provides a number of advantages over standard open-end spinning systems which do not make use of such a system. These advantages appear both in yarn quality and improved production efficiency. In general, the fact that the rotor or turbine is continuously cleaned maintains the quality of the yarn being spun therein at the same level hour after hour of operation. Furthermore, since the system of the present invention does not require the open- end spinning apparatus to be shut down for frequent periodic cleaning, the present system increases production time, and decreases labor costs associated with the frequent periodic cleaning required in the absence of the inventive system. The continuously cleaned open-end rotor or turbine of the present invention maintains the evenness and breaking strength of the yarn being produced thereby. Yarn breaking strength is quite important when such yarns are woven or knitted into fabric, because most fabrics have established bursting strength standards which must be met in order to be competitive in theOMPI marketplace. The present invention maintains a clean rotor which produces strong yarn. Furthermore, the reduction in ends down (i.e. broken yarns in the open-end spinning machine) , reduces the number of stops and thereby increases production time and reduces costs.The following example further specifically defines the improved op_n-end spinning system of the present invention. This example is intended to illustrate a preferred embodiment of the novel open- end spinning cleaning system of the present invention.EXAMPLES I AND II The present invention -was embodied in a Suessen Open-End Spintester open-end spinning machine, manufactured by Spindelfabrik Suessen, Schurr, Stahlecker & Grill GmbH, 7334 Suessen, West Germany, which was modified by. installation of cleaning brush bristles in accordance with the present invention. The cleaning bristles were installed approximately as shown in Figs. 3 and 4 hereof so that they just contacted the interior surface of the spinning rotor at the region of its greatest internal diameter. '^I the following table the data in Column I is for operation of the Suessen Open-End Spintester Machine without the present invention. Column II contains data for operation of the same machine mo¬ dified as described above to embody the present invention. In both cases I and II, the machine also included an additional combing sector <as disclosed in my copending application Serial No. 871,142, filed January 20, 1978, but that sector does not form a part of the present invention.O IIMachine Suessen Suessen modified Fiber Somewhat leafy Somewhat leafy 100% Cotton 100% CottonRotor Speed 30,000 RPM 30,000 RPMComber Speed 6,000 RPM 6,000 RPMSliver wt/yd. 70 grains 70 grainsYarn size .18/1 18/1Yarn decreases with maintains initial Uniformity build-up of foreign degree of matter in rotor evennessEnds down increase with Virtually build-up of eliminated foreign matter in rotorYarn Hairiness increases with maintains initial foreign matter less fuzzy build-up in rotor conditionRotor Cleaning Once every 8 never in 80 Frequency hours hoursAs shown in the table, yarns produced by the system including the present invention exhibit in¬ creased yarn uniformity, decreased* yarn fuzziness, and dramatic improvement in ends down during open- end spinning, and therefore apparently greater strength. Additionally, rotor shut-down for cleaning is substantially eliminated.Although specific components, proportions and arrangements of elements have been stated in the above description of preferred embodiments of this invention, other equivalent components and arrange¬ ments of elements may be used with satisfactory results and various degrees of quality, or other modifications may be made herein to enhance the construction of the invention to thereby increase its utility. It will be understood that such changes of details, materials, arrangements of parts, and uses of the invention described and illustrated herein, are intended to be included within the principles and scope of the claimed invention. | WHAT IS CLAIMED IS:1. In an open-end spinning apparatus for manufacturing textile yarns, Of the- type comprising a cup-like turbine into which combed fibers- are .-- transported on an airstream, in which fibers are spun into yarn, and from which yarn is removed through an exit port or navel near'*'the..center around which said turbine spins, the improvement comprising means associated with said turbine for agitating, and thereby removing, foreign matter accumulated on the interior surface of the turbine, said means being located at the sector of the periphery of 'the turbine through which fibers do not pass during spinning.2. The apparatus of claim 1 wherein said means for removing foreign matter from the interior surface of the turbine is primarily directed to removing such matter from that portion of the internal surface of the turbine which has the largest diameter.3. he^apparatus of claim 2 wherein said means comprises fibrous bristles extending 'from the region of said navel into-^contact with the interior * surface σf said turbine.4. The apparatus of claim 3, wherein said bristles approach said internal surface from a direction generally similar to the direction of rotation of the turbine.5. The apparatus of claim 4, wherein sa_d bristles comprise a material 'selected from the group consisting of: hog bristles and nylon fibers.6. The apparatus of claim 2, wherein said -means for removing foreign matter from the interior surface of the turbine comprises an 7. The apparatus of claim 6, wherein said air jet impinges upon said internal surface from a direction generally similar to the direction of rotation of the turbine.OMP■ | DIXIE YARNS; DIXIE YARNS INC | ALSTON O |
WO-1979000609-A1 | 1,979,000,609 | WO | A1 | XX | 19,790,823 | 1,979 | 20,090,507 | new | C07G7 | C08B37, C08F8, C07G7, C08H1 | B01J20, B01J31, C07D251, C07K14, C07K17, C08B1, C08B37, C08F8, C12N11 | B01J 20/32, C08B 37/00M4B, C12N 11/10 | PREPARATION OF TRICHLORO-S-TRIAZINE ACTIVATED SUPPORTS | When coupling protein and non-protein affinity ligands to solid-phase supports activated with trichloro-s-triazine (TsT), the TsT activated solid-phase support is prepared by reacting a water-free insoluble solid support with TsT in a nonaqueous medium comprising an organic solvent, neutralizing HCl generated during the reaction with a tertiary amine that does not form an insoluble complex with TsT and washing the resultant TsT activated support with organic solvent. After washing, the TsT activated support may be reacted with a nucleophile in an organic solvent to replace one or both chlorine atoms on the triazine ring. | -1-TITLE: METHODS OF USING TRΪCHLORO-S-TRIAZINE FOR COUPLING ENZYMES AND AFFINITY LIGANDS TO SOLID-PHASE SUPPORTSBACKGROUND AND SUMMARY OF THE INVENTIONThe present invention is concerned with new methods and reagents for coupling proteins and a wide variety of non-protein affinity ligands by strong covalent chemical bonds to solid-phase supports for the preparation of solid-phase catalysts and biospecific adsorbents.Biospecific adsorbents have become very important tools for the isolation of biologic macromolecules, while immobilized enzymes have found wide use as durable, solid-phase catalysts. Such materials are prepared by chemically linking enzymes, inhibitors, or other bio¬ specific compounds to a solid-phase support. Various methods and reagents have been described for the purpose of coupling, but each has its peculiar drawbacks, including: (a) weak chemical bonding; (b) ionic bonds; (c) necessity for strong conditions such as high temperature and pH to drive the reaction; (d) side reactions; and (e) limited range of chemical groups with which the coupling agent can react. 7 Previous coupling reagents include the reagent most widely utilized as a coupler, cyanogen bromide, as described by Jacoby et al. in Methods Enzy ol. 34, 1974v This reagent is reacted with supports such as agarose and cellulose in strongly alkaline solution where numerous side reactions occur. The cyanogen bromide-activated support subsequently reacts poorly with nucleophiles other than alkylamines, a severe limitation on the kinds of enzymes, ligands and other compounds which can be coupled. The coupling bonds. - 2 - probably isourea bonds, are only moderately stable, and substantial amounts of the bound substance may bleed under practical conditions. This instability limits the useful life of the adsorbent or solid-phase catalys and may add undesirable or potentially toxic contam¬ inants to the product. Moreover, these isourea bonds are positively charged at neutral pH and can cause non-specific adsorption.In contrast, reagents of a type that can provide strong covalent bonds between diverse supports and various nucleophilic groups of ligands under mild conditions have been employed in the dye industry since the introduction of reactive dyes. The most versatile and widely employed of these coupling reagent is trichloro-s-triazine (TsT) . This reagent contains three reactive chlorines, the first of which is displac to give a substituted dichloro-s-triazine (DsT) , and the second to give a disubstituted monochloro-s- triazine (MsT) . Conditions for controlled substitutions by various nucleophiles have received comparatively little study.Like cyanogen bromide, TsT has been reacted with supports in strongly alkaline aqueous media where hydrolytic side reactions predominate. In the procedure as described by Kay et al. in Nature 217:641, (1968) , the amount of TsT which reacts with support and that which hydrolyzes are competitive functions of temperature, pH and reagent concentration, and the extent of activation of the support cannot be predicted accurately. Moreover, the activated support is also subject to hydrolysis. Recently, Kay and Lilly have introduced the less reactive coupler, 2-amino-4, 6- dichloro-s-triazine, as discussed in Biochim. Biophys. Acta. 198:276 (1970). However, in alkaline aqueous media, this reagent is subject to the same drawbacks as TsT during the activation reaction and, in addition, vigorous conditions are required for coupling the ligands. The major probl-ems with such prior art methods are: (1) couplers are used empiripally as others have used cyanogen bromide; (2) although triazine coupling provides strong bonds between support and proteins, no attention has been previously paid to competitive hydrolytic side reactions and to the introduction of adsorptive ionic sites; '(3) the amount of ligand incorporated cannot be accurately controlled or predicted; and (4) the procedures are not satisfactory for the incorporation of small ligands in organic phase.In-order to circumvent the problem of TsT hydrolysis and to perform step-wise reactions at individual chlorines of TsT, by the present invention there have been developed methods for reaction in non- aqueous media. The critic l conditions were found to include appropriate polar organic solvents and suitable organic bases to neutralize the HCl generated. With polyol supports like cellulose or cross-lined agarose, as described by Porath et al. in J. Chromatogr. 60:167 (1971), reactions with TsT have been found to occur- smoothly and predictably in organic phase to give a (DsT)-dichloro-s-triazine substituted support. This activated support could be reacted in organic phase at one or both remaining chlorines, depending upon the nucleophiles involved and the reaction conditions.It has also been found, in accordance with the present invention, that weak nucleophiles such as aniline react at room temperature in organic solvent with one of the chlorines of the DsT-support, leaving a single site for subsequent reaction. In short, the initial activation reaction could be well controlled without side reactions to give a DsT-support; and a subsequent reaction with a weak nucleophile could be performed without side reactions to give an MsT-support. Finally, the single remaining chlorine of the MsT- support is less reactive -than the DsT-support or TsT and is less susceptible to hydrolysis at moderate pH and temperature. Therefore, it can be reacted with nucleophiles in organic or in aqueous solution under mild conditions of pH and temperature to give the desired products. In J. Biol. Chem. 252, 3578 (1977) Abuchowski et al. have reported the covalent attachment of poly¬ ethylene glycol (PEG) to proteins using TsT as a linking agent. While the coupling of an aliphatic alcohol to TsT in organic phase is the initial reaction in both the Abuchowski et al. procedure and in the present invention, this initial coupling is the entire extent of any similarity.In their initial coupling reaction, Abuchowski et al. use benzene as a solvent for both PEG and TsT and use a2CO-, to neutralize the HCl generated. This method, while adequate only for the coupling of TsT and PEG in solution phase, is not satisfactory for the coupling of TsT and any of the solid-phase supports utilized in affinity preparations, such as Sepharose, cellulose or polyvinyl alcohol. Benzene has proved to be a poor medium for reactions involving Sepharose and other hydrophilic polymers, most likely because of the non-polar nature of benzene. A major problem in the case of Sepharose or other polymers initially in aqueous phase is the transfer to benzene. It has also been observed that benzene seems to have an adverse . effect on Sepharose structure. Furthermore, benzene is not a particularly good solvent for TsT, as discussed in s-Triazines and Derivatives , in The Chemistry of Heterocyclic Compounds (E. M. Sraolin and 0. Rapoport, eds.), Interscience Publishers, Inc., New York, Vol. 13, 1959.Neutralization of the HCl generated is inefficient when the base is insoluble, as is the case of Na2C03 in benzene. Inefficient neutralization of the HCl could permit conversion of the alcohol to the corresponding alkyl chloride, a side reaction known to occur under these conditions. Also, incorporation of chlorine into the Sepharose matrix is likely to impart undesirable properties. .By the present invention, there has been achieved the ability to circumvent many of the problems inherent in the Abuchowski et al. procedure, by conducting the initial activation reaction in dioxane or other organic solvents and by neutralizing the HCl generated with a soluble organic base such as N,N-diisopropylethylamine or other tertiary amine which does not form an insoluble complex with TsT in organic phase. Of the several reaction media which have been tried, dioxane was found to be best as it is both compatible with Sepharose and other hydrophilic polymers and is also a . superior solvent for TsT. The use of a soluble organic base is also novel, and selection of the correct base is critical as most form insoluble complexes with TsT.After the initial activation step, the two procedures are obviously different. Abuchowski et al. are satisfied w^th empirical coupling of dichloro-s- triazine-PEG to proteins in aqueous phase under alkaline conditions. The reference also states that a consider¬ able excess of activated PEG must be used because hydrolysis of the second chlorine of the triazine occurs readily. This is a common feature of triazine reactions in aqueous or mixed aqueous-organic phase and it prevents accurate control and predictability of the reaction.Unreacted and hydrolyzed PEG-dichloro-s-triazine are, of course, soluble and separable from the PEG- coupled protein. This is not the case, however, if one wants a broader objective, i.e., coupling of an insoluble solid-phase compound such as cellulose- dichloro-s-triazine to a ligand where any side reactions such as hydrolysis affect the desired product. In the procedure of the present invention, control is established by replacing the second triazine chloride by a weak nucleophile such as analine. This leaves a single chlorine available for reaction with nucleophilicQMPI fa ' groups of the proteins or other substances to be immobilized. This single chlorine .can be replaced quantitatively by aliphatic amines under mild conditions, yet it does not hydrolyze readily below pH 9 at room temperature.Various supports (polyols) can be reacted with TsT in accordance with the present invention, but all such supports must be rid of water prior to the initial reaction. Where suitable, drying can be performed by heating in vacuo, or water may be dispersed from the support by washing with dry, miscible organic solvents such as 1., -dioxane, acetonitrile and similar solvents. In addition, the parameters of the reaction conditions can be altered to effect changes in the amount of TsT which reacts with the support, including changes in reaction temperature, reagent concentration, and the duration of the reaction.The reaction of TsT with the support in organic phase requires the presence of a suitable organic base. The bases generally employed in analogous acyl chloride type reactions such as triethylamine, pyridine, N-ethyl lrorpholine, and lutidine, were found to form insoluble complexes with TsT in organic solvents. However, it was cound that tertiary amines such as N,N-dimethylaniline and N,N-diisopropylethylamine did not form such complexes and performed satisfactorily.BRIEF DESCRIPTION OF THE DRAWINGSThe advantages and features of the present invention will be more fully understood from the following description of the preferred embodiments, taken in conjunction with the accompanying drawings, wherein:Fig. 1 is a graph showing a comparison of the stability of ligands attached with CNBr to those attached with TsT; andFig. 2 is a graph showing various characteristics of protein coupled to TsT-activated resin. DESCRIPTION OF THE PREFERRED EMBODIMENTSThe following is a general procedure for-the preparation of the reactions of triazine-linked bio- affinity resins beginning with an aqueous suspension of support such as cross-linked agarose. This procedure is set forth schematically as follows:SUPPORT TsT SUPPORT -DsT SUPPORT -MsTic or +RNH. us se IAn aqueous suspension of the 'support is washed with a series of dioxane-water solutions in which the amount of dioxane increases from 0 to 100%. The support 10 is transferred to a round bottom flask equipped with a glass-sealed stirrer and water condenser. Transfer is accomplished with a small amount of dioxane. The reaction flask is immersed in a thermostated oil bath, and its contents stirred at low speed. N,N-diisopropyl- ethylamine or N,N-dimethylaniline in dioxane'-is added and the reaction is allowed to equilibrate. The reaction.OMPI _ - 8 - is initiated by the addition of trichloro-s-triazine dissolved in dioxane. Generally, fluid and solid phases are of equal volume, and base concentration is twice that of the trichloro-s-triazine. The amount of triazine incorporated into the support resin depends on trichloro-s-triazine concentration, length of reaction and reaction temperature.The activated DsT support is then washed with several bed volumes of dioxane. At this point the activated support can be reacted in several different ways: (1) it can be reacted in organic dioxane with a strong nucleophile such as an alkyl amine to give a dialkyl-triazine-resin; (2) it can be reacted in dioxane with a weak nucleophile such as an aryl amine to give a monoaryl-triazine-resin with a chlorine still avail¬ able for further reaction; (3) the monoaryl-triazine- resin can be washed with dioxane-water.solutions containing decreasing amounts of dioxane and the resin, now in aqueous solution, can be reacted with either proteins or other nucleophiles; or (4) the organic solvent can be removed from the raonoarylmonochloro-s- triazine-resin by freeze-drying or other gentle means and the dried, activated resin stored for later use.EXAMPLE 1 As a specific example, 100 ml of Sepharose CL-4 was washed with 200 ml of a mixture of water: dioxane (30:70) followed by 200 ml water: dioxane (70:30) and finally by 1000 ml dioxane. Washing was accomplished on a sintered glass funnel under vacuum. The resin was allowed to stand overnight in a glass stoppered graduated cylinder to accurately measure the bed volume and, after removing the excess dioxane, the settled gel was transferred with 60 ml dioxane to a 500 ml 3-necked round bottom flask equipped with a water jacketed condenser and a glass-sealed stirrer. The reaction flask was immersed in a thermostated oil bath maintained at 50 + 2°C and the contents were stirred at 100 rpm. The amount of 20 ml of' 2 M N, N-diisopropyl ethyl amine in dioxane was then added . After 30 in, 20 ml of 1 M trichloro-s-triazine in dioxane was added to initiate the reaction . After 60 min at 50 °., the activated resin was washed on a sintered'' gla-ss funnel with 1000 ml of dioxane.. The resin was found to contain 112 j_moles triazine per gram of resin. A portion of the resin was then reacted with 2 volumes per bed volume of resin, of1 M ethylene diamine in dioxane, for 30 min, at room temperature and was found to couple 224 ;umoles of diamine per gram of resin.A second portion was reacted with 2 volumes of aniline in dioxane at room temperature for 30 min. and was subsequently washed with 5 bed volumes of dioxane on a sintered glass funnel . A portion of this latter resin was reacted with 2 bed volumes of 1 M ethylenediamine in dioxane at room temperature for 30 min and was found to couple 112 jimoles of diamine per> gram of resin. A second portion of the aniline-treated resin was washed with 2 bed volumes of water: dioxane (70:30) at 4°C and finally by 10 bed volumes of water at 4°C on a sintered glass funnel.A portion of the resin in aqueous phase was incubated with 2 bed volumes of 0.66 M epsilon amino caproic acid, 0.30 M sodium borate, 0.30 M sodium chloride buffer, pH 8.5, for 22 hours at room temperature, after which time 116 umoles of 6-amino- hexanoic acid was incorporated into the resin. Another portion of the resin in aqueous phase was reacted with 4 bed volumes of a solution of bovine serum albumin, 10 mg/ml in 0.30 M sodium borate, 0.30 M sodium chloride buffer, pH 8.0, for 22 hours at room- temperature. This resin was found to have coupled 42.3 mg of protein per gram of resin. EXAMPLE 2To compare the stability of ligands attached to agarose with CNBr to those attached with TsT, 14 C-bovine, OMPI - - 10 - serum albumin (BSA) and 14C-EACA were each coupled toSepharose CL-6B using these two coupling reagents. The resins were then treated under conditions which would accelerate hydrolysis of the coupling bonds, namely elevated temperature and pH as shown in Fig. 1. The graph of Fig. 1 shows the results of hydrolysis of14 C-EACA-Sepharose and 14C-BSA-Sepharose in 0.33 M a2C0_,, pH 11.2 at 50°C. Packed resin was suspended in buffer and at the indicated intervals aliquots were removed and assayed for radioactivity. Total radio¬ activity represents the total amount of ligand bound to the resin. 14C-EACA and 14C-BSA alkylated with 14C- iodoacetamide and containing 0.6 mole carboxyamidomethyl groups per mole of protein (1.8 X 10 cpra/mg) prepared in accordance with precedures set forth, for example, by Finlay et al., J. Biol. Chem. '245, 5258 (1970), were coupled to CNBr-activated Sepharose CL-6B in 0.3 M Na borate, 0.3 M NaCl, pH 8.0, by the procedure outlined by Parikh et al. in Methods Enzymol. 34:77 (1974). The BSA-Sepharose linked with CNBr contained 35.3 mg of protein/g resin and the EACA-Sepharose contained 317 ji oles of amine/g resin. 14C-BSA and 14C-EACA were coupled to triazine-activated Sepharose CL-6B in 0.22 MNa borate, 0.22 M NaCl, pH 8.0. The BSA-Sepharose prepared by triazine activation contained 42.3 mg of prqtein/g resin and the EACA-Sepharose contained 140 uncles of amine/g resin. Packed resin, 1 ml, was suspended in 2.0 ml 0.5 M a2C03, pH 11.2, at 50°. At the intervals indicated in Fig. 1, the resin suspension was centrifuged and an aliquot from the supernatant fraction removed and counted. The data clearly show the triazine linkage to be superior to the CNBr linkage for both proteins and small molecule ligands.Referring to Fig. 2, this graph shows that the amount of protein coupled to triazine activated resin is dependent on the amount of free protein present in the coupling reaction.The data of Fig. 2 is concerned with the effect ofOM ~ - 11 - coupling of bovine serum albumin to Sepharose CL-MsT. Samples of Sepharose CL-6B- MsT (100' mg) , lyophilized from dioxane, were suspended in 5.0 ml of 0„.15 M'NaCl, 0.1 M Na Borate, pH 8.0. After mixing at 0° for 1 min, the suspensions were centrifuged and the supernatants aspirated to yield a total*volume of resin plus liquid14 of 1.5 ml. C-CM-bovme serum albumin in 1.0 ml of this same buffer was then added and the reactions were incubated with rocking at room temperature. After 44 hrs, the resins were washed with 1.0 M Tris-HCl, pH 8.8, water and 50% ethanol and then.' lyophilized. The amount of protein coupled was calculated after counting of weighed aliquots of the dried resin. It is interesting to note that with this particular lot of resin, 125 mg of albumin was coupled per gram with no indication that the resin had become saturated.In Table I it is shown that in the pH range of 6-9, temperature has a greater effect on coupling efficiency than*does pH. In preparing the information. as shown in Table I, samples of Sepharose CL-MsT (100 mg) lyophilized from dioxane, were suspended in 5.0 ml buffer (pH 6 and 7: 0.1 M Na Phosphate; pH 8 and 9: 0.1 M Na Borate) containing 0.15 M NaCl. After mixing at 0°C for 1 min, the suspensions were centrifuged and the supernatants aspirated to yield a total volume of resin plus liquid of 1.9 ml. 14C-CM bovine serum albumin(0,1 ml, 9.98 mg, 1.17 X 10 cpm) -was added and the reactions were incubated with' rocking for 24 hrs.Samples were washed and counted as described in connection with Fig. 1...In Tables II and III there are listed some of the enzymes, other proteins and other substances which have been coupled to ;TsT-activated Sepharose. Of the enzymes which have been coupled in accordance with the present invention, the one with the greatest commercial value is probably bacterial < -amylase which converts starch to dextrins and is used in the paper and textile industries and in the production of glucose. TABLE ICoupling of Bovine Serum Albumin to Sepharose CL-MsT;Effect of temperature and pHTemperature pH mg protein coupled g res-in6 19.77 19.88<8 20.7 9 21.56 28.0 7 26.227' 8 30.2 9 33.36 36.1 7 45.945( 8 51.1 9 48.9 TABLE IICOJPLII G OF ENZYMES TO Sepharose CL- 6B WITH TsT IN AQUEOUS PHASE ΑT pH 8ENZYME COUPLING CONCENTRATION % PROTEIN ENZYME COUPLED MG/G RESIN % ACTIVITY(MG/ML) BOUND AS PROTEIN AS-7CTIVITYp^-Amylase 3.9 13.2 10.2 6.2 60.2 c~> i-S Lactic Deriydrogenase 3.7 48.9 36.2 3.3 9.1Cellulase 4.5 8.3 7.5 1.2 16.0Trypsin 4.3 35.9 30.9 3.6 11.7Chymotrypsin 4.3 36.2 31.1 2.9 9.3 Ligand Amount Coupled/g Resin Biological Activity Fibrinoger. 28-142 mg As fibrin-Sepharose, adsorbs 24-130 mg fibrinogen per G resinAntifibrir.ogen 15 mg Adsorbs fibrinogenAlbumin 28-125 mg Adsorbs antialalbumin•**-H Histone 48 mg Substrate for proteolytic enzymes (as -*-25l histone-Sepharose)Trypsin 30-60 mg 10% activity of unbound enzyme Chymotryps:.n 45-75 mg 10-25% activity of unbound enzyme Lysine 115 u oles Adsorbs 675 CTA units plasminogen per g resin6-Amino Ccproic Acid •120 umoles Benza idire 150 umoles Adsorbs 15 mg trypsin, 7 mg thrombin per g resin Λ » Heparin 3-6 mg Adsorbs 3-6 mg antithrombin-lll per g resin.('** - 15 -In preparing the information as shown in Table II, reaction mixtures contained 100 mg of activated resin in a total volume of 2.0 ml 0.1 Ma Bora eT 0.15 M NaCl, pH 8.0 at the protein concentration indicated the first column of Table Iϊ.. Reactions were conducted at 25 + 2βC with gentle rocking for 24 hours. The resins were then washed by filtration first with 1.0 M tris-Cl, pH 8.8 followed by 0.05 M tris-Cl, 0.15 M NaCl, pH 8.3. Resins were assayed for protein and enzymic activity as described previously.It^is thought that the invention and many of its attendant advantages will be understood from the fore¬ going description, and it will be apparent that various changes may be made in the methods as described herein without departing from the( spirit and scope of the invention or sacrificing its material advantages, the forms hereinbefore described being merely preferred embodiments thereof. | - -THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:Claim 1. In a method for coupling protein and non-protein affinity ligands by covalent chemical bonds to insoluble solid supports for the preparation of soli phase catalysts and biospecific adsorbents comprising the steps of reacting the insoluble solid support material with trichloro-s-triazine to produce an activat support and thereafter, coupling the ligand to the activated support, the improvement wherein the production of the activated support is carried out by the steps comprising:(a) reacting a water-free insoluble solid support material with trichloro-s-triazine in a non-aqueous medium comprising an organic solvent which is compatible with the support material and is also a solvent for trichloro-s-triazine;(b) neutralizing the HCl generated during the reaction with a tertiary amine which is soluble in said organic solvent and which does not form an insoluble complex with trichloro-s-triazine in said organic solven and(c) washing the obtained dichloro-s-triazine activated support with an additional amount of said organic solvent.Claim 2. The method of Claim 1, wherein said supp support material initially contains water and is treated prior to step (a) to remove said water therefrom Claim 3. The method of Claim 2, wherein said pretreatment of said support material is accomplished by washing the support material with an organic solvent.Claim 4. The method of Claim 2 , wherein said pre¬ treatment of said support material is accomplished by drying the support material under vacuum.Claim 5. The method of Claim 1, wherein the tertiary amine is selected from the group consisting of N,N-diisopropylethylamine and N,N-dimethylaniline.Claim 6. The method of Claim 1, wherein said organic solvent is selected from the group consisting of dioxane and acetonitrile. Claim 7. The method of Claim 1, including the further step of adding at nucleophile to the washed dichloro-s-triazine activated support in an organic solvent to replace one or both of the chlorine .atoms on the triazine ring. Claim 8. The method of Claim 7, wherein said nucleophile is selected from the group consisting of aliphatic amines, aryl amines, phenols and alkoxyl amines.Claim 9. The method of Claim 1, including the further step of adding a weak nucleophile to the washed dichloro-s-triazine activated support in an organic solvent to replace a single chlorine atom on the triazine ring, leaving the remaining chlorine atom available for further replacement by a second nucleophile. Claim 10. The method of Claim 9, wherein said weak nucleophile is aniline.Claim 11. The method of Claim 9, wherein the obtained monochloro-s—riazine activated support is dried for storage and later use. Claim 12. A dichloro-s-triazine activated support obtained in accordance with''the method of Claim 1*Claim 13. A monochloro-s-triazine activated support obtained in accordance with the method of Claim 11. - Claim 14.^ A ligand-activated support coupled product obtained in accordance with the method of Claim 7.Claim 15. A ligand-activated support coupled product obtained in accordance with the method of Claim 9. | UNIV NEW YORK | FINLAY T; HODGINS L; JOHNSON A |
WO-1979000630-A1 | 1,979,000,630 | WO | A1 | XX | 19,790,906 | 1,979 | 20,090,507 | new | B60K1 | B60L11 | B60K1, B60K6, B60L11, B62D25, H01M2 | B60K 1/04, B60K 6/40, B60L 11/18L6, H01M 2/10C4C | ELECTRICALLY DRIVEN VEHICLES | An electrically driven motor vehicle having an electric motor (31) arranged to drive the vehicle through a transmission system (29, 33) and a battery pack (22) to provide power for driving the electrical motor (31), the battery pack being provided with a charging unit (25, 26) including an internal combustion engine (26) and the battery pack (22) and the charging unit (25, 26) being mounted on the vehicle as a unit so as to be readily detachable therefrom to enable it to be replaced at suitable servicing establishments. | ELECTRICALY DRIVEN VEHICLESThis invention relates to electrically driven motor vehicles of the kind having a rechargeable battery pack which is arranged to supply electrical power to drive the vehicle, through an appropriate transmission system.In known vehicles of this kind it has been possible to recharge the batteries by means of a charging unit which inns on liquid fuel or other power source which is not the battery pack itself. Such a battery charging unit is bulky and therefore there have been several proposals for accommodating it, including mounting it in a trailer towed by the vehicle.Within the practical limits set by the motor vehicle size, the space occupied by a battery pack and its charging unit must be kept to a reasonable minimum. It has furthermore been ound that the provision of a battery pack without a charging unit severely limits the range of possible use of the vehicle between charging sessions, during which the vehicle is, perforce, stationary and it is for this reason that a charging unit may be provided. Without incurring a substantial penalty in terms of occupation of space as well as of weight, such a charging unit would not, under most circumstances, do more than retard the rate of discharge of the batteries of the battery pack.Another alternative which has been tried is to provide a battery pack and electric motor arranged to be driven therefrom and also an internal combustion engine. In this construction, the electric drive is used for acceleration and also possibly for deceleration but when cruising at steady speeds the internal combustion engine is used, preferably at its most efficient speed of operation. However, such a vehicle is greatly complicated by the need for complex controls and dual transmission' provision.)The object of this invention is to provide a motor vehicle with a battery pack and a charging unit in a convenient form which will provide a practical range of use of the vehicle.According to the invention there is provided an electrically driven motor vehicle including an electric motor arranged to drive the vehicle through a trans.mission system, a battery pack arranged to provide power for driving the electric motor, and a charging unit for charging the battery pack, and characterised in that the battery pack and charging unit are mounted on a common structure which is provided with means whereby it is detachab. carried on the vehicle.Conveniently, the structure on which the battery pack and charging unit are mounted includes a frame vhich is, at least in part, hollow to provide a storage space for fuel for* the charging uniteAccording to a further aspect the invention resides in a battery pack and charging unit for an electrically driven motor vehicle, characterised in that a common structure is provided for supporting the battery pack and the charging unit, the structure being provided with means whereby it can be detachably secured to a vehicle.The invention will now be described, by way of example, with reference to the accompanying drawings, in which:-Figure 1 is a side elevation of a vehicle con¬ structed in accordance with the invention, andFigure 2 is a plan view of the underpart of the vehicle Figure 3 is a plan view of a further alternative const-ruction in accordance with the invention.The type of vehicle shown in the drawing's is a light goods carrying vehicle having a driver's cab portion in¬ dicated generally at 10 having side access doors 12 and a goods carrying area indicated generally at 11. This has rear access doors (not shown).A floor indicated at 13 extends through the vehicle, this being supported on chassis members 1^. A pair of front steerable wheels 15 and a pair of driven vrear wheels l6 are provided. The vehicle body is of conventional kind and would normally be provided with an internal combustion engine mounted ahead of the driving compartment, and connected with the rear wheels l6 through a conventional transmission system. However, the vehicle is electrically propelled as will be described.Referring particularly to Figures 1 and 2 the electrical drive apparatus is shown therein to include a rectangular frame 17. This is mounted on the underside of the vehicle, below the floor 13. being attached to appropriate fixing brackets by quickly releasable fastenings indicated at 18, 1 and 21, the former two being at the sides and the latter being at the front of the frame 17. Each fastening preferably includes a single screw and there is included means for ensuring registration of the holes through which the bolt passes to secure the frame 17 in position.Contained within and secured to the fra-mre 17 so as to be detachable as a complete unit are a plurality of batteries 22. These are arranged in rows with fore and aft extending spacers 230 In this example there are twenty 12 volt batteries 22.The frame 17 also houses, ahead of the batteries 22 a'EJR^ΛTT' charging unit comprising an internal combustion engine 26 and an electrical generator or dynamo 25. An electrical control device is also provided on this assembly and electrical connections to the batteries 22 are shown generally at 27.The frame 17 has hollow box section members forming its two longitudinal parallel sides, which form storage tanks for fuel for the internal combustion engine 26 of t charging unit. Fuel supply pipes are indicated at 28 from these tanks to the engine 26.The whole assembly of frame 17» batteries 22 and charging unit 25 and 26 are therefore detachable as a unit from the vehicle._>Also mounted on the chassis of the vehicle, behind the battery and charging unit assembly is a transmission system 29 for driving the rear wheels and a propulsion electric motor 31 to which the batteries supply power thro a cable indicated generally at 32. Between the motor 31 and the transmission 2 is a coupling or drive connection 33. A driver operated electrical control unit ~k is also shown fitted at the front of the vehicle0In the Figure 3 construction it is envisaged that th vehicle is of the kind originally fitted with an internal combustion engine and convention drive to the rear wheels. The vehicle is however modified by removal of these components are replaced by a complete unit which has attached to it the necessary equipment for electrical driv instead of internal combustion engine drive for the vehiclBeneath the floor of the vehicle a frame 35 is secur to the chassis or body of the vehicle by a number of fastening elements indicated at 36. These may include bolted fastenings or other types of fixing„• This frame 35 defines three rectangular openings comprising a large central opening and two smaller openings at the ends of the frame, which are thus disposed at the front and rear of the vehicle respectively.The opening in the portion of the frame 35 at the front of the vehicle contains electrical control equipment indicated generally at 37• I this example, the control equipment is housed in two separate units and it is driver operated.The opening at the rear of the frame 35 contains an electrical drive motor 38 which is controlled through the control units 37 by the driver. The electric motor 38 drives the rear wheels 16 through a transmission system including a differential 39 and intermediate coupling or drive connection mechanism indicated generally at 41 which includes a step-down drive.The central opening in the frame 35 contains a detachable assembly. This assembly comprises a rectangular frame 42 in which are secured a plurality of batteries 3. The batteries are arranged in rows with fore and aft extending spacers 44. As in the Figures 1 and 2 example, there are twenty 12 volt batteries_ Electrical connection from the batteries to the electric motor 38 is indicated at 5• comprising a connecting lead on the assembly, having a plug engageable in a socket in the vehicle.The frame 2 also houses, ahead of the batteries ~ a charging unit. This comprises an internal combustion engine indicated generally at 46. This is coupled to a dynamo 4 0 An electrical control for the charging unit is also provided on the assembly.The frame 42 has hollow box section members along its two parallel longitudinally extending sides. These members form storage tanks for liquid fuel for running the internal combustion engine 46 of the charging unit, as in the Figures 1 and 2 construction. Fuel supply pipes are indicated at 48„The whole of the assembly including the battery pac and the charging unit are detachably mounted within the__ main frame 35* Detachable fastening elements between th frame 42 and the frame 35 are indicated 4 . These are pre erably of the quickly releasable type referred to in the equivalent positions in Figures 1 and 2.In use, the vehicle is driven by the electric motor 38 under driver control, the motor being supplied with electrical power from the battery pack which comprises th batteries 43.The charging unit may be oparated if required. Generally, on a relatively long journey, the battery pack would be. continuously charged by the charging unit. Th has the effect of retarding the discharge rate of the battery pack or maintaining the state of charge thereof. The charging unit would not generally be of a size to provide the battery pack with a rate of charge greatly in excess of normal requirements„ The arrangement greatly increases the practical range of such a vehicle as compar with a vehicle fitted only with a battery pack and withou any charging unit.It is intended in use that the battery pack and charging unit assembly may be exchanged at suitable servicing establishments either for another similar unit or for a battery /pack having no charging unit but having the same overall dimensions and a fixing arrangement as the assembly shown in the drawings. If a vehicle is intended for short journeys, the battery pack is used and this is charged when the vehicle is not in use or exchanged for another charged battery pack but if the vehicle is to be used on longer journeys, the battery pac and charging unit assembly is used.Though shown fitted in a goods carrying vehicle the battery pack and charging unit assembly can be used in other forms of vehicle including passenger carrying private motor vehicles.'Eά-R-.-UT | CLAIMS1o An electrically driven motor vehicle including an electric motor 31 arranged to drive the vehicle through a transmission system 29, 33, ~- battery pack 22 arranged to provide power for driving the electric motor 31, and a charging unit 25, 26 for charging the battery pack 22, an characterised in that the battery pack 22 and charging un 25, 26 are mounted on a common structure 17 which is provided with means 18, 19, 21 whereby it is detachably carried on the vehicle.2. An electrically driven motor vehicle as claimed in claim 1, in which the battery pack 22 and charging unit 2 26 are mounted includes a frame 17 which is, at least in part, hollow to provide a storage space for* fuel for the charging unit 25, 26.3. An electrically driven motor vehicle as claimed in claim 1 or claim 2, in which the charging unit 25, 26 inc an internal combustion engine 26.4β A battery pack and charging unit for an electrically driven motor vehicle, characterised in that a common structure 17 is provided for supporting the battery pack 2 and the charging unit 25, 26, the structure 17 being provi with means 18, 19, 21 whereby it can be detachably secured to a vehicle.5 - A battery pack and charging unit as claimed in claim 4, wherein a frame 17 is provided which, at least in part, is hollow to provide a storage space for fuel for the charging unit 25, 26.• B_1 E. OMPI . fa W1P0 60 A battery pack and charging unit as claimed in claim 4, or claim 5, wherein the charging unit 25, 26 includes an internal combustion engine 26.7. An electrically driven motor vehicle substantially as hereinbefore described with reference to and as shown in Figures 1 and 2 of the accompanying drawings.8. An electrically driven motor vehicle substantially as hereinbefore described with reference to and as shown in Figure 3 of the accompanying drawings.9o A battery pack and charging unit substantially as hereinbefore described with reference to and as shown in Figures 1 and 2 of the accompanying drawings,,10o A battery pack and charging unit substantially as hereinbefore described with reference to and as shown in Figure 3 of the accompanying drawings. | FOWKES R; HARDING G; LUCAS INDUSTRIES LTD; LUCAS IND LTD | FOWKES R; HARDING G |
WO-1979000634-A1 | 1,979,000,634 | WO | A1 | XX | 19,790,906 | 1,979 | 20,090,507 | new | D21B1 | B02C7, D21D1 | B02C7, D21B1, D21D1 | D21D 1/20, D21D 1/30 | METHOD OF MAKING PULP | A method of making refiner pulp by refining lignocellulose-containing material having a concentration of 8-15%, measured as discharge concentration. The material is refined in a disc refiner during the passage out through the gap (10) between the refining discs (6, 7) of the refiner to a surrounding refiner housing (15). Water is continuously supplied to the housing (15) outside the refining discs (6, 7) to dilute the refined material to a fibre suspension of a concentration easy to pump. The housing (15) is maintained filled with said suspension in order to reduce the pulp flow through the refiner and thereby the retention time of the material between the refining discs (6, 7). | Method of making pulpThis invention relates to a method of making refiner pulp of high yield (*785/S) by refining lignocellulose-containing material such as chips, sawdust or defibred chips. The material is preheated arid/or/treated with ligπin-softeniπg chemicals prior to the refining, which usually is carried out in disc refiners.At conventional embodiments of the refining process the fibre material is refined at. very high fibre concentrations, in such a manner, that the amount of water supplied to the refiner is held at the lowest possible level. This is necessary for obtaining good properties of the exposed fibres and for rendering them suitable for the manufacture of a series of different paper qualities. The re¬ fining process, however, requires much energy. Therefore, in view of the ever increasing energy prices and the restricted energy supply it is increasingly disadvantageous to make mechanical or ' chemi-mechaπical pulps of the above yields by this process.It was, however, found very surprisingly that it is possible by the present invention to substantially reduce the energy con¬ sumption at the refining without abandoning the quality of the re¬ sulting pulp. In certain cases even an improvement of the quality was observed.The fibre material is decomposed at the refining to fibres or fibre fragments while the material is passing through the narrow gap between the refining segments in the disc refiner. As regards the process parameters, such as pressure, temperature, concentration, production, refining disc pattern etc. in the refiner, it is essen¬ tial to choose them so as to obtain a gap of adequate size at the desired effect input and processing of the fibre material. Too narrow a gap implies difficulties for the pulp transport through the gap and often results in a poor pulp quality, because many fibres during their passage between the discs are cut off or damaged fri.OMPI some other way. Too wide a gap, on the other hand, causes proble due to a high shives content in the pulp or, in other words, the result of the refining operation is not satisfactory.The pulp concentration affects the gap for a certain energy input as follows. At a high pulp concentration a certain treatme of the material with resulting energy consumption at a certain ga is obtained. In order to obtain with conventional refining tech¬ nology the same treatment of the fibre material or the same energ consumption at a low pulp concentration, the gap must be reduced. The reason thereof should be that the pulp fibres form a bed of greater thickness at a higher concentration, and that the fibres • remain for a longer time between the refiner discs-, because the transport resistance is higher at increased concentration. At low pulp concentrations the material is transported at a higher rate through the gap. When still the same beating degree of the fibre (the same energy consumption) is to be obtained, the gap must be reduced. This implies an increased intensity of the energy trans fer from the refining segments to the fibres and, thereby, a grea ter risk of fibre damage. When applying the process technology of to-day, it is, ther fore, necessary to work in the refiner with relatively high pulp concentrations, usually above 20?& calculated as discharge concen¬ tration,in: order to enter the correct gap interval where a satis- factory pulp quality is obtained and fibre damages are prevented. This applies to all types of processes using the highest yield interval ( 85 ), for example thermo-mechanical or chemi-mechσni cal processes. At these high pulp concentrations, however, the steam formation is high and causes a series of problems difficult to cope with, when flows of the chips, fibres, water and steam through the refiner shall be controlled individually in order to proceed troublefree. The pulp fibres, moreover, per se are difficult to handle from a flow aspect, and the energy con¬ sumption at the processing is very high.The main part of the steam formed during the process flows out of the refiner, together with the fibre material and unvapori water, through the gap and flows into the surrounding refiner hou ing. The steam amount is great, and the steam rates through the gap are very high. This, of course, limits the erεrgy inpu in many cases is limited so substantially that the desired cessing of the fibre material is not obtained during a single pas¬ sage, but the refining operation must be repeated two or more times with the entire pulp amount or with a part thereof, i.e. the re¬ fining must be carried out in several steps. The steam, besides, occupies a very large part of the space in the gap between the operating refining discs. For this reason, and because the fibre material at high concentrations is not distributed uniformly in the gap and over the refining segments, the possibilities offered by the refining segments cannot all be utilized for processing the fibre material.Although the greater part of the steam formed flows out at the periphery of the refining segments, a non-neglectible part thereof flows back and out of the refiner where the chips are being fed in. This feed, of course, is obstructed thereby, which gives rise to serious effect variations. Such a varying fibre flow through the refiner, of course, has a detrimental effect on the pulp quality. When the fibre flow is too great, the fibres are refined insuffici¬ ently, and when the flow is too small, the fibres will be refined much too intensely. The steam flow, partially in forward and partially in rearward direction, is due to the fact that the pressure in the gap between the refining segments increases with increased energy transfer in the direction to the periphery and reaches a maximum somewhere in the outer part. The energy transfer and the steam formation are here at their maximum, and this area constitutes a natural divider for the forward/rearward stearaflow.Thus, great steam amounts difficult to manage are formed when the refining of fibre material must be carried out at high fibre concentrations. The fibre concentrations, determined immediately after the refining, mostly are in the range of 25-35^. The steam problems, therefore, determine to a high degree the design of the disc segments, i.e. of the instruments applied to refining the fibre material. Grooves and ridges, thus must be formed so that the grooves are sufficiently wide and deep for not obstructing the steam transport. Often, on the other hand, a narrower groove and a wider ridge would be more advantageous with respect to the refining of the fibres, but are not permissible in view of the steam transport. It further is desirable to maintain the fibre material for as long as possible upwardly about ridge surfaces and edges, so that tire raaOMPI ~WΪPO~ rial will be accessible to the refining effected by the edges and surfaces of the ridges. Grooves with great depth would render th difficult. Furthermore, according to new refining theories an ef fective refining of the fibre material requires a continuous and rapid redistribution of the material, which also is rendered diff cult by too deep grooves and high fibre concentration.It is apparant from the aforesaid, that it is highly desira to carry out the refining of fibre material at fibre concentratio which are lower than permissible according to the technology of t day. By lowering the concentration, the steam formation is reduc and the fibre flow through the refiner is facilitated. The fibre material is distributed more uniformly across the refining surfac the material in the grooves is more easily and rapidly redistri¬ buted, and the possibilities of refining fibres and chips are better utilized. The substantially reduced steam formation permi a more rational design of the refining segments.These advantages of a low pulp concentration express themse ves in such a way, that at a lowering of the pulp concentration b low 15/δ a distinct reduction of the energy consumption for a cert refining degree of the fibre material, calculated as freeness, ca be observed. It is difficult,, however, to utilize this effect wi the technology of to-day, because simultaneously the gap decrease so much at the refining of these low concentrations, that the strength properties of the pulp deteriorate due to fibre damages, as mentioned above.The present invention provides a sufficient retention time the fibre material in the refiner, so that the specific effect in put can be held at a level where fibre damages are prevented al¬ though the refining is carried out in the concentration range 8-1 calculated as discharge concentration. This implies, that the energy consumption at the refining can be reduced substantially a at the same time the quality of the pulp produced is maintained o even improved.This is possible due to the fact that the pulp flow through the refiner according to the invention is reduced effectively.The characterizing features of the invention become apparen from the attached claims.The invention is described in greater detail in the followi with reference to the attached Figure, which schematically shows - refiner for carrying out the method according to the invention. The refiner shown is a disc-refiner, of which both refining discs rotate in relation to one another, but the invention is applicable also to a refiner comprising one stationary and one rotating refining disc. The refiner comprises a stand 1 , in which two shafts 2, 3 are supported. The shafts are driven in opposed directions by motors 4, 5 and are provided at one end with refining segment holders 6, 7, on which refining segments 8, 9 are attached. Between the refining segments 8, 9 a gap 10 is formed which can be adjusted by displacing one shaft 2 and associated segment holder 6 in axial direction. The second segment holder 7 is provided with openings 11 for material supply which communicate with a charging device 12. A supply con¬ duit 13 for diluting water is connected to the material inlet. The amount of diluting water supplied is controlled by a valve 14. The segment holders 6, 7 are enclosed by a closed refiner housing 15, to which, preferably to its lower portion, a supply con¬ duit 16 for diluting water is connected. The supply can be con¬ trolled by a valve 17. For the discharge of the refined material an outlet conduit 18 is connected to the refiner housing, preferably to its upper portion. The pressure in the refiner housing is con¬ trolled by a valve 1 .The lignocellulose-containing material to be refined is pre¬ heated with steam and/or treated with lignin-softening chemicals, for example prior to the refining in a known manner. The material is advanced by a feed screw 12 and flows in through the openings 11 in the segment holder 7 and flows out through the gap 10. The pressure in the feed zone, i.e. where the material is charged through the openings 11, usually is maintained between 10 and 260 kPa, preferably between 20 and 140 kPa. This corresponds to a temperature of approx. 100-140 C, preferably 105-125 C.The material concentration is held at the refining within 8- 15S, calculated as discharge concentration, i.e. the concentration of the material when leaving the gap. This concentration is adjus¬ ted by the supply of diluting water of a suitable temperature through the conduit 13.By continuous and controlled supply of diluting water, pre¬ ferably backwater of the mill, through the conduit 16, the pulp is diluted after the refining to a concentration easy to pump, suit¬ ably 1 -6%, and preferably 2-5S, so that the refiner housing held filled with the fibre suspension. Hereby the fibre suspensi in the refiner housing forms α wall about the outlet opening of t gap and brakes the acceleration of the fibre material through the gap. The material remains longer in the gap, and the low concen- tration permits a more uniform distribution of the material. The flow through the gap assumes the character of plug flow.The staying time of the material in the gap also is affecte by the pattern of the refining segments. In the present case a dense pattern is desired, i.e. the grooves shall have small depth and width dimensions. The refining segments, for example, may be designed with a refining zone where the groove width is smaller than 2 mm and the groove depth below 4 mm. The grooves of the re fining segments also are to be provided with a great number of ridges. Such a pattern, as mentioned before, also contributes to a more effective refining of the fibres.In the refiner housing 15, outside the refining discs a pressure is maintained which substantially corresponds to the pre sure in the feed zone. It may, however, be suitable under certai circumstances to maintain in the refiner housing a higher pressur than in the feed zone. Hereby the retention time of the material in the gap can be extended still more. The pressure in the refin housing is controlled by the valve 19 in the discharge conduit 18 from the refiner housing. The low concentration in the refiner housing provides a uniform flow through said housing. The low co centration also implies that the pressure drop over the valve 19 easier to control, whereby also the pressure in the refiner housi and the entire refining operation are easier to control.Due to the fact that the concentration at the refining is . held at a low level (8-15?0, the amount of steam formed is much smaller than it normally would be. No steam, or very little stea flows backward against the incoming chips, and the steam flowing o through the gap has low speed and condenses substantially immedi.a tely in the fibre suspension surrounding the segment holders.Owin to the fact that the refiner housing is filled with a fibre sus- pension of low concentration, also heat is conducted away more effectively from the refining zone, which further contributes to limitation of the steam formation in the refining zone.It is also possible to utilize defibred chips as starting material. The feed screw 12 then can be replaced by a pulpO the discharge conduit of which is connected directly to the feed zone of the refiner. Defibred chips in this case are to be under¬ stood as a fibre material which in a preceding operation partially has been defibred with very little energy. The defibring operation may take place subsequent to a preheating and/or treatment with lignin-softeπing chemicals. The gap at this operation is great, and the fibre damages are insignificant. The refining, i.e. the main application of energy, thereafter takes place in the way de¬ scribed above. The refining of fibre material at low concentration, prefer¬ ably in the range 2-5δ, per se has been applied since long. The material, however, was fibre material of low yield, most usually about 50$, so-called chemical pulps, or of yields up to 8Ct%, so- called semi-chemical pulps. In both cases the fibres have a charac- ter quite different from that in the yield range, to which the present invention refers {~~> 857-0 • Said low yields, below 80/-, render flexible fibres, which can be refined at low concentration and in small gaps without destroying the fibres. Moreover, never or very seldom the energy requirements are higher than 400-500- • RWh/ton, which is about half or one third of the energy amount re- q uired for a satisfactory refining of high-yield fibre according to the invention. It is, further, to be observed that the fibre con¬ centration in these cases (2-57?). is the same both in the gap and in the refiner housing. A fibre material, which after refining can be characterized as mechanical or chemi- echanical pulp, is refined according to conventional technology from raw material to pulp at high concentration, 20-407S.The invention, of course, is not restricted to the embodi¬ ments described, but can be varied within the scope of the inven- tioπ idea. | AM D (received by the International Bureau on 19 June 1979 (19.06.79))1. A method of refining lignocellulose-contαining material, which first is preheated and/or treated with ligπin-softening chemicals and possibly defibred and thereafter charged into a disc refiner and refined during the passage out through the gap (lθ) between the refining discs (6, 7) of the refiner to a surrounding housing (15), characterized in that the refining is carried out at so low concentration of the material that the concentration at the discharge of the material from the gap (lθ) is 8-15%, that water continuously is supplied to the refiner housing (15) outside the refining discs (6, 7) for di¬ luting the refined material to a fibre suspension of a concentration easy to pump, preferably 1-6%, and that the refiner housing (15) is maintained filled with said suspension. 2. A method as defined in claim 1, characterized in that at the entrance of the material into the space between the re¬ fining discs (6, 7) an overpressure is maintained, and substantially the same overpressure is maintained in the refiner housing (15) out¬ side the refining discs. 3. A method as defined in claim 2, characterized in that the overpressure is maintained between 20 and 1 0 kPa.4. A method as defined in any one of the preceding claims, characterized in that the material concentration at the refining is maintained by controlled supply of diluting water when the material enters the space between the refining discs (6, 7).5. A method as defined in any one of the preceding claims, characterized in that the water for diluting the material in the refiner housing is supplied to the lower portion of the refiner housing (15), and that- the material is discharged from the upper portion of the refiner housing.JU EA T STATEMENT UNDER ARTICLE 19With re ference to the search report of 1979-0-4-27 we want to re¬ place the claims on file by the attached new claims. In the new claim we have more clearly defined the concentration of the material in the refiner, see the description page 4, lines 29-30. Re ference numerals are inserted in the new claims.- REAT? | HOEGLUND H; PETERSON P; SCA DEVELOPMENT AB; SCA DEV AB | HOEGLUND H; PETERSON P |
WO-1979000638-A1 | 1,979,000,638 | WO | A1 | EN | 19,790,906 | 1,979 | 20,090,507 | new | A61F1 | B05D3, A61M1, C08L5 | A61L33, A61M1 | A61L 33/00H2A | A METHOD OF PRODUCING THROMBOSIS-RESISTANT SURFACES | A method of treating surfaces of medical devices which are to be brought into contact with blood or blood plasma for the purpose of rendering the surfaces resistant to thrombosis. The surfaces are treated with a wetting solution of a salt of a metal capable of causing peptide hydrogen ionisation and of forming complex compounds with heparin, hirudin and other anticoagulant proteins than hirudin, as a rhodium salt or a palladium salt, prior to applying thereto a coating of heparin, hirudin or other anticoagulant proteins than hirudin. | A METHOD OF PRODUCING THROMBOSIS-RESISTANT SURFACESThe present invention relates to a novel method of effect¬ ively treating surfaces with heparin, hirudin and other anticoagulant proteins for the purpose of rendering said surfaces resistant to thrombosis. The method comprises the treatment of said surface with a palladium salt or a rhodium salt prior to heparising said surface.In present day medicine and medical-care institutions a large number of treatments are carried out in which blood and blood plasma comes into contact with foreign surfaces, causing problems which are difficult to overcome clinically, for example when using vascular prostheses, catheters and the like. This problem originates from the fact that blood will coagulate when coming into contact with foreign bodies. Although it is not clearly understood why contact with a foreign body will cause blood to coagulate, it is known • that blood platelets will release substances which accele¬ rate the formation of thromboplastin upon adhesion and aggregation, which in turn initiates the formation of a thrombus. In this way there is formed a network which can result in the formation of a thrombus. It is thus logical to try to prevent blood platelets from adhering to such surfaces. To this end there has been devized a method which compares heparinizing the surface of polymeric materials.Heparin, which is a mucopolysaccharide from D-glucoseamine and glucuronic acid with a molecular weight of about 17000, has the ability of preventing the aforementioned formation of a thrombus. It is essential that a heparinized surface is stable and that the heparin is firmly bound to the surface of the object. In an article by Olsson et al en¬ titled Prevention of Platelet Adhesion and Aggregation by a Glutardialdehyde-Stabilized Heparin Surface , Thrombos, Hae ostas (Stuttgart) (1977) 37, pages 274-283 and Larsson et al (1976) there is described a rnulti--stage method of heparinizing a surface, which method, in addition to washing stages, comprises treating the surface with hexadecyl amine hydrochloride heparin, an aminesoluti tglutaraldehyde and cooking salt. The product is considerab better than one whose surfaces have not been treated. The layers produced when applying this method tend to be uneve and are also liable to be washed-off by the blood flowing thereagainst, consequently, there is a need of improving the method. Heparin shares this property with hirudin and other anticoagulant proteins. Hirudin is a protein having a molecular weight of 16000 - 1000.When applying the method of the invention there is obtaine an extraordinarily uniform and dense coating which adheres with such good effect that it is not removed by the blood flowing thereacross.When reference is made herein to heparin, it will be under stood that reference is also made to hirudin and like anticoagulant proteines.When putting the method into effect a well cleansed surfac to be heparinised is treated with a wetting solution of a metal salt of a metal capable of causing peptide hydrogen ionisation, whereafter the surface, subsequent to being rinsed, is treated with a solution containing heparin, preferably 1,000-1,000 IE per litre, over a period of time of such length that a coherent heparin layer- is formed on said surface. It will be understood that lower or higher concentrations can be used.The surface to be treated may be of practically any materi whatsoever, although preferably the surface is of metal, such as a stainless steel, a plastics material, such as polyvinyl chloride, polyolefins, acryl resins and co-poly¬ mers thereof, silicon plastics, rubber, particularly butyl rubber, and fluorocarbon plastics. When cleaning surfaces of fluoro carbon plastics, they should be treated with an etching substance to ensure a uniform layer on the plastics surface.The treatment metal may be one of a number of different metals. Those metals tested in particular included palladium, rhodium, nickel, cobalt and copper. Among these metals palladium and rhodium take a particular position, owing to the fact that peptide hydrogen ionisation takes place at an optimal pH range of 3-4. The pH range in the case of nickel is 4-6, in the case of cobalt 6-8 and in the case of copper 8-10. With regard to these properties see E.W. Wilson and R.B. Martin, Inorg. Chem 9, page 528 (1970).As before mentioned, the well-cleaned, and optionally etched surface is treated with a solution of a metal salt of the metal soluble in the solvent used, with a preferably pharmaceutically acceptable acid. As a suitable solvent there can be mentioned primarily water, and water in mix¬ tures with a polar solvent m-iscible therewith. Polar organic solvents can also be used. Among those polar solvents which can be used are alkanols, such as methanol and ethanol.Examples of suitable salts are primarily chlorides, sul¬ phates, nitrates, acetates, citrates, although it lies within the expertise of one skilled in this art to select other suitable soluble salts of the metal used.The use of palladium chloride in aqueous solution or palla¬ dium citrate in an ethonal-containing aqueous solution is particularly preferred. Rhodium can be used in the same manner.The treatment with the metal salt takes only some seccnds up to some minutes, depending upon the temperature of the solution and its pH, and takes place at an ion strength o 0.3-3 mmol metal salt per litre, which in the case of the mentioned palladium salts corresponds to 0.1-0.5 grams of salt per litre. The temperature may be room temperature, although a temperature of 50-80cC is preferred.Subsequent to rinsing the surface, preferably with distill water, the surface is treated with a heparin solution containing 1000-10000 IE heparin per litre. The solution contains mainly water and other suitable substances such as sodium chloride and glucose. The treatment time also varies here, although normally requires a treatment time 15-45 minutes. Glucose can be added to stabilise the solu tion.The treatment method proposed in accordance with the in¬ vention results in the formation of a heparin layer which, has been judged, on the tests carried out, to be some ten times better than a heparin layer produced in accordance with the present standpoint of technics. It is assumed th palladium binds to the amine group in the glucose amine part of the heparin molecule, possibly in combination with van den Waals bonds to oxygen atoms in the heparin chain and in the sulphone group which is bound to the amine gro in the glucose amine part of the molecule.It lies within the scope of the expertise of one skilled in this art to vary the method when treating different surfaces, in dependence upon the nature of the surface to be treated and of the salt and the solvent used, by select ing suitable temperatures and times when treating with the metal salt and with the heparin solution. Thus, it is much easier to treat glass surfaces and also metal surfaces th it is to treat plastics surfaces, particularly surfaces comprising fluorocarbon plastics.. _0MP ■ | CLAIMS :-1. A method of treating surfaces which are to be brought into contact with blood which is passed to or returned to the blood circulatory system of a human being or an animal, comprising treating a well-cleansed surface with a wetting solution of a metal salt of a metal capable of causing peptide hydrogen ionisation and of forming complex compounds with heparin, hirudin and other anticoagulant proteins, and treating the surface with a solution containing heparin, hirudin or said, other anticoagulant protein in a manner such as to form a coherent layer of anticoagulant compound on said surface.2. A method according to claim 1, characterised in that said metal having the ability of causing peptide hydrogen ionisation is palladium in the form of a soluble salt of a pharmaceutically acceptable acid.3. A method according to claim 2, characterised in that the palladium salt is a palladium citrate in aqueous solution.4. A method according to claim 1, characterised in that the heparin is used in aqueous solution containing 3-8% glucose.5. A method according to claim 1, wherein said metal having the ability of causing peptide hydrogen ionisation is rhodium in the form of a soluble salt of a pharmaceutic¬ ally acceptable acid. | BERGSTROEM A; SOEDERVALL B; THIN CONDUCTIVE COATING OESTER; THIN CONDUCTIVE COATING OESTERMALM | BERGSTROEM A; SOEDERVALL B |
WO-1979000639-A1 | 1,979,000,639 | WO | A1 | XX | 19,790,906 | 1,979 | 20,090,507 | new | E05B47 | H01F13 | E05B19, E05B47, H01F13 | E05B 47/00B, H01F 13/00B | KEY,METHOD OF PRODUCING SAME AND PROCESS AND APPARATUS FOR USE IN THE METHOD FOR MAGNETISING THE KEY | After assembly of a key, magnetic poles are imprinted on a magnetisable body (1) of the key by passing an electric current through a pair of parallel electrical conductors (22) which are spaced apart in a direction transverse to their lengths, have between them a magnetic conductor (26) and further magnetic conductors (25, 27) at the sides of the electrical conductors remote from the central magnetic conductor. Apparatus for carrying out the method comprises two magnetising heads, each having this arrangement of conductors and being angularly adjustable relative to each other and relative to the body to be magnetised about an axis of that body. The magnetising heads are also adjustable together along the axis of the magnetisable body. | Application of LOWE & FLETCHER LIMITEDTitle: Key, method of producing same and process and apparatus for use in the method for magnetising the key.Technical field:-A FIRST ASPECT OF THIS INVENTION relates to a key which, after being permanently magnetised, is suitable for use in combination with a lock which has magnetic elements movable by magnetic force. A second aspect of the inven¬ tion relates to a method of producing a key for use in such a lock. A third aspect of the invention relates to a process for magnetising a magnetisable body, which process may be used in the method according to the second aspect to magnetise permanently the key. A fourth aspect of the invention relates to apparatus for use in the process according to the third aspect.The Background art:-In known combinations of a lock and key wherein there is associated with the key a permanent magnetic field and the lock has one or more magnetic elements which must be moved by the field of the key to a predetermined releasing position before the lock can be operated, the key has one or more permanent magnets embedded in a body of non- magnetic material. The key will operate the lock only if the magnet or magnets occupy predetermined positions and have a predetermined orientation with respect to the body of the key. Once the components of a key have been assembled together, that key is specific to locks having a corresponding arrangement of releasing positions of the magnetic elements. Since the locks and the keys would normally be assembled by different persons at different places in a workshop, there arises the problem of ensuring that the appropriate key is associated with each lock befo that lock is sold or despatched from the workshop. A further difficulty arises in the provision of additional keys which may be required after the lock has been sold and been used for some time. It would be necessary for each stock holder of duplicate keys to hold duplicates of each key which has been sold with locks. If the number of different keys which are available is large, this stock would be correspondingly large. Thus, the supply of duplicate magnetic keys is inconvenient and expensive, as compared with the supply of duplicate keys for known mechanical tumbler locks by stocking key blanks and cutting duplicate keys as and when required.Summary of the invention:- According to the first aspect of the present invention, there is provided for use, after being magnetised, in combination with a lock having one or more movable elements of magnetic material, a key comprising a body of unmagnet- ised magnetic material and a handle rigidly connected with the body.From a stock of such unmagnetised keys, there can be produced duplicates of a magnetised key by impressing upon the unmagnetised keys permanent magnetic poles.The body of magnetic material is preferably cylindrical. The handle may be of non-magnetic material.The key preferably further comprises a sheath of non¬ magnetic material enclosing the body.According to a second aspect of the invention, there is provided a method of producing a key for use in combination with a lock having one or more movable elements of magnetic material, wherein a body of unmagnetised magnetic material is rigidly connected with a handle and subsequently has impressed upon it a plurality of permanent magnetic poles.Preferably, the body is enclosed in a sheath of., non-magnetic material before the magnetic poles are impressed upon the body.According to a further aspect of the invention, there is provided a process for magnetising a magnetisable body, the process including the steps of providing a first group of conductors comprising an electrical tconductor and first and second magnetic conductors, arranging the conductors of the first group adjacent to a surface of the body with the electrical conductor extending at least a part of the way across said surface in a first direction, the magnetic conductors being spaced apart across said, surface in a second direction perpendicular to said first direction and the magnetic conductors lying on opposite sides of the electrical conductor and then passing an -electric current through, the electrical conductor.The surface of the body may be curved. Thus, said first direction or said second direction may extend around a centre or axis of curvature of the surface.There is preferably provided a second group of conductors also comprising an electrical conductor and first and second magnetic conductors, the second group being spaced from the first group in said first direction and the conductors of the second group being arranged relative to each other and relative to the magnetisable body in the same manner as the conductors of the first group are arranged. An electric current may be passed through the electrical conductors of the first and second groups. Alternatively, respective electric currents may be passed through the conductors of the first and second group either concurrently or successively.The or each group of conductors preferably comprises a second electrical conductor and a third magnetic conductor, the second electrical conductor being arranged alongside the first electrical conductor and' spaced there¬ from in the second direction with the second magnetic conductor lying between the electrical conductors and the third magnetic conductor adjacent to the side of the second electrical conductor remote from the first electrical conductor. An electric current may be passed in opposite directions through the first and second electrical conductors or respective electric currents may be passed in opposite directions through these conductors.After the electric current or currents have been passed through the electrical conductor or conductors, relative displacement of the or each group of conductors and the surface of the magnetisable body in the second direction may occur until the magnetic conductor at one end of the or each group at least partly overlies an area of said surface which was previously overlain by the magnetic conductor at the opposite end of that group and a further electric current or further electric currents may then be passed through the electrical conductor or conductors. During the interval between the passing of electric currents, relative displacement of the first and second groups of conductors in said first direction or relative displacement of the conducrors and the surface of the 'body may be effected in the first direction. According to a fourth aspect of the invention, there is provided apparatus for .carrying out a process according to the third aspect of the invention, the apparatus comprising a carrier and a first group of conductors, the carrier being adapted to support a key with an axis of a magnetisable body of the key in coincidence with -an axis of the carrxer, the group of conductors comprising an electrical conductor and first and second magnetic conductors, each of said conductors being spaced from the axis of the carrier to lie adjacent to a surface of the body and the magnetic conductors being spaced apart by a gap in which the electrical conductor lies.The electrical conductor and the magnetic conductors may each present towards the axis a substantially arcuate concave surface which has its axis of curvature on the axis of the carrier. The concave surface of the electrical conductor may subtend at the axis of the carrier an angle of at least 10 .Brief description of the drawingsThe invention will now be described by way of example, with reference to the accompanying drawing wherein:-FIGURE 1 shows diagrammatically a side elevation of apparatus for magnetising the body of a key, certain parts being broken away. FIGURE 2 shows on an enlarged scale a plan view of one magnetising head of the apparatus shown in Figure 1, together with an adjacent key body which is shown in cross section.,FIGURE 3 is a side elevation of the parts shown in Figure 2, certain of these parts being shown in cross section on the line III-III of Figure 2, and FIGURE h shows a perspective view of the key with certain parts broken away.Detailed descriptionThe apparatus illustrated in Figures 1, 2 and 3 of the accompanying drawings is intended for use in- magnetising a magnetic body of a key which is illustrated in Figure 4. The key comprises a cylindrical body 1 of magnetic material, for example a sintered isotropic ferrite. The body is enclosed by a sheath in the form of a sleeve .2 of non-magnetic material, for example stainless steel or brass. One end of the sleeve is closed and an opposite end of the sleeve is embedded in a handle portion 3 of the key. The handle portion is formed by moulding plastics material around a core 6 of non-magnetic metal. One end portion of the core 6 engages in a diametral groove formed in an end face of the body 1. The core is formed with a laterally projecting lug 5 which extends through a slot formed in the sleeve 2 adjacent to the handle portion of the key. Adjacent to the lug 5 but spaced therefrom in a direction away from the closed end of the sleeve 2, the handle portion includes a boss h of plastics material. The key is produced by inserting the body 1, whilst in an unmagnetised condition, into the sleeve and then placing the core 6 and a free end portion of the sleeve in a mould cavity. Plastics material is then injected into the mould cavity to form the plastics portion of the key. The plastics material forces the body 1 against the closed end of the sleeve and fills the space in the sleeve around the core 6, so that the core, the sleeve and the body 1 are rigidly united with one another. Subsequently, the body 1 of, the key 'is magnetised.In use of the key the lug 5 engages in a complementary formation in a lock to establish a predetermined angularBUREΛTOMPI relation between the key body 1 and a key-receiving ' ember of the lock. The end face of the boss 4 co¬ operates with the lock to establish a predetermined axial positio n of the body 1 relative to the key- receiving member of the lock. Because permanent magnetic poles are impressed on the body 1 after the body has been rigidly connected with the lug 5 and the boss 4, the positions- of magnetic poles with respect to the lug and the boss can be controlled with a high degree of accuracy. Typically, the diameter of the body 1 is 4 mm and the thickness of the sleeve 2 is 0.1 mm. If the mechanical properties of the body of magnetic material are adequate, the sleeve may be omitted, the core 6 and the body 1 being modified to interfit in a more complex manner than shown in Figure 4.The magnetising apparatus comprises a carrier 10 which is adapted to support the key for rotation relative to a base 11 of the apparatus about an axis 12 which co-incides.with a longitudinal axis of the key body 1. The carrier is connected with the base by a bearing 13 and includes a platform 14 which is spaced from the bearing along the axis 12 by a gap 15. In the platform 14, there is formed an aperture through which the key body 1 and sleeve 2 extend and, surrounding the aperture at the upper side of the platform, a recess for receiving the boss 4 and lug 5« The recess includes a portion complementary to the lug 5 to establish a predetermined, angular relation between the carrier 10 and the key body I. On the carrier there is mounted a spring-loaded presser member 17 which, when engaged with the handle portion 3 of a key as shown in Figure 1, ensures that BUREΛ∑ΓOMPI4.A> wipo y . the boss 4 is properly seated in the recess l60 In this way, the position of the key body 1 along the axis 12 relative to the carrier 10 is accurately controlled.For subjecting the key body 1 to magnetic flux, there are provided two magnetising heads 18 and 19 whi'ch lie within the gap 15 and near to the axis 12 but spaced sufficiently far from the axis to permit the sleeve 2 of the key .to extend between them.Each magnetising head comprises an upper electrical conductor 20 and a lower electrical conductor 21. Each of these electrical conductors has a substantially truncated V shape, having an arcuate limb 22 which lies near to the axis 12 and rectilinear limbs 23 and 24 which extend from opposite ends of the arcuate limb in directions away from the axis 12. The cross section of each of the limbs 22, 23 and 24 may be rectangular. The arcuate limb 22 presents towards the axis 12 a concave arcuate surface which, when the apparatus is in use, lies close to or even in contact with the sleeve 2 of the key in order that the arcuate surface of the electrical conductor should be as close as possible to the magnetic body 1 of the key. The electrical conductors 20 and 21 are formed of a material having a high electrical conductivity, for example platinum or silver.The radius of curvature of the arcuate surface of each of the electrical conductors 20 and 21 which is presented towards the axis 12 may be substantially equal to the external radius of the sleeve 2. Each electricalOMPII iwpo- conductor is then positioned with ibs centre of curvature lying on the axis 12 so that all parts of the arcuate surface lie at the same distance from the axis of the key body 1. If the radius of curvature of the arcuate surface~ differs substantially from that of the sleeve 2, then the centre of the arcuate surface would lie closer to the axis 12 than other parts of the arcuate surface. The angle a. subtended at the axis 12 by the arcuate surface of each of the electrical 'conductors 20 and' 21 is 0 preferably at least 10 . More pre erabiy this angle is approximately 60 . ' It will be noted that the dimension of each limb 22 which extends parallel to the axis 12 is smaller than the dimension of each limb 22 which extends around the axis 12. Thus, ea.h arcuate surface presented jr by the electrical conductors 20 and 21 towards the axis 12 is elongate and its longitudinal centreline lies substantially in a plane perpendicular to the axis 12.Each of the magnetising heads 18 and 1 further comprises upper, middle and lower magnetic conductors20 25, 6 and 27 which are formed of material having a low- resistance to magnetic flux, for example mild steel. The upper and middle magnetic conductors arc spaced apart by a gap in which the upper electrical conductor 20 lies. The middle and lower magnetic conductors are spaced2 apart by a further gap in which the lower electrical conductor 21 lies. The electrical conductors 20 and 21 are insulated electrically from the magnetic conductors 25 , 6 and 27 b layers 28 of electrically insulating material. The middle magnetic conductor 26 is in the 0 form of a flat plate having a profile corresponding to that of the electrical conductors 20 and 21, that is the magnetic conductor has an arcuate edge lying diroctly between the arcuate surfaces of the electrical conductorsOMPI which face towards the axis 12, roctiiino.ir edges extending radially witJi respect to the axis 12 and Jying between lio corresponding surfaces of the olectric-jlcoiuliictors and a further rectilinear edge spaced further* from the axis 12 than is the arcuate edge and coinciding with a tangent to a circle drawn around the axis 12. The upper .and lower magnetic conductors 25 and 6 have a shape similar to that of the middle conductor 26 bu with the addition of flanges along the radially extending edges. The flanges of the •-j_0 upper magnetic conductor just touch the flanges of the lower magnetic conductor. An aperture is forinod centrally in each of the magnetic conductors and in cacii layer of electrical insulation adjacent to the magnetic .conductors. The assembly of electrical conductors, magnetic conductors je and layers of electrical insulation are hold together by a bolt 29 which extends through these apertures and is insulated electrically from both o£ the electrical conductors and from the magnetic conductor 26 by a sleeve of insulating material fitted around a shank of the bolt.20 Means is provided for conducting an electric current to the electrical conductors 20 and 2.1 of each magnetising head and also for conducting a fJuid cool ant to the electrical conductors. Tiiis means comprises a series of metal and non-metal tubes connected end-to-end to provide 2^ a coolant duct through which a fluid coolant can bo conveye Water is a suitable coolant and the apparatus may include' a pump (not shown) for pumping water from a reservoir throu the coolant duct.The non-metal tubes of the eu_Lant duct are electricall ■~Q insulating. The metal tubes of the coolant duct are formed of copper or other good''electrical conductor. The coolant- duct comprises a metal tube 30 having at one end a unionBAD RIGIN 31 by which the tube is connected with a flexible conduit 32. Adjacent to the union 31, there is provided on the tube 30 an electrical terminal 33. The tube 30 extends from the terminal 33 to the limb 23 of the upper c electrical conductor 20 with which the tube is united by fusion. An end of the tube 30 remote from the union -31 is connected by a non-metal tube with an end of a metal tube 3^ which is united by fusion with the limb 24 of the upper electrical conductor 20. The tube 3'i extends away Q from .the electrical conductor 20, around a bend 37 i a vertical plane and returns to the limb 2k of the lower electrical conductor 21, with which limb the tube is united by fusion. A lower end of the tube 3 is connected by a non-metal tube witli a lower etal tube 35 similar jL5 to the tube 3 . The tube 35 is united by fusion with the limb 23 of the lower electrical conductor 21 and has an electrical terminal 36 and a union 37. Tlie terminals 33 and 3 are connected by means of flexible electric conductors (not shown) to a power pack (also not' shown)20 capable o.f causing a large current pulse to flow through the circuit comprising the tube 30, the upper electrical conductor 20, the tube 34, the lower electrical conductor 21 and the tube 35• It will bo noted that α current which flows in one direction through the upper electrical25 conductor flows in an opposite direction through the lower electrical condtictor.As shown in Figure 1, the magnetising heads 18 and 19 lie at the same position along tlie axis 12. These heads can be moved along tlie axis relative to tlie carrier30 10 and the body 1 of the key. Furthermore, the head 18 can move about the axis 12 relative to the head 19 so that the angular relation between each head and the body 1 of the key can be adjusted independently. The assembly oT magnetic and electrical conductors and the tubes which are comprised by the head 19 are supported on a support 40 which is constrained by a fixed pillar 55 against movement around the axis 12 but is adjustable along the axis. The support 40 is rotatable around a tube 41 which extends upwardly from the bearing 13 towards the platform 14. This tube 'is maintained by the bearing in coaxial relation with the body 1 of the 'key and is con strained against rotation about the axis 12 by a_ pin 42 engaging in a vertical slot formed in the tube.The assembly of magnetic and electrical conductors and the coolant duct of the magnetising head 18 are supported on a support 47 which is mounted on tlie tube 41 for rotation relative thereto about the axis 12 and inter fits with the support 40 in such a manner that tlie suppor 40 and 47 move together along the axis. The tube h i is constrained to move alozig the axis with the supports. Fo raising and lowering the tube '-ι1 and supports ^|0 and ^ι7, there is provided a handle |3 which is rigidly sccurd to a lever kk . ' One end of the lever is pivotally connected. with the support 40 and the other end of the lever is pivotally connected with a post 45 which is rigid with the base 11.Means is provided for establishing alternative positions of the support 40 along the axis 12. This mean comprises two vertical rows of aχ_ertures or recesses k6 formed in the tube 41 at diametrically opposite posi ions between the bearing 13 and the support 40. On the base 11 there are provided-.detents (not shoλ-n) for engaging. releasably in the apertures or recesses 46. Each such detent preferably comprises a ball which is urged toward the tube k l by a spring-loaded position. In the particular example illustrated, there are five apertures or recesses defining five alternative positions of the support ^|0 along the axis 12. In one extreme position, the magnetis¬ ing head 19 is adjacent to the underside of the platform 14 and to a part of the body 1 of the key near to the lug 5. In the other extreme position, the head' 19 is adjacent to an end portion of the body 1 remote from the lug * , '■For tiirning the support /|7 about the ax;is 12 there is provided a handle 4S. Alternative positions of the support about the axis ar.e defined by detents 49 and 0 engageable in selected ones of recesses 51 formed in the support 40. These detents are urged towards the support 40 and when a detent is aligned with one of the recesses 1 f that detent engages partly in the support 40 and partly in the support 47. 'A further pair of detents 52 and 53 are provided on the base 11 to define alternative positions of the carrier 10 about the axis 12. The detents /|9, 50, 52, 53 and the detents associated with the apertures 46 are all arranged in a similar manner which is illustrated in Figure 1.When the body 1 of a key is to be magnetised, the presser member 17 is raised away from the platform l/_ and the key is inserted into the carrier 10 with tlie body 1 and sleeve 2 of the key extending between the magnetising heads 18 and 19 and the boss 4 of the key seated in the recess 16 of the carrier. By means of the handle 3 t the magnetising heads 18 and 1.9 are moved to their up or- most positions and arc then retained in tJtat position by engagement of a detent in one of the apoi tures or recesses -.6.. By means of a handle 51' the carrier 10 is turned about the axis 12 to establish tlie required angular relationship between the body 1 of tlie key and tlie magnetising head 19. By means of the handle l\ S , the magnetising head 18 is moved about the axis to establish the required angular relationship with the head 19. These angular positions are maintained by engagement of on of the detents k 9 and 50 in an associated recess and one c of the detents 52 and 53 i an associated recess. A pulse of electric current is passed through the electrical conductors of the magnetising heads. The conductors of the head 18 may be connected in series with the conductors of the head 19, which case a single pulse-10 is passed through the conductors of both heads and the heads are energised concurrently. Alterna ively, a current pulse may be passed through the conductors 20 and 21 of the head 18 and then a further current pulse passed through the electrical conductors of the head 19]_κ to enengise the heads successively. The flow of electric current through the conductors 20 and 21 of the head 18 establishes a magnetic flux which magnetic poles on the body 1 of the key as illustrated in Figure 3- Like poles are established adjacent to the upper and lower20 magnetic conductors 25 and 27 whilst adjacent to the middl magnetic conductor 26 there is established an opposite magnetic pole. Since the magnetic conductors provide paths of low resistance for the magnetic flux, the magnetic poles do not extend significantly above the upper25 magnetic conductor or below the lower magnetic conductor.After each of the magnetising heads 18 and 19 has been energised, the carrier 10 and support 47 may be turned about the axis 12 to establish a now aiigular relationship between the magnetising heads and the bodyOQ 1 of the key. The magnetising heads may then be energise once more to imprint on the body 1 further agnetic poles at the same position along the axis of the key but spaced angularly about that axis from the previously imprinted poles. The magnetising heads 18 and 19 may then be 5 moved along the axis 12 relative to tlie key body 1 by means of the handle h3 to a second axial position, further required angular relations between the magnetisingBADORIGINAL heads and key body establi-shed and the magnetising heads then energised once more. In the second axial position of the magnetising head 18, the upper magnetic conductor 25 may occupy the same position along the axis 12 as is occupied by the lower magnetic conductor 27 in the first axial position.Each magnetic pole imprinted on the body 10 of the key extends somewhat further around the axis of the key then do the arcuate surfaces of the electrical conductors 20 and 21, depending upon the extent to which leakage of magnetic flux occurs in regions adjacent -to the rectilinear edges of the magnetic conductors. Thus, in a case where the electrical and magnetic coudictors sub¬ tend at the axis of the key an angle of approximately 6θ , the magnetic poles imprinted on the key may subtend at the axis of the key an angle of approximately 0 . The angular extent of the magnetic poles and the flux density at different positions within those poles can be varied by varying the leakage of magnetic flux from the magnetising head. The leakage of magnetic flux can be increased by partly or entirely omitting the flanges of the ui-per and lower magnetic conductors and 27.Whilst we prefer to employ two magnetising heads, it would be within the scope of the invention to provide in the apparatus a single magnetising head. This could be energised in four alternative positions around the axis of the key to imprint on the body of the key four poles at the same position along the key axis.The arrangement of two electrical conductors and three magnetic conductors shown in Figure 3 and used in the manner hereinbefore described is convenient, in that successive poles along the length of the key which correspond to the middle magnetic conductor 26 do not interfere with each other. Such interference is avoided by the presence of opposite poles between successive poles corresponding to the middle magnetic conductor. However, the lower magnetic conductor 27 and lower electrical conductor 21 could be omitted from the or each magnetising head. Upon being energised by a single current pulse, each magnetising head would then imprint on the body of the key only one pair of unlike magnetic poles.In a case where two electrical conductors are provided in each magnetising head, we prefer that these electrical conductors should be connected ii series with each other as shown. However, the pair of electrical conductors could be connected in parallel with each other or could be connected separately to the electrical power pack so as to bo energisable respectively by successive current pulses. | CLAIMS : -1. For use, after being magnetised, in combination with a lock having one or more movable ements of magnetic material, a key comprising a body (l) of unmagnetised magnetic material and a handle (3) rigidly connected with the body,2. A key according to claim 1 wherein the handle (3) is formed of non— agnetic material.3. A key according to claim 1 or claim 2 wherein the body (l) is generally cylindrical.4. A key according to any preceding claim further comprising a sheath (2) of non-magnetic material enclosing the body (l).5. A method of producing a key for use in combination with a lock having- one or more movable elements of magnetic material, wherein a body (l) of unmagnetised.magnetic material is rigidly connected with a handle (3) and subsequently a plurality of permanent magnetic poles are impressed on the body.6. A method according to claim 5 wherein the body (l) is enclosed in a sheath (2) of non-magnetic material before the magnetic poles are impressed upon it.7. A process for magnetising a magnetisable body of a key, the process including the steps of providing a first group (l8) of conductors comprising an electrical conductor (20) and first and second magnetic condue-tors (25, 26) arranging the' conductors of the first group adjacent to a surface of the body (l) with the electrical conductor extending at least a part of the way across said surface in a first direction, the magnetic conductors being spaced apart across said surface in a second direction perpendicular to said first direction and the magnetic conductors lying on opposite sides of the electrical conductor and then passing an electrical current through the electrical conductor.8. A process according to claim 7 wherein there is further provided in the first group of conductors a second electrical conductor (2l) and a third magnetic conductor (27), the second electrical conductor is arranged alongside the first mentioned electrical conductor (2θ) and spaced therefrom in said second direction with the second magnetic conductor (26) lying between the electrical conductors, the third magnetic conductor (27) is arranged adjacent to the side of the second electrical conductor remote from the first electrical conductor and an electric current is or respective electric currents are passed in opposite directions through the electrical conductors.9. A process according to claim 7 wherein there is provided a second group (l9) of conductors also comprising an electric conductor and first and second magnetic conductors, the second group is spaced from the first group in said first direction, .the conductors of the second group are arranged relative to each other and relative to the magnetisable body in the same manner as the conductors of the first group are arranged and an electric current is or respective electric currents are passed through the electrical conductors of the first and second groups.OΛΪPI 10. A process according to claim 8 wherein there is provided a second group (l9) of conductors also comprising first and second electrical conductors and first, second and third magnetic conductors, the second group is spaced from the first group in said first direction, the conductors of said second group -. are arranged relative to each other and relative to the magnetisable body in the same manner as the conductors of the first group are arranged and an electric current is or electric currents are passed through the electrical conductors of the first and second groups.11. A process according to any of claim 7 to 10 wherein, after pasing the electric current or currents through the conductor or conductors, relative displacement of the or each group of conductors and the surface o the magnetisable body in the second direction occurs until the magnetic conductor (25) at one end of the group at least partly overlies an area of said surface which was previously overlain by the magnetic conductor (27) at the opposite end of the group and then a further electric current is or further currents are passed through the electrical conductor or conductors.12. A process according to claim 11 as appendant to claim 9 or claim 10 wherein, during the interval between the passing of electric currents, in which interval the relative displacement in the second direction occurs, relative movement of the first (l8) and second (19) groups in the first direction is effected.13. Apparatus for carrying out the process of claim 7 and comprising a carrier (lθ) and a first group (l8) of conductors, the carrier being adapted to support the • key with an axis of the body in coincidence with an axis (l2) of the carrier, the group of conductors comprising an electrical conductor (20) and first (25) and second (26) magnetic conductors, each of said conductors being spaced from the axis of the carrier to lie adjacent to a surface of the body (l) and the magnetic conductors being spaced apart by a gap in which the electrical conductor lies.14. Apparatus according to claim 13 wherein the electrical conductor (20) and magnetic conductors (25, 26) each present towards the axis (12) a substantially arcuate or other concave surface.15. Apparatus according to claim 14 wherein the concave surface of the electrical conductor (2θ) subtends at the axis (l2) an angle of at least 10 .l6. Apparatus according to claim 14 or claim 15 wherein the concave surface is arcuate and has an axis of curvature which coincides with the axis of the carrier.1 • Apparatus according to any one of claim 14 to l6 wherein the concave surface of the electrical conductor is elongated and its longitudinal centre line lies substantially in a plane perpendicular to the axis of the carrier.18. pparatus according to any one of claims 13 to 17 wherein said first group of conductors further comprises 5 a second electrical conductor (2l) arranged alongside the first mentioned electrical conductor (2θ) and spaced therefrom in a direction along the axis (l2) of the carrier and a third magnetic conductor (27) situated at the side of the second electrical conductor remote from ,0 the first electrical conductor (25). 19. Apparatus according to any one of claims 13 to 18 comprising a second group of conductors (19) which is adjustable relative to the first group (lO) angularly about the axis (l2) of the carrier (lθ) and comprises substantially the same arrangement of conductors as does the first group.20. Apparatus according to' any one of claims 13 to 19 wherein the carrier (lθ) includes a locating;formation (l6) to co-operate with a locating element (5) of the key to establish a predetermined angular position of the key relative to the carrier about the axis (l2) of the carrier.21. Apparatus according to any one of claims 13 to 20 including means (43) for adjusting the relative positions of the carrier (lθ) on the one hand and of the conductors on the other hand in a direction along the axis (l2) of the carrier, there being provided means (46) for maintaining a selected relative axial position. | HERRIOTT L; LOWE & FLETCHER LTD | HERRIOTT L |
WO-1979000644-A1 | 1,979,000,644 | WO | A1 | EN | 19,790,906 | 1,979 | 20,090,507 | new | C21D9 | null | C21D1, C21D9 | C21D 9/52, M21D 1/18B | HIGH STRENGTH STEEL AND PROCESS OF MAKING | A novel high strength steel especially adapted for automotive applications and the like is provided by cold rolling a low carbon aluminum-killed steel containing added phosphorus and silicon as ferrite strengtheners, continuously heating the cold rolled strip to an inter-critical temperature such that from about 5% to about 25% austenite is present, water quenching to obtain a dual phase ferrite-martensite microstructure having an average volume fraction of martensite of from about 5% to about 25%, and reheating to a sub-critical temperature to temper the steel. The resultant steel has good formability as evidenced by a minimum total elongation of 18%, is free from ductility loss due to room temperature aging, and after stamping followed by a typical paint bake cycle the formed part has a minimum yield strength of 550 MPa (80 ksi). | HIGH STRENGTH STEEL AND PROCESS OF MAKING This invention relates to a novel high strength steel and to a process for making.The urgent need of the automotive industry to meet fuel economy regulations while still producing roomy cars has intensified the search for improved high strength steels. Heretofore,the application of high strength steels with yield strengths of 550 MPa (ksi) in the formed part has been limited by inferior formability and also by the increased cost of such steels.High strength in steel is readily obtained by suitable alloy additions, but the cost is usually prohibitive for automotive and other applications. It is known that martensitic steels possess high strength, but have poor ductility. It has also been proposed to quench renitrogenized steel from a tem¬ perature in the inter-critical region to obtain a ferrite-martensite microstructure which, upon sub¬ sequent straining and aging, has the desired mechan- ical properties. However, such steels have the dis¬ advantage of somewhat restricted ductility which is further reduced by strain aging at room temperature which occurs between temper rolling in the steel plant and the time the steel sheet is used in a forming or stamping operation.Accordingly, a primary object of the present invention is to provide, without the use of costly alloy additions, a novel and improved steel having good ductility which is suitable for use in sheet form for automotive applications and the like and which is not subject to room temperature aging but which has a high work hardening rate and age harden- ing response so that stamping and paint baking result in high strength in the finished part.A more specific object of the invention is to provide a high strength low alloy steel of the fore- going character which exhibits a minimum total elongation of 18%, is free from ductility loss due to room temperature aging, and which, in the final fabricated part, exhibits a yield strength of at least 550 Pa (80 ksi) . A further object of the invention is to pro¬ vide a novel process for making a steel of the fore¬ going character.Other objects and advantages of the invention will be apparent from the subsequent detailed de- scription and specific example.In general, the above-described objects of the invention are achieved by cold rolling a low carbon aluminum-killed steel containing added phosphorus and silicon as ferrite strengtheners continuously heating the cold rolled strip to an inter-critical temperature such that from about 5% to about 25% austenite is present, water quenching to obtain a dual phase ferrite-martensite microstructure having an average volume fraction of martensite of from about 5% to about 25%, and reheating to a sub- critical temperature to temper the steel. The re¬ sultant sheet or strip has good formability, is free from ductility loss due to room temperature aging, and after straining and aging during fabrication of a formed part, the desired high strength level is developed. Specifically, the steel product exhibits a minimum of 18% total elongation prior to stamping and a minimum yield strength of 550 MPa (80 ksi) after stamping followed by a typical automotive paint bake cycle. This combination of properties allows design engineers to take advantage of po- tential weight reductions by utilizing the high strength of the steel while permitting part fabri¬ cation without extensive modification of existing dies.High strength levels can be obtained in a ferrite-martensite, but the ductility and form¬ ability of the product suffers. In accordance with the present invention, the martensite content is kept low enough so that the cold rolled product has a minimum total elongation of 18%, but a moderately high strength level of from about 400 to about 500 MPa (58-73 ksi), dependent upon the carbon content, is realized by including silicon and phosphorus in the steel as ferrite strengtheners. The dual phase product has a high strain hardening capacity, and the final fabricated part exhibits the desired mini¬ mum yield strength of 550 MPa (80 ksi) . As herein¬ after described in more detail, in the present in¬ vention the dual phase microstructure is obtained by rapid quenching from an inter-critical temperature within a controlled narrow range at a cooling rate which is in excess of the critical cooling rate and which is high enough so that phosphorus does not migrate and relocate at the grain boundaries where it would cause poor ductility. Instead, the phosphorus remains within the ferrite grains, and the desired stiffening effect of phosphorus is realized while re¬ taining acceptable ductility. Moreover, the cold rolled sheet product of the present invention is not subject to detrimental room temperature aging due to nitrogen since the steel is aluminum-killed.The steel composition of the present invention consists essentially of the following, with the bal¬ ance essentially iron:Carbon .05 - .15 wt.%Manganese .30 - .60 wt.%Phosphorus .04 - .10 wt.%Silicon .10 - .50 wt.%Aluminum .02 - .08 wt.%Sulfur .030 wt.% max.Expensive alloy additions are avoided, but the amounts of silicon and phosphorus added as ferrite strengtheners are greater than the residual amounts of these elements so that the steel can be regarded as a low alloy steel. Although appropriate additions of either phosphorus alone or silicon alone can pro¬ vide high strength levels, there are adverse side effects in each case. Thus, if phosphorus is too high, the steel is too brittle and difficult to spot weld. If silicon is too high, the steel becomes more susceptible to surface defects making it unsuit¬ able for exposed automotive application and also be- comes more difficult to galvanize. Accordingly, the invention relies on the combined use of phosphorus and silicon within the specified ranges. The maxi¬ mum silicon and manganese contents are such that rapid quenching with water, rather than air cooling, is necessary in order to obtain the desired ferrite- martensite microsctructure. To eliminate room tem¬ perature aging problems, the steel is fully killedOMPI, 2A fa IPO with aluminum, as reflected by the above-listed range of aluminum content in the steel. However, the steel is still subject to carbon strain aging so that the desired high strength levels are ob- tained in automotive applications and the like after stamping and heating, as in paint baking.The usual steelmaking practices may be fol¬ lowed. Typically, the hot metal from the blast furnace is refined in a basic oxygen converter. If desired, the hot metal may be subjected to conven¬ tional desulfurization, e.g. by calcium carbide injection, prior to being charged to the basic oxygen converter. The required additions of alum¬ inum, silicon, and phosphorus, may be carried out in the ladle prior to ingot casting or continuous casting.The usual hot rolling and cold rolling prac¬ tices may be used to provide cold rolled coils for subsequent continuous annealing in accordance with the invention. Typically, in the usual hot band sizes the finishing temperature may be from about 785°C to about 955°C, and the coiling temperature may be from about 480°C to about 705°C. In the cold rolling stage the percent cold reduction may range from about 40% to about 80%, but a relatively high degree of cold reduction of from about 50% to about 75% is preferred in order to obtain a fine grain size after the annealing step. The thickness of the cold rolled strip may be from about 0.3 mm to about 3 mm.The cold rolled strip is processed, in accord¬ ance with the invention, in a continuous annealing line in which the strip is (1) heated in a soak section to a temperature between the A]_ and A3 critical points, (2) water quenched in a quench section at a rapid rate to obtain a dual phase ferrite-martensite microstructure, and (3) reheated in a tempering section to a subcritical tempera¬ ture and cooled to ambient temperature. When nee- essary the strip is temper rolled for flatness.As pointed out previously, a limited amount of martensite is required in the dual phase micro¬ structure so as to achieve the desired combination of physical properties in the final steel strip. Consequently, the inter-critical soak temperature must be carefully controlled in the soak section of the continuous annealing line, preferably with + 10°C, for partially austenitizing the steel to the desired extent and thereby realizing the aim ductility and yield strength in the quenched and tempered product. Dependent upon the carbon con- tent of the steel and also upon line speed and strip gauge, the cold rolled strip is heated to a narrow temperature range between the A]_ and the A3 critical points such that from about 5% to about 25% austenite is present. In general, the strip is heated at a soak temperature of from about 745°C to about 845°C for a period of from about 20 to about 120 seconds.The partially austenitized strip passes from the soak furnace into a water quench zone of any suitable design capable of rapidly quenching the strip at a rate in excess of the critical cooling rate so that all of the austenite present is con- verted into martensite which is uniformly distrib¬ uted in fine grain polygonal ferrite. The average volume fraction of martensite present in the quench¬ ed product is from about 5% to about 25%. Although the invention is not so limited, a preferred quench system utilizes submerged nozzles such as dis¬ closed in Taylor et al U.S. Patent Nos. 3,360,202 and 3,410,734. The cooling rate will ordinarily be in excess of 1000°C/sec. As previously discussed, the rapid quench rate also has the advantage of avoiding relocation of phosphorus to the gain boun¬ daries which would impair the ductility of the product.In the tempering section of the continuous annealing line the quenched strip is reheated to a sub-critical temperature, e.g. from about i50°C to about 480°C for a period of from about 5 to about 300 seconds, in order to effect tempering of the relatively high carbon content martensite. The strip is then cooled to substantially ambient tem¬ perature and, when necessary, temper rolled for flatness in the conventional manner to obtain a cold reduction not in excess of 2%.The esultant steel sheet or strip product has a minimum total elongation of 18% and a yield strength of from about 400 to about 500 MPa (58 - 73 ksi) , dependent upon the carbon content. The product has excellent formability for automotive and other applications, and after stamping and a typical paint bake cycle the yield strength of the fabricated part exceeds the required minimum of 550 MPa (80 ksi) and in most cases is in excess of 620 MPa (90 ksi) . The excess aluminum present in the killed steel ties up all the nitrogen present so that there is no loss of ductility due to room temperature aging. In addition, the uniformity of properties within a coil is excellent, e.g. the variation in yield strength being less than 40 MPa (6 ksi) . The latter is an important property for a stamping die which is set up for springback con¬ trol. Furthermore, the product has excellent spot weldability and compares favorably in this respect with aluminum-killed AISI 1006 steel.For purposes of further illustrating the in¬ vention, but without limiting the same, the fol¬ lowing specific example is presented.EXAMPLE Two grades of aluminum-killed steel were made in a BOF shop with a nominal chemistry of 0.45/0.55% manganese, 0.25/0.35% silicon, 0.05/0.07% phos¬ phorus, 0.03/0.06% aluminum and containing 0.07% carbon and 0.10% carbon, respectively. Low sulfur levels were achieved by calcium carbide injection to the hot metal in open ladles between the blast furnace and the BOF shop. The aluminum, silicon, and phosphorus additions were made to the ladle, and the steel was ingot cast using bottom pouring. Test coils were produced from these steels in several different gauges using conventional hot rolling and cold rolling practices. The details of the hot and cold rolling steps and the actual steel chemistry are presented in Tables I and II, respect- ively. In Table II the chemistry of aluminum- killed AISI 1006 steel is shown for comparison.OA'iPI TABLE I HOT AND COLD ROLLING'PRACTICECold FinalHot Rolling Conditions Hot Band Reduction Coil Size Steel Finishing Temp. Coiling Temp, Size (mm) (%) (mm)2.3 x 1018 78.3 0.5 x 10002.3 x 1237 71.7 0.65 x 12190.07%C 860° ± 15°C 560°C + 15°C 2.8 x 1237 71.4 0.8 x 12192.8 x 1237 64.3 1.0 x 12193.2 x 1237 62.5 1.2 x 12192.3 x 1237 71.7 0.65 x 1219 I so0.10%C 860° + 15°C 560° + 15°C 2,8 x 1237 71.4 0.8 x 1219 2.8 x 1237 64.3 1.0 x 1219TABLE II STEEL COMPOSITIONMn Si AlAim Analysis (wt.%) 0.07 0.45/0. ,55 0.05/0.07 0.25/0. ,35 0.03/0.06Ladle Analysis (wt.%) 0.074 0.52 0.065 0.005 0.26 0.029Strip Width 0.5 mm 0.08 0.53 0.07 0.004 0.27 0.0280.65 mm 0.08 0.53 0.06 0.003 0.26 0.0290.80 mm 0.08 0.55 0.07 0.004 0.28 0.0331.00 mm 0.08 0.56 0.07 0.004 0.29 0.0311.2 mm 0.08 0.56 0.07 0.004 0.29 0.031 I t- oAim Analysis (wt.%) 0.10 0.45/0. ,55 0.05/0.07 0.25/0. .35 0.03/0.06Ladle Analysis (wt.%) 0.105 0.52 0.055 0.005 0.26 0.047Strip Width 0.65 mm 0.10 0.55 0.07 0.005 0.30 0.0440.8 mm 0.10 0.55 0.06 0.004 0.30 0.0471.0 mm 0.10 0.55 0.06 0.005 0.31 0.043AISI 1006(range) 0. 05/0.06 0.29/0. ,35 0.008/0.012 0.013/0.020 - — 0.020/0.050The test coils were then processed in a con¬ tinuous annealing line having in sequence a soak furnace, a water quench system with submerged nozzles, a tempering furnace, a final water cooling tank for cooling the strip to room temperature, and a temper mill. The line was operated at speeds ranging from 90 metres/min. for the 1.2 mm thick strip to 130 metres/min. for the 0.5 mm strip, with the heating times varying inversely with the line speed. For example, at a line speed of 110 metres/ min. for the 0.8 mm strip, the heating times in the soak furnace and the tempering furnace were 70 and 65 seconds, respectively. The strip temperature in the soak furnace and in the tempering furnace, as determined from radiation pyrometer measurements, were about 788° and 260°C, respectively, and these temperatures were controlled within about + 10°C.A complete evaluation of the mechanical, micro- structural, weldability, and formability character- istics of the steel was carried out on samples selected from various positions in the coils after completion of processing on the continuous anneal¬ ing line. The determination of mechanical prop¬ erties consisted of test sets which included tensile properties, cup height and hole expansion measure¬ ments, longitudinal and transverse stretchbend tests at a high R/t ratio, and r determination. Cup height tests, which measure the formed height of the cup at the onset of diffuse necking and are indi- cators of bulk formability, were performed using a Hille-Wallace hydraulic press to form 178 mm dia¬ meter blanks into dome shapes with a 50.8 mm diameter hemispherically nosed punch. Hole expan¬ sion tests, which determine the percent expansion of a 12.7 mm original diameter hole after the ap¬ pearance of the first through-thickness crack, were performed using the same apparatus with a self- aligning punch to go through the initial hole. Stretch-bend tests consisted of applying force to the center of an edge clamped 50.8 x 209.5 mm test sample with a round end steel punch mounted in the movable platen of a hydraulic testing machine to produce a V-shaped specimen. The hole expansion and stretch-bend tests are measures of edge. form¬ ability. An unsupported sample length of 139.7 mm with an R/t ratio of about 1.6 was employed for all stretch-bend tests. Tensile testing was performed using 50.8 mm gauge length specimens which were pulled at a cross head speed of 12.7 mm per minute on an Instron testing device.The results of the tensile tests, averaged for each coil, are presented in Tables III and IV for the 0.07% carbon and the 0.10% carbon steels, re¬ spectively. In Tables III and IV the designation A.R. refers to the as-received steel condition following the quench, temper and temper-roll treat- ment performed on the continuous annealing line, and the designation S&A refers to the steel prop¬ erties which resulted from straining the as-re¬ ceived steel 2% in tension and aging for one hour at 204°C, which is a simulation of a stamping and pain- baking treatment. Formability and microstructural characterization parameters are presented in Table V. Included in this table are full curve n values,-^jRii nor al (rm) and planar (Δr) anisotropy parameters, stretch-bend depths at an R/t ratio of 1.6, cup height and hole expansion data. In addition, the values of volume fraction martensite and ferrite grain size, which describe the optical microstruc¬ ture, are also shown. In Tables III, IV, and V the designation L and T refer to longitudinal and trans- verse tests. TABLE IIIMECHANICAL PROPERTIES OF 0. 07% CARBON STEELY.S.Gauge Test Test 0.28% Offset T.S. Y.P.E. Eu E In 2 (mm) Direction Condition (MPa) (MPa) (%) (%) X(%)0.5 T A.R. 416 636 0.0 15.3 20.00.5 L A.R. 433 634 0.0 16.2 21.30.5 T S&A 645 663 6.3 11.4 18.40.65 T A.R. 434 629 0.0 15.3 22.20.65 L A.R. 445 628 0.0 15.8 22.20.65 T S&A 648 669 6.1 10.6 18.40.80 T A.R. 448 644 0.0 15.2 22.70.80 L A.R. 446 648 0.0 15.2 22.50.80 T S&A 652 672 5.8 10.8 18.6 I1.0 T A.R. 419 614 0.0 15.7 24.11.0 L A.R. 430 616 0.0 16.2 24.31.0 T S&A 619 651 4.9 11.0 20.21.2 T A.R. 417 594 0.0 16.3 25.31.2 L A.R. 428 595 0.0 16.9 26.11.2 T S&A 604 640 4.5 11.5 21.4TABLE IVMECHANICAL PROPERTIES OF 0.10% CARBON STEELY.S.Gauge Test Test 0.2% Offset .S. Y.P.E. Eu Eτ In 2 (mm) Direction Condition (MPa) (MPa) (%) (%) (%)0.65 T A.R. 450 702 0.0 13.8 19.90.65 L A.R. 484 708 0.0 14.4 20.30.65 T S&A 707 743- 4.1 9.8 16.80.80 T A.R. 460 709 0.0 13.9 19.60.80 L A.R. 483 714 0.0 14.8 20.00.80 T S&A 669 706 4.3 10.8 18.41.0 T A.R. 439 656 0.0 14.7 22.01.0 L A.R. 452 655 0.0 15.5 22.71.0 T S&A 645 691 3.4 10.6 18.8 π ITABLE VFORMABILITY AND MICROSTRUCTURAL PARAMETERSStretchBend Percent Volume n Depth Hole Cup Fraction GrainGauge (Full- K (mm) Expansion Height Marten¬ Size(mm) Curve (MPa) rm Δr L T (%) (mm) site (%) (n)0.07% Carbon0.50 0.158 1003 0.93 0.15 2.36 2.34 18.4 1.57 14.4 3.250.65 0.140 954 0.94 0.31 2.44 2.44 32.0 1.83 15.0 3.600.80 0.136 971 0.98 0.26 2.31 2.26 37.4 1.85 18.4 3.63 H σs1.0 0.141 932 1.01 0.35 2.36 2.39 47.4 1.91 15.9 3.81 I1.2 0.139 896 1.00 0.36 2.54 2.49 66.4 1.96 13.2 3.85 0.10% Carbon0.65 0.140 1071 0.99 0.29 2.26 2.24 24.6 1.80 20.0 3.660.80 0.149 1103 1.05 0.37 2.16 2.18 28.0 1.80 17.5 3.641.0 0.141 1001 1.21 0.49 2.18 2.29 36.8 1.88 18.7 4.08 From Tables III and IV it is seen that for all coils total elongation in the as-received con¬ dition exceeded 18%, specifically ranging from 21 to 27% for the 0.07% carbon coils and ranging from 20 to 23% for the 0.10% carbon coils. The yield strength (0.2% offset) of the as-received steel was in the 416 to 448 MPa range for all guages of the 0.07% carbon steel and in the 439 to 484 MPa range for the higher carbon grade. With proper attention to springback, these strength levels pre¬ sent no stamping press limitation problems. In ad¬ dition, the as-received steel showed no yield point elongation and a yield strength to tensile strength spread averaging about 205 MPa (30 ksi) . From Table V it is seen that the plastic ani¬ sotropy values (r ) are close to unity and that the L and T values of the bend-stretch data are essen¬ tially equal. Furthermore, both the L and T samples underwent 180° flat bends without edge cracking. These data show that the test steel behaved essen¬ tially isotropically. The slight deviation from isotropic behavior, as shown by the marginally high¬ er strengths in the longitudinal samples and the non¬ zero values of the planar anisotropy parameter Δr, do not seriously affect formability. By comparison with AISI 1006 (an aluminum-killed cold rolled steel) , the values of cup height and hole expansion are only about 25 to 35% less for the test steel at any particular gauge, while the yield strength dif- ferences are greater by a factor of two or more.The values of full curve n values and grain size, as shown in Table V, are relatively uniform while the strength coefficient K is somewhat de¬ pendent on carbon level. The average volume frac¬ tion of martensite ranges from about 13% to about 20%. From Tables III and IV, it is also seen that the yield strengths of the formed and aged parts were well in excess of 550 MPa (80 ksi) , being in most cases over 620 MPa (90 ksi) . The strained and aged steel shows a much lower yield to. tensile strength spread but still possesses high values of total elongation ranging from 16 to 21%. Thus, in the case of subsequent unexpected deformation, e.g. an automobile collision, parts formed from the steel of the present invention would be able to withstand a large degree of plastic flow before fracture, an energy-absorbing characteristic not usually associated with steels of this strength level.The attainment of the high part strength fol- lowing forming and paint-baking is dependent on the ability of the steel to respond to the aging treatment. Since all portions of a formed part may not receive 2% strain and the paint cycle may not always consist of one hour at 204°C (400°F) , the effects of lesser amounts of pre-strain and lower aging temperatures on strained and aged properties of the 0.8 mm test steel were also investigated. It was found that for an aging temperature of 204°C, the minimum strength of 550 MPa (80 ksi) is attain- ed without any prestrain. This indicates that the strain imparted by the temper rolling is sufficient to produce the minimum required strain aging re-faA sponse in any stamping. At a lower aging tempera¬ ture of 149°C, the test steel attains the minimum strength as long as the tensile pre-strain is in excess of approximately 0.6%. If the tensile pre- strain level is maintained at 2%, the minimum strength requirement is met even at aging tempera¬ tures as low as 121°C. It was concluded from the data that the steel of the present invention is quite versatile and that, with proper die design to put additional strain into the flat areas of a part, even lower temperature paint-bake cycles are usable.The weldability of the test steel was also evaluated along with that of AISI 1006 using a range of weld evaluation criteria. The welding lobe curves showed that the steel of the resent invention is quite similar to plain carbon steel in terms of weld time - weld current flexibility with no hold- time restrictions being required. Moreover, mechan¬ ical testing of the welds showed, in most cases, high strength levels commensurate with the base metal strength. | Claims1. A process for making a high strength steel with good ductility suitable for automotive appli¬ cations and the like, which comprises: providing a cold rolled strip of aluminum-killed steel containing added phosphorus and silicon as ferrite strengtheners, said steel comprising from about 0.05 to about 0.15 wt.% carbon, from about 0.30 to about 0.60 wt.% manganese, from about 0.04 to about 0.10 wt.% phosphorus, from about 0.10 to10 about 0.50 wt.% silicon, from about 0.02 to about 0.08 wt.% aluminum, and the balance essentially iron; heating said strip to an inter-critical temper¬ ature within a controlled narrow range between the15 A]_ and the A3 critical points such that from about 5% to about 25% austenite is present; water quenching said strip at a rate in excess of the critical cooling rate so that all of the austenite present is converted to martensite,20 whereby to obtain a dual phase ferrite-martensite microstructure having an average volume fraction of martensite of from about 5% to about 25%; and tempering said strip by reheating to a sub- critical temperature;25 the resultant steel strip product having a mini¬ mum total elongation of 18%, being free from ductil¬ ity loss due to room temperature aging, and after straining and heating incident to fabrication of a finished part having a minimum yield strength of30 550 MPa (80 ksi) .'BURtAO PI fa W1PO 2. The process of Claim 1 further characterized in that said heating, quenching, and tempering steps are carried out in a continuous annealing line hav¬ ing a soak furnace for heating the strip to a temp- erature of from about 745°C to about 845°C for a period of from about 20 to about 120 seconds and a tempering furnace for reheating the quenched strip to a temperature of from about 150°C to about' 480°C for a period of from about 5 to about 300 seconds. 3. An improved steel especially adapted for automotive applications and the like comprising an aluminum-killed steel having a dual phase ferrite- martensite microstructure with an average volume fraction of martensite of from about 5% to about 25% and containing added phosphorus and silicon as ferrite strengtheners; said steel comprising from about 0.05 to about 0.15 wt.% carbon, from about 0.30 to about 0.60 wt.% manganese, from about 0.04 to about 0.10 wt.% phosphorus, from about 0.10 to about 0.50 wt.% silicon, from about 0.02 to about 0.08 wt.% aluminum, and the balance essentially iron; and said steel having a minimum total elongation of 18%, being free from ductility loss due to room temperature aging, and after straining and heating incident to fabrication of a finished part having a minimum yield strength of 550 MPa (80 ksi) .4. The steel of Claim 3 further characterized in that said steel has a yield strength of from about 400 to about 500 MPa (58-73 ksi) prior to said straining and heating. 5. The steel of Claim 3 further characterized in that said composition is approximately as fol¬ lows:Carbon 0.07% 5 Manganese 0.45 - 0.55%Phosphorus 0.05 - 0.07% Silicon 0.25 - 0.35% Aluminum 0.03 - 0.06% Balance essentially iron χ0 6. The steel of Claim 3 further characterized in that said composition is approximately as fol¬ lows:Carbon 0.10% Manganese 0.45 - 0.55% 15 Phosphorus 0.05 - 0.07%Silicon 0.25 - 0.35% Aluminum 0.03 - 0.06% Balance essentially iron 7. A steel strip product made in accordance ° with the process of Claim 1. | GUPTA I; INLAND STEEL CO; PREBAN A | GUPTA I; PREBAN A |
WO-1979000645-A1 | 1,979,000,645 | WO | A1 | XX | 19,790,906 | 1,979 | 20,090,507 | new | G21K5 | G21K5 | G21K1, H01J37, H01L21 | H01J 37/302, H01J 37/30A4 | VARIABLE-SPOT SCANNING IN AN ELECTRON BEAM EXPOSURE SYSTEM | An attractive high speed technique for writing microcircuit patterns with a scanning electron spot of variable size is described in the prior art. In such an electron beam exposure system, two spaced-apart apertured mask plates (26, 40) with a deflector (48) there between are included in the electron column of the system. As described herein, a third apertured mask plate (56) and an associated deflector (54) are serially added to the components in the column. In this way, the speed and other performance characteristics of such a system are significantly enhanced. | VARIABLE-SPOT SCANNING IN AN ELECTRON BEAM EXPOSURE SYSTEM This invention relates to an apparatus and a method for fabricating microminiature devices, and more particularly, to a variable-spot scanning technique for use in an electron beam exposure system designed for fabricating large-scale- integrated devices.It is known to increase the pattern-writing speed of an electron b.eam exposure sjstem tEBES) by varying the writing spot dimensions of the electron beam during the, process of scnnning the beam over the surface of a resist-coated workpiece Such a variable-spot scanning technique is described in Proceedings of the Fourteenth Symposium on Electron, Ion and Photon Beam Technology, Edited by: 6. L. Varnell and J. L. Bartelt, 1978, pp.891-895. In one system, two spaced-apart mask plates in the electron column of the system contain res- pectiveiy different apertures therethrough. By interposing a high-speed deflector between the mask plates, it is feasible to rapidly deflect the image of the first electron-beam - illuminated aperture thereby to alter the portion of the second aperture that is illuminated by the beam. In turn, the beam propagated through the second aperture is demagnified to form a variable-size writing spot on the surface of a resist-coated workpiece. With this structure, four scan lines may be traversed simultaneously by the beam in a raster mode of operation. At each address position along such a four-line-at-a-time scan, any specified one of sixteen different combinations (each comprising zero through four electron spots) is formed by the mask plate apertures and transmitted to the workpiece surface. In that way, the pattern-writing speed of an EBES system is significantly increased with respect to a conventional raster scan in which only a single constant spot size can be used. Considerable interest exists on the part of workers in the microelectronics field in trying to increase still further the speed of operation of an EBES-type machine. In attempting to achieve this goal with the aforedescribedOA'.PI A * >. 11PPOO ?NATIO two-mask-plate system, the swath width or the number of scan lines traversed during one scan may be increased.But, as this width is increased, the size and complexity of the aperture configurations in the mask plates tend as a practical matter to become excessive and the design of the illumination system becomes more complicated. Moreover, as this width is increased, the number of addres positions over which the image of the first aperture must be deflected to achieve different variable-spot combinations also becomes excessive. In turn, this complicates the deflection system design and entails longer deflection times, which are undesirable because they impose a limitation on the overall operating speed of the system.Thus, the problem to which this invention is directed is that of providing a variable-spot scanning technique tha improves the speed and other operating characteristics of an electron beam lithographic system.Briefly, this problem is solved in a specific illustrative electron column designed for variable-spot scanning. Such- a column comprises three spaced-apart apertured mask plates. A first high-speed deflector is interposed between the first and second mask plates, and a second high-speed deflector is positioned between the second and third plates. The aperture in the first plate is fully illuminated with an electron beam. The image of that illuminated aperture is then selectively deflected with respect to the aperture in the second plate. In turn, the image propagated through the second plate is selectively deflected with respect to the aperture in the third plate. Finally, the resulting image transmitted through the third plate is demagnified to form a writing spot on the surface of the workpiece. In that way, a variable-size electron spot is generated in a high-speed manner to facilitate precision patterning of an electron- sensitive medium. Specifically, the number of scan lines (swath width) can be significantly increased without sacrificing resolution or other important characteristics. In the drawing:FIG. 1 is a diagrammatic representation of a specific illustrative electron beam exposure system made in accordance with the principles of the present invention;FIGS. 2 through 4 are specific illustrative depictions of the respective geometries of three apertured mask plates included in the electron beam column of the FIG. 1 system;FIG. 5 shows the FIG. 3 mask plate with a deflected version of the image produced by the FIG. 2 plate super¬ imposed thereon;FIG. 6 shows the FIG. 4 mask plate with a deflected version of the particular image depicted in FIG. 5 super¬ imposed thereon;FIGS. 7 through 12 represent sixty-seven different electron spot configurations emanating from the FIG. 4 mask plate as a result of selectively deflecting the images produced by the plates of FIGS. 2 and 3;FIG. 13 shows various additional spot configurations achievable in the FIG. 1 column; andFIGS. 14 through 16 are specific illustrative depictions of the respective geometries of three other mask plates that may be included in the column shown in FIG. 1.FIG. 1 depicts a specific illustrative lithographic apparatus for controllably moving a variable-size electron spot to any designated position on the top surface of an electron-sensitive layer 10 supported on a substrate 12. In turn, the substrate 12 is mounted on a conventional x-y- movable table 16.Various positive and negative electron-sensitive materials suitable for use as the layer 10 are well known in the art. By selectively scanning the electron spot over the surface of the layer 10 in a highly accurate and high¬ speed manner, it is possible to make integrated circuit masks or to write directly on a coated wafer to fabricate extremely small and precise low-cost micorminiature devices. Some suitable electron-sensitive materials for use as the layer 10 are described, for example, in a two part article by L. F. Thompson entitled Design of Poly¬ mer Resists for Electron Lithography, Solid State Technology, part 1:. July 1974, pages 27-30; part 2: August 1974, pages 41-46.The electron beam apparatus of FIG. 1 may be consid¬ ered to comprise two main constituents. One is the column itself and the other is equipment 14 connected to the column for controlling the operation of various elements in the column. The column is characterized by'highly accurate high-speed deflection and blanking capabilities generally similar to those exhibited by the columns described in U.S. Patent 3,801,792, issued April 2, 1974 to L. H. Lin, in U.S. Patent 3,900,737, issued August 19, 1975 to R. J. Collier and D. R. Herriott, and in the previously cited publication. But, in accordance with the principles o the present invention, the column depicted in FIG. 1 is further characterized by a variable-spot size scanning capability that is a significant and unique extension of the technique described above.The other main constituent of the FIG. 1 apparatus comprises control equipment 14. Illustratively, the equip¬ ment 14 is of the type described in the aforecited Collier- Herriott patent. The equipment 14 supplies electrical signa to the described column to systematically control deflectin scanning and blanking of the electron beam. Moreover, the equipment 14 supplies control signals to the x-y table 16 to mechanically move the work surface 10 during the electro beam scanning operation, in a manner now well known in the a The specific illustrative electron column of FIG. 1 in¬ cludes a conventional electron source 18. For example, the source 18 comprises a standard lanthanum boride electron emitter.- In the immediate downstream vicinity of the source 18, the trajectories of electrons emanating from the source go through a so-called crossover or source image point 20 which, for example, is about 50 micrometers in diameter. The after the electron paths successively diverge and converge as the electrons travel downstream along longitudinal axis 22 toward the work surface 10.Illustratively, the electron column of FIG. 1 includes standard coils 24 by means of which the electron trajec¬ tories emanating from the crossover point 20 may be exactly centered with respect to the longitudinal axis 22. Thereafter the electron beam is directed at a mask plate 26 which contains a precisely formed aperture 28 therethrough. (Actually, in the first of several specific illustrative embodiments to be described hereinbelow, the aperture 28 comprises four separate spaced-apar-t apertures. In other embodiments, however, the aperture 28 comprises only a single opening. Thus, the schematic depiction in FIG. 1 of the mask plate 26 is to be regarded as a general representation of a plate having either a single or multiple aperture therethrough.) The beam is designed to uniformly illuminate the full extent of the opening or aperture 28 in the plate 26 and to appear on the immediate downstream side of the plate 26 with a cross-sectional area that corresponds exactly to the conf guration of the aperture 28.By way of example, only, the mask plate 26 of FIG. 1 is shown mounted on and forming an integral unit with an electromagnetic field lens 30. Inclusion of the lens 30 in the FIG. 1 column is not always necessary. And, even when included, the lens 30 may if desired be separate and distinct from the plate 26. If included, the lens 30 is not usually designed to magnify or demagnify the cross* sectional configuration of the electron beam on the down¬ stream side of the plate 26. But in combination with a next subsequent downstream lens, to be described later below, the lens 30 serves to maximize the transmission of electrons along the depicted column and to selectively control the locations of successive crossover points on the axis 22. A bottom view of one advantageous geometry for the apertured mask plate 26 of FIG. 1 is shown in FIG. 2. Illustratively, in accordance with one specific illustrati embodiment made in accordance with the principles of the present invention, the plate 26 comprises a disc of moly¬ bdenum in which four apertures 31 through 34 are formed in a high-precision way by, for example, conventional laser machining techniques.The dashed lines within the openings 31 and 33 of FIG. 2 are included simply to facilitate subsequent discussion. In actuality, of course, each of the op.enings 31 and 33 is a single continuous aperture having straight edges as indicated by the solid straight lines. Thus, the aperture 31 may be regarded as composed of eight basic rectangular segments each defined by two or three solid straight lines and one or two dashed straight lines. Similarly, the aperture 33 may be regarded as composed of two basic rectangular segments each defined by three solid straight lines and a common dashed straight line. Each of the apertures 32 and 34 comprises a single basic rectangul segment. In FIG, 2 the segments included in the aperture 31 are designated Al through A8. The aperture 32 comprises segment A9, the aperture 33 comprises segments Al0 and All and the aperture 34 comprises segment A12. In one particular illustrative embodiment of the present inventio each of the rectangles Al through A12 measures lQ0-by-200 micrometers (μ ). When the plate 26 of FIG. 2 is mounted in the FIG, 1 column, the longitudinal axis 22 of the column is perpendicular to and extends through the midpoin of the square formed by the segments A4 and A5 shown in FIG. 2.The cross-sectional configuration of the electron beam that passes through the mask plate 26 of FIG. 1 is determined by the geometry of the apertures 31 through 34. In turn, this beam configuration propagates through a conventional electromagnetic lens 36 (for example, an annular coil with iron pole pieces) which forms an image o the aforedescribed apertures on a second mask plate 40.OΛ Λ Wi The plate 40 contains a precisely formed aperture 42 and, illustratively, is mounted on and forms an integral unit with electromagnetic field lens 44.A predetermined quiescent registration of the image of the aperture(s) in the mask plate 26 on the plate 40 of FIG. 1 is assured by, for example, including registration coils 46 in the depicted column.The location of the image of the electron-beam- illu inated aperature(s) 26 on the second mask plate 40 of FIG. 1 is selectively controlled in a high-speed way during the time in which the electron beam is being scanned over the work surface 10. This is done by means of deflectors 48 positioned, for example, as shown in FIG. 1 to move the beam in the x. and/or ,y_ directions. Advantageously, the deflectors 48 comprise two pairs of orthogonally disposed electrostatic deflection plates. Electromagnetic deflection coils may be used in place of the electro¬ static plates, but this usually leads to some loss in deflection speed and accuracy. Whether electrostatic or electromagnetic deflection is employed, the deflectors 48 may also be utilized to achieve registration of the image of the aperture(s) in the plate 26 on the second mask plate 40. This is done by applying a steady-state centering signal to the deflectors 48. In that case the separate registration coils 46 may, of course, be omitted from the column.In one specific illustrative embodiment of the principles of this invention, the aperture 42 formed in the second mask plate 40 has the particular configuration shown in FIG. 3, which is a bottom view of the plate 40 included in the FIG. 1 column. For subsequent ease of discussion, the ope-iiing 42 is represented as being divided into multiple constituent rectangular segments designated Bl through B36. In one particular embodiment of this invention, each such segment measures 100-by-200 μm. Centrally located dot 50 in FIG. 3 indicates the location of the longitudinal axis 22 of FIG. 1. In its quiescent condition, that is, in the absence of deflection signals applied to the unit 48 of FIG. 1 , images of the apertures 31, 32 and 34 of the mask plate26 (see FIG, 2) are transmitted through portions of the aperture 42 of the plate 40 of FIG. 3. Illustratively, the aperture image projected by the lens 36 (FIG. 1) onto the plate 40 corresponds exactly in size with the dimensions of the apertures 31 through 34. (If desired, the lens 36 may, of course, be designed to achieve other than a 1:1 projection of the apertures 31 through 34. Or, in some cases of practical interest, the lens 36 may be omitted altogether.) By means of the coils 46, the image so projected is precisely centrally registered on the plate 40. More specifically, in that central or quiescent registration, the image of the aperture 31 corresponds exactly in size and directly overlies the portion of the aperture 42 composed of segments B19 throug B26. Accordingly, the image defined by segments Al throug A8 is transmitted in its entirety through the mask plate 40. In addition, the images of the apertures 32 and 34 directly overlie the segments B'34 and B36, respectively, of the aperture 42 and are, accordingly, also quiescently transmitted through the plate 40. But, quiescently, the image of the aperture 33 is projected onto a nonapertured portion of the plate 40 and, hence, is not propagated through the plate 40.In accordance with the principles of the present invention, the electron image transmitted through the mask plate 40 of FIG. 1 propagates downstream through electro- magnetic lens 52 and deflectors 54 to impinge on a third apertured mask plate 56, which is, for example, mounted on field lens 58 to form an integral unit therewith. Plate 56 includes aperture 60 therethrough.In the absence of signals applied to the deflectors 54, the aforedescribed quiescent image transmitted through segments B19 through B26, B34 and B36 of FIG. 3 is project onto the mask plate.56 to achieve a quiescent registrationBUK_OM Λ-- - therewith. (For this purpose, registration coils 47 may advantageously be included in the column of FIG. 1.) In that condition, the image emanating from the segments B19 through B26 of the aperture 42 of FIG. 3 directly overlies the aperture 60 in the mask plate 56 of FIG. 4 and is, accordingly, quiescently transmitted through the plate 56.In FIG. 4, the aperture 60 is indicated as being divided into eight equal-sized rectangular segments designa¬ ted Cl through C8. In one particular embodiment of the invention, each such segment measures 100-by-200 μm.Centrally located dot 62 in FIG. 4 indicates the location of the longitudinal axis 22 of FIG. 1.The cross-sectional area of the electron beam transmitted through the apertured plate 56 of the electron column of FIG. 1 is subsequently demagnified. This is done by means of three conventional electromagnetic lenses 64, 66 and 68 positioned downstream* of the plate 56. In one specific illustrative embodiment of the principles of the present invention, these lenses are designed to achieve overall demagnif ication of the beam propagated therethrough by a factor of 400. More particularly, these lenses are selected to de agnify the aforementioned cross-sectional area of the beam transmitted by the mask plate 56 and to image a reduced counterpart thereof on the work surface 10. For an overall demagnif ication of 400, and for the specific ill¬ ustrative case in which the cross-section of the beam immed¬ iately downstream of the plate 56 measures 200-by-800 μm the electron spot imaged on the surface 10 will quiescently be a rectangle 0.5 μm wide and 2.0 μm high. The other elements included in the column of FIG. 1 are conventional in nature. Except for one deflector unit, these elements may, for example, be identical to the corresponding parts included in the columns described in the aforecited patents and application. These elements include a beam-limiting apertured plate 70, electrostatic beam blanking plates 72 and 74. An apertured blanking stop plate 76 and electromagnetic deflection coilsIjTTKfcATTOA-tPl 78 through 81.If the beam blanking plates 72 and 74 of FIG. 1 are activated, the electron beam propagating along the axis 22 is deflected to impinge upon a nonapertured portion of the plate 76, In that way the electron beam is blocked during prescribed intervals of time from appearing at the surface 10. If the beam is not so blocked, it is selectively deflected by the coils 78 through 81 to appear at any desired position in a specifie subarea of the work surface 10. Access to other subarea of the surface 10 is gained by mechanically moving the surface by means, for example, of a computer-controlled micromanipulator, as is known in the art.In addition, the column of FIG. 1 includes deflectors 82. The purpose of these deflectors will be described later below.The column shown in FIG. 1 may be controlled by equipment 14 to operate in its so-called raster-scan mod of operation. This mode, which is described in the cited Coll ier-Herriott patent and in the cited publicati involves successively scanning the beam on the work surface 10 along parallel equally spaced-apart scan line Illustratively, each such scan line may be considered to comprise multiple equally spaced-apart address positions At each address position during traversal of a scan line the electron beam is blanked or not in the manner described above. Additionally, in accordance with the principles of the present invention, the area of the bea that impinges upon the work surface 10 at each address position is selectively controlled.As the variable-size electron spot is deflected along a row of the scan field, the spot is intensity modulated by the beam blanking plates 72 and 74 at, for example, a 20 megahertz rate. This modulation rate corresponds with a single-address exposure time of 50 nanoseconds, which is compatible with the sensitivities of available electron resist materials.ξ\} \ Q &RN In the particular illustrative example specified herein, the maximum size of the rectangular electron spot imaged onto the surface of the layer 10 of FIG. 1 is, as specified above, 0.5 μ wide and 2.0 μm high. For 5 this particular case, the aforementioned scan lines in the raster mode of operation are usually spaced apart 2 μm from each other and successive address positions along a scan line are spaced 0.5 μm apart.For purposes of a specific example, it will be assumed10 that the system represented in FIG. 1 is programmed to form any one at a time of sixty-eight different electron spot configurations. In accordance with the principles of this invention, this is done by selectively applying signals to the deflection units 48 and 54. The result15 of applying no deflection signals (i.e. , an all-zero deflection set) to these units was specified above in connection with the description of FIGS. 2 through 4 and represented in FIG. 7(a). The result of applying one other particular set of deflection signals to the units20 48 and 54 will be specified immediately belowwith the aid of FIGS. 5 and 6. Further, the sixty-six additional different spot conf gurations achievable by respectively applying sixty-six other deflection signal sets to these units will be specified below in connection with the25 representations of FIGS. 7 through 12.By means of the deflection unit 48 shown in FIG, 1, the image transmitted through the apertured mask plate 26 and projected onto the plate 40 can be deflected in the x. and/or y_ directions. Assume, for example, that30 with respect to the _x and y_ axes shown in FIG. 5, the transmitted image is deflected zero half-address positions in the positive _x direction and two half-address positions in the negative y_ direction. The resulting registration of the Al through Al 2 image with respect to the35 aperture 42 in the mask plate 40 is indicated in FIG. 5. As specified above, successive address positions are spaced apart 0.5 μm on the surface of the workpiece 10. Accordingly, a so-called half-address position equals a distance of 0.25 μm on the workpiece 10 and 100 μm in the plane of the mask plate 40 or in the plane of the plate 56. Hereinafter, the x,y deflection imparted to the electro beam by the deflection unit 48 will be designated Dl :x,y, where x. and are integers indicating the number of half- address positions that the beam configuration has been moved in the x. and y. directions, respectively. Accordingly, in FIG. 5 the designation Dl:0,-2 has been included' to represent the particular aforespecified deflection amplitude imparted to the image transmitted through the plate 26 and projected onto the plate 40.As seen in FIG. 5, only the rectangular segments Al , A2, A7 and A8 of the image formed by the apertured mask plat 26 are transmitted through the aperture 42 in the second mask plate 40. In turn, if this image is deflected by the unit 54 two half-address positions in the negative x. direction, and two half-address positions in the positive y_ direction, the registration of the segments Al , A2, A7 and A8 on the third apertured mask plate 56 is as depicted in FIG. 6. It is apparent that only the segments Al and A2 are transmitted through the aperture 60 toward the surface of the workpiece 10. In FIG. 6, and in the representations of FIGS. 7 through 12., the stippled portion or portions of the aperture 60 indicate the part(s) thereof illuminated by the propagating electron.In FIG. 6 and hereinafter, the x,y deflection imparted to the electron beam by the deflection unit 54 is designated by the format D2:x,y, where x. and y_ are integers indicating the number of half-address positions that the beam has been moved in the _x and y_ directions, respectively. Accordingly, FIG. 6 includes the designation D2:-2,2. Each solid line rectangle included in FIGS. 7 through 12 may be considered to represent the aperture 60 in the third mask plate 56 of FIG. 1. Associated with each such rectangle is a pair of deflection signal indicators designated Dl , D2, which are formatted as specified above.And, as indicated earlier, the stippled portion of each rectangle represents the part thereof illuminated by the propagating electron beam.The limiting number of spot configurations represented in FIGS. 7 through 12 is simply a specific illustrative set formulated in accordance with certain criteria established therefor. Thus, for example, this particular set was devised based on the specif cation that constituent parts simultaneously emanating from the aperture 60 must be at least 200 μm apart in the x. direction in the plane of the downstream side of the third mask plate 56. For an example of a configuration in which the constituents are exactly 200 μm apart, see FIG. 7(j). Additionally, the design rules for this set specify that only the topmost and/or bottommost rectangular segments of a spot configuration can be as small as 100 μm in the x. direction. See Fig, 9(h) for an example of a configuration which includes two such 100 μm-highconstituents. All other permitted spot constituents in the set depicted in FIGS. 7 through 12 measure at least 200 μm in the x. direction. Significantly, the set of spot configurations shown in FIGS. 7 through 12 exhibits 0.25 μm precision in the x. direction at the surface of the workpiece 10.It is emphasized that the particular set of electron beam configurations represented in FIGS. 7 through 12 is illustrative only. In accordance with the principles of this invention, various modifications thereof can be devised.By applying appropriate deflecting and/or centering signals to the column of FIG. 1, variations of the particular configurations described above can easily be achieved. For example, the beam configurations transmitted through the third mask plate 56 of FIG. 1 can be designed to extend in the y_ direction less than the full width of the aperture 60. In addition, these configurations can be designed to e-xtend in the x_ direction by less than the particular above-specified one-quarter-micron address size. Several such limited-extent spots are represented in FIGS. 13(b) through 13(.j). Each of these spots may be considered a variant of the previously specified configura tion depicted in FIG. 7(a), which is also shown in FIG. 13(a) .In accordance with an aspect of the principles of the present invention, the _ or scanning-direction extent of the electron spot directed at the workpiece 10 can be varied during the scanning process. This capability is the basis for selectively varying the electron exposure level at the workpiece surface, thereby improving the sharpness of feature edges that extend in the x. direction. Ordinarily, the leading and trailing edges of an irradiated feature exhibit a ramp exposure profile. In turn, this leads as a practical matter to a lack of sharpness or definition in these edges. But, in accordance with the principles of this invention, edge sharpness in exposed features is significantly improved by controlling the herein-described system to achieve exposure profiles that are rectangular in nature. This is done by applying time-varying signals (as well as constant signals to achieve a specified spot configuration) to the unit 54 (FIG. 1) between masks 40 and 56 to continuously deflect the image transmitted through the aperture 42 in the negative y_ direction during selected intervals at the beginning and end of a feature exposure. Illustratively, the velocity imparted to the writing spot on the surface o the workpiece 10 by the time-varying deflection signal applied to the unit 54 is equal and opposite to that imparted to the spot by the scanning coils 78 through 81. Initially, at time t-j , at the leading edge of a feature, both the constant and time-varying components of the deflection signals applied to the unit 54 are turned on, whereby the image transmitted by the aperture 42 isO.MPI. A * WiPO projected onto the mask plate 56 directly adjacent the aperture 60, As the coils 78 through 81 sweep the writing spot over the workpiece 10 in the positive y_ direction the time-varying component of the deflection signals continuously moves the image transmitted through the aperture 42 in the negative y_ direction into the aperture 60 until at t2 the aperture 60 is filled with the configuration specified by the plates 26 and 40 and their respectively associated deflectors. Between t2 and t3 only the constant deflection signal required to' produce the desired spot shape is applied to the unit 54. The beam, of course, continues to scan over the feature. At time to, the time-varying component of the deflection signals is turned on again thereby once more sweeping the image of the aperture 42 in the negative ,y_ direction, this time out of the aperture 60. Finally, at time t* the spot is blanked by this action.In writing patterns with an EBES machine, a deliberate overlapping of feature stripes by, for example, a few tenths ofa micrometer is sometimes called for in connection with the butting of adjacent stripes. But, because of the deliberate double exposure in the overlap region, a broadening occurs which tends to bridge small gaps between parallel edges crossing the butt. in accordance with one aspect of the principles of the invention, broadening effects during purposeful over¬ lapping of stripe features in a lithographic process can be eliminated by selectively reducing the exposure only in the region of overlap. This is done, for example, by generating a reduced-width overlap beam tab at the beginn¬ ing and/or end of each stripe to be overlapped. Thus, for example, a beam configuration of the general type depicted in FIG. 13(b) may be utilized at the beginning and/or end of a stripe having terminal portions which are to overlap other stripe portions. During non-overlapping portions of the stripe scan, however, the beam conf guration is advan¬ tageously of the full width-type depicted in FIG. 13(a). In that way, the electron exposure in overlapping regions may be controllably reduced relative to that achieved with constant-width beams, thereby to minimize broadening effects in the overlapping regions. Embodiments of the present invention are advantageously suited to perform lithographic processing in a raster scan mode of operation of the- type described in the afore¬ cited Coll ier-Herriott patent. But the principles of this invention are also applicable to a lithographic system adapted to operate in a modified raster scan mode in which the beam also is vector scanned over a limited field or in effect stepped along the raster lines. Or these principles are also applicable to a system operated in a standard vector scan mode without any raster scanning. In these other modes, the deflection unit 82 shown in FIG. 1 may be utilized during specified intervals to exactly counter the y direction deflection otherwise imparted to the electron beam by the scanning coils 78 through 81. Accordingly, during those intervals the variable-size writing electron spot is in effect held stationary on the surface of the workpiece 10. A feature to be defined on the surface is formed by abutting successive such stationary spots in a mosaic-like manner.A particular advantageous alternative pair of apertured mask plates adapted for inclusion in the illustrative column of FIG. 1 is depicted in FIGS. 14 and 15, respective Plate 27 with aperture 29 therethrough (FIG. 14) may be substituted for the plate 26 of FIG. 1, and plate 41 with aperture 43 (FIG. 15) may be substituted for the plate 40. In that particular case, it is further advantageous to configure the third apertured mask plate as shown in FIG.16Plate 57 with aperture 61 therethrough (FIG, 16) is designed to be substituted for the plate 56 of FIG. 1 and to form a set with the particular pair of mask plates shown in FIGS. 14 and 15 . Illustratively, the aperture 61 comprises a square whose size is sufficient to pass the | (received by International Bureau on 21 May 1979 (21.05.79))1. -. -. -, Apparatus for fabricating micro¬ miniature devices by selectively irradiating a radiation- sensitive layer (10) with a variable-spot-size radiant beam to define a pattern in said layer, said apparatus comprising first and second mask plates (26, 40) spaced apart from each other along a main longitudinal axis (22), the first and second mask plates respectively having a first and second pattern-delineating aperture configuration therethrough, means (18) for directing a radiant beam at said first mask plate (26) to illuminate its aperture configurati'on (28) in its entirety, means (36) for imaging the first aperture configuration on the second mask plate, means (48) for selectively deflecting the image of the beam transmitted through the first aperture configuration (28) to control the alignment of said image with respect to the second aperture configuration (42) thereby to vary the cross-sectional area of the beam transmitted through said second mask plate,CHARACTERIZED IN THAT said apparatus further comprises a third mask plate (56) spaced apart from said second mask plate (40) along said axis (22), the third mask plate having a third pattern- delineating aperture configuration (60) therethrough, means (52) for imaging on the third mask plate that part of the second mask configuration through which the beam is transmitted, and means (54) for selectively deflecting the image of the beam transmitted through the aperture configuration (42) in said second mask plate (40) to control the alignment of said image with respect to the third aperture configuration, thereby to vary the cross- sectional area of the beam transmitted through said third mask plate toward said radiation-sensitive layer (10). mentioned deflecting means (48, 54) for applying sets of signals thereto to deflect said images along orthogonally disposed axes that are perpendicular to said main axis (22) thereby to establish for each set of signals a specified variable-spot-size image emanating from the aperture configuration (60) in said third plate (56) .4. Apparatus as in claim 3 further including means (78 through 81) for scanning said beam in a raster-scan fashion over said radiation-sensitive layer (10) along plural scan lines each of which has a multiplicity of address locations therealong.5. Apparatus as in claim 4 wherein the aperture configurations (28, 42, 60) in said first, second and third mask plates (26, 40, 56) are respectively different. 6. Apparatus as in claim 3 further including means (82) for scanning said beam in a vector-scan fashion over said radiation-sensitive layer.7. Apparatus as in claim 6 wherein the aperture configurations (28, 42) in said first and second mask plates (26, 40) are the same and the aperture configura¬ tion (60) in said third mask plate (56) is different therefrom.8. Apparatus for scanning a variable-spot size radiant beam over a work surface to irradiate selected portions of the surface in connection with the fabrication of a microminiature device, said apparatus comprising first, second and third mask plates spaced apart from each other along a main longitudinal axis of said apparatus and each having an aperture configuration therethrough, means for directing a radiant beam at said first mask plate to illuminate in its entirety the aperture configuration therethrough. and means interposed between said first and second mask plates and between said second and third mask plates for deflecting the image of the beam transmitted through the aperture configuration in said first plate with respect to the aperture configuration in said second plate and for deflecting the image of the beam transmitted through the aperture configuration in said second plate with respect to the aperture configuration in said third plate to illuminate any specified portion of the aperture configuration in said third plate thereby to define a variable-spot-size beam for propagation toward said work surface,9. Apparatus as in claim 8 further including means for demagnifyi g the image transmitted through the aperture configuration in said third plate and for focusing said image onto said work surface, and means for scanning said demagnified and focused image over said work surface to selectively irradiate portions thereof. 10. Apparatus as in claim 9 wherein the-aperture configuration in said third mask plate comprises a single rectangular opening therethrough, and wherein said apparatus further comprises means for controlling said deflecting means to cause said beam to illuminate at least one variable- width portion of said rectangular opening during specified scanning intervals.11. Apparatus as in claim 10 further comprising means for projecting the image of the beam transmitted through the first mask plate onto the second mask plate and for projecting the image of the beam transmitted through the second mask plate onto the third mask plate.12. A method for fabricating microminiature devices by the technique of scanning a variable-spot-size radiant beam over a work surface to irradiate selected portions of the surface in accordance with a prescribed pattern, said method comprising the steps of directing a radiant beam at a first mask plate which includes an aperture configuration therethroug to illuminate said configuration in its entirety, directing an image of the beam transmittedOΛ' _A . WIP through the aperture configuration in said first mask plate onto a second mask plate which includes an aperture conf guration therethrough to align said image in a specified relationship with respect to the aperture configuration in said second mask plate whereby only that portion of the image that overlies the aperture configuration in said second mask plate is transmitted through said second mask plate, and directing the image transmitted through the second mask plate onto a third mask plate which includes an aperture configuration therethrough to align said last-mentioned image in a specified relationship with respect to the aperture configuration in said third mask plate whereby only that portion of said last-mentioned image that overlies the aperture configuration in said third mask plate is transmitted through said third mask plate toward said work surface.13. A method as in claim 12 further including the steps of scanning said beam over said surface along successive scan lines in a raster-scan mode of operation, and intensity modulating said beam at each address position of a scan line.14. A method as in claim 13 further including the step of controlling said directing steps to illuminate the aperture con iguration in said third mask plate less than a standard prescribed width thereof in the direction of scanning during intervals in which overlapping portions of the surface are being irradiated.15. A method as in claim 13 further including the step of controlling said first-mentioned directing step to continuously deflect the image transmitted through the aperture configuration in the second mask plate in a direction opposite to the scanning direction duringll J R EΛ ,_OMPI__ ■ Λ, W1PO . selected intervals at the beginning and end of an irradiated surface portion to achieve edge sharpness of said portion.16. A method as in claim 12 further including the steps of scanning said beam over said surface in a vector-scan mode of operation.QfΛPl STATEMENT UNDER ARTICLE 19The new claim recites first, second and third pattern- delineating apertures in the first, second and third mask plates, respectively. Further, it now recites means (36) for imaging the first aperture configuration on the second mask plate and means (52) for imaging on the third mask plate that part of the second mask configuration through which the beam is transmitted._QMPL- | WESTERN ELECTRIC CO; WESTERN ELECTRIC CO INC | COLLIER R |
WO-1979000652-A1 | 1,979,000,652 | WO | A1 | EN | 19,790,906 | 1,979 | 20,090,507 | new | F01C3 | null | F01C3 | F01C 3/02 | MACHINE FOR EXPANSION OR COMPRESSION OF GASES OR VAPOURS | A machine of positive displacement type for the expansion or compression of elastic fluids, wherein torque created or applied effects directly the power shaft, bearings of the power shaft are loaded only by weights of corresponding rotary masses, sealing lubrication is not used and the structure of the machine should accountably facilitate achieving of low losses. The machine includes working spaces (5) defined by a rotary working member (1) and a surrounding body structure (4), and moving circumferentially with the working member, their main direction joining with said circumferential direction. The working spaces (5) are divided into a process space (6) and a transferring space (7) by a partition wall (15) belonging to rotary non-working reacting members (8) which are perpendicular to the working member and synchronized therewith and of so firm structure that they can transmit to the outside of the working member great forces due to a pressure difference between said spaces (6, 7). Said forces can be compensated by a programmed pressure effect onto a counter-surface (11) of the reacting member. Depending on the direction of rotation of the working member either expansion or compression of elastic fluid circulating through the machine is performed. Rotary valves (23) are preferably used for achieving a cyclic closing of the process space (6). A momentary area of the valve opening can essentially correspond to a momentary area of the partition wall (15). A partition wall forming part (10) of the reacting member is preferably provided with only one transition sector (77) for changing the process cycle, whence requirements as to synchronization are low. Light sealing members (110) are preferably used to reduce remaining loss effects due to error in synchronization. Clearances not depending on synchronization may be maintained small by using temperature control of respective parts. A major part of the clearances can be provided with a labyrinth seal (61, 103, 104) for reducing the speed of gas leak. | MACHINE FOR EXPANSION OR COMPRESSION OF GASES OR VAPOURSTechnical FieldThe present invention relates to a machine for expan¬ sion or compression of gases or vapours and to a use of 'the machine for storing and recovering energy. The machine may also be used more generally as an engine or a compressor or in some other machinery involving volume alterations of gases or vapours.The present invention also relates to perhaps the most important use of the invented machine, namely for storing electric or mechanical energy.Background ArtMachines performing expansion or compression of gases or vapours may be classified into turbo-machines and posi¬ tive displacement machines. Advantages associated with tur¬ bo-machines include great specific power, no need of power transmitting mechanisms, small wear and suitability for use of relatively cheap fuels in connection with a heat power process. Disadvantages include losses of 10-20% in conse¬ quence of kinetic way of action, poor suitability for light gases as helium or hydrogen and a necessity to have the first part of a turbine at the maximum temperature of gas or steam in connection with a heat power process.Typical drawbacks associated with known positive dis¬ placement machines include the need of power transmitting mechanisms, low specific power and disadavantages associated with sealing lubrication, namely power losses, temperature limitations as well as rapid wear. On the other hand, type not using sealing lubrication are generally characterized by a great gas leak due to structures where sizes of leaki clearances depend on mutual synchronization between moving members, said synchronization being imperfect e.g. because of free play in gears. The necessity of transmitting powe through those mechanisms makes it further more difficult t avoid said play. The lack of possibilities to reduce the speed of gas leak to a value lower than the velocity of so is another main reason for great losses. Moreover, structu of some machines are suitable for low pressure levels only Also, the state of the art does not offer a profitabl method for storing electric energy on a large scale, parti larly for longer periods. Known possibilities include stor as potential energy by pumping water into a reservoir si ating on a higher level, a production of hydrogen, compres air storage in caves, super-conducting magnetic energy sto age, flywheel storage and electrochemical accumulators. Th drawback of the first mentioned alternative is that a size of a reservoir is so enormous that even diurnal storing wo encounter difficulties, not to mention an annual storing. situtation is quite similar in the case of compressed air storage, which might be fitted for short term storage in s special sites. The only known method suitable for a long t storage would be a production of hydrogen, but its drawbac is a poor efficiency due to losses in production of hydrog in storing as well as in a heat power process after storin Also a danger of an explosion and diffuculties in storing consequence of a low boiling point of hydrogen may be con¬ sidered serious disadvantages. The other alternatives men tioned are far from profitable, particularly for long term storage.Disclosure of InventionAll drawbacks mentioned above may be avoided by uti¬ lizing the machine in accordance with the present inventio The present machine is characterized by small losses, no need of power transmitting mechanisms, in certain appli¬ cations even a very great specific power, good suitability for light gases, small wear, no need of sealing lubrication and good suitability for high pressure levels as well as for various temperature levels.One possible and at the same time important application of the invented machine is the use of a component in heat power processes. By now, a steam power plant with turbines as engines is do inantly used for accomplishing an elctri- city producing heat power process having a high annual de¬ gree of use, because in said case it is important to achieve good efficiency and to use as cheap heat energy as possible. To maximize electric efficiency a condensing turbine must be used having an outlet pressure of about 0.04 bars only. Due to a low medium pressure the specific power of a turbo- machine in the application mentioned is not so good despite a great volume flow. A closed gas process, e.g. Brayton- cycle, may include three important advantages as compared with a steam process called Rankine cycle. Firstly, in a closed gas process the pressure level may be chosen freely, resulting in a great specific power even with a moderate volume flow, if the pressure level used is high enough. Secondly, a gas process has no limitations of steam as for temperature scale usable. Thirdly, if a Brayton-cycle is used, the waste heat of the process is released in a form usable for low or me¬ dium temperature purposes, as heating or water distillation, without any need for compromizing between electric efficiency. The reason why a gas process is not widely used in this field lies in the fact that the only machine suitable for the pro¬ cess known heretofore has been a turbo-machine having so great losses that the efficiency of the gas process would remain essentially lower than that attainable with a Rankine cycle. If alternatively the invented machine were used as engines and compressors in a gas process using Brayton-cycle, provided with a heat exchanger between hot and cold sides, the efficiency attainable would be comparable with that of the steam process. Additionally, 1 ~ the temperature range utilized were extended over that used in connection with water steam process , an even considerably higher electri or mechanical efficiency than earlier could be achieved. Furthermore , the waste heat would be in a suitable form various purposes . Heat energy used in a closed process m naturally be originated from any source. Thus , besides f also solar or nuclear energy might be utilized .One reason that would facilitate the use of a highe maximum temperature than earlier at least in some appli¬ cations is the advantage offered by the invented machine , namely that in contrast to turbine , essential structures the invented machine need not be at the maximum temperat of the working gas , but in the case of a Brayton-cycle w heat exchanger between hot and cold sides , said structur may be at the temperature of the working gas after expans or remarkably lower , even near ambient temperature .The invented machine might be very advantageous in energy applications , because it can be manufactured as a smaller unit than a turbine and still have a good effici as well as good specific power . The weight of the machin unit power is remarkably lower than that of a condensing bine. As by using Brayton-cycle also a waste heat of the cess is released in a useful form, all heat energy focus to an absorbator by using mirrors could be utilized, partly as electricity, partly as heat. Thus there would be better changes tha earlier to make prof itably heliostats reflecting radiation onto an absorbator.The invented machine with low losses may be valuable also in certain' heat pump applications, e.g. for utilizing some low terrpera- ture waste heat or for air conditioning.The invented machine fits particularly well to the purpose of storing energy, first of all due to minimum losses involved with the machine, and also due to good suitability for light working gases su as helium. Without the invented machine it would not be possible to carry out the storing process in a profitable form.The storing process in accordance with the invention would be particularly advantageous in connection with use of solar, wind or wave energy. The drawback associated with these alternative energy sources is a temporal variation'BU• O\Y of production. If the storing of energy is not arranged, the role of the alternatives mentioned is restricted to a partial saving of fuel<? , because then a full capacity of other types of power stations must exist.By using the process in accordance with the invention a considerably higher efficiency of storing may be achieved than in the hydrogen alternative. Additionally, the inven¬ ted method may be regarded harmless due to very simple materials used. The process is suitable also for. annual storing, which is an important aspect especially when so¬ lar energy is used. With the aid of the invention it is possible to base energy production even totally on solar energy. For supplying needs of vehicles the stored energy can be converted into some fuel, e.g. hydrogen. Even in this relation the invented process would be advantageous in eliminating the need for large hydrogen reserves, be¬ cause a conversion into hydrogen may be done fairly well in time with consumption.The invented machine is of positive displacement type having rotating moving parts. Expansion or compression is performed within the machine in periodically closing spaces, the volumes of which are varying^ periodically. No power transmitting mechanisms are necessary, but a torque caused by gas forces can effect directly a rotating working member and thus also a power shaft firmly connected to said mem¬ ber, the aspect mentioned being extremely important especial¬ ly in the case of a high-power machine. Gas forces loading the rotor are symmetric in such a way that the only forces effecting the corresponding bearings are orginiated from the weight of the rotor, whence friction losses in the bearings remain unessential, particularly in connection with a closed process with a high pressure level . No sealing lubrication is used, but clearances are kept so small and the speed of rotation so high that gas leak remains rela¬ tively small. The speed of rotation can be selected so that relative importance of kinetic energy of the gas remains unessential. The invented machine includes a body structure defin¬ ing at least one rotation space therein, a working member rotatably mounted within said rotation space, one portion of the working member facing the surrounding body forming, together with the surrounding body, at least one working space moving with the working memeber circumferentially, and another portion of the working member being. provided with at least one separating wall extending close to the wall of the rotation space. One functional basic unit of the machine includes n rotating reacting members equally distributed around the periphery of the rotation space in such a way that each reacting member is rotatable around its own axis, which is essentially perpendicular to the rotation axis of the working member and preferrably situ¬ ated totally outside the rotation space of the working member. Within each functional basic unit the number of aforesaid working spaces situated one after another in circumferential direction is equal to the number of said reacting members or to an integral multiple thereof.Each reacting member extends partially into the rota¬ tion space of the working member and has a part, which forms a transversal partition wall dividing the working space in question into two parts, a process space and a transferring space, respectively, the volumes of which vary periodically according to rotation of the working member. Said partition wall forming part is shaped to have one, at the most two rotation sectors, called in the following transition sectors, in which the distance of the outer edge line to the rotation axis of the reacting mem¬ ber has a minimum value. The machine also includes flow conduits in the body structure for the inlet and outlet of gas or vapour and at least one first opening in the body part surrounding the rotation space on the process space side of the partition wall for providing connection between the process space and the corresponding flow con¬ duit, and at least one second opening positioned in the body structure on the transferring space side of the par¬ tition wall for providing connection between the trar.s-PI ferring space and the corresponding flow conduit.The machine further includes means for closing perio¬ dically the said first opening and synchronizing means in¬ terconnecting said working member, reacting members and closing means so that the connection between the process space and the corresponding flow conduit is established during such a part of the process cycle, during which the working space moves circumferentially over a certain dis- 'tance, at one end of which the partition wall is in the process space end of the working space and that once for each process cycle a passage of one separating wall of the working member through one transition sector in the parti¬ tion wall forming part of the reacting member is established.The working member rotating around its middle axis may be firmly connected to a power shaft or they may be originally made of one single body. In an alternative em¬ bodiment an electric machine may directly load the working member, in which case the role of the shaft, if any, is only to support and position the working member.Reacting members of one functional basic unit are situated at equal positions in the direction of the rota¬ tion axis of the working member and in the direction of the circumference thereof at intervals of an angle of 360 /n, in other words the whole circle divided by the number of reacting members. In the foregoing definition n is a po¬ sitive integer, one or greater. In a preferred embodiment n=2, which is already resulting in a symmetric construction and avoiding of transversal reaction forces on the power shaft. The partition wall forming part of the reacting member is in practice a surface, which joins a fictive surface of revolution in realtion to the rotation axis of the reacting member. A transition gap permitting a passage of the separating wall in the working member there through in connection with change of the process cycle is situated . at a certain rotation sector of the partition wall forming surface.Working spaces of one functional basic unit are situ- ated one after another in the circumferential direction of the working member and, in contrast to a screw-compresso so that their main direction joins with said circumferentia direction. The working spaces are situated at equal positio in the direction of the rotation axis of the working member and in the circumferential direction at intervals of an angle, which is the whole angle divided by the number of reacting members or by an integral multiple of it.Within one functional basic unit subsequent process cycles form a continuous train, since all reacting members of said unit preferably operate in the same phase.If the reacting member is provided with one transition sector, one revolution of the said member corresponds to one process cycle, whereas one revolution of the working member corresponds to the number of cycles equal' to the number of working spaces one after another.The process space being closed, an expansion or com¬ pression process takes place inside it depending on the direction of the rotation of the working member. During one process cycle the volume of the process space in expansion use increases from zero to a maximum value, and corres¬ pondingly in compression use decreases from a maximum value to zero. When changing from one process cycle to the follow a sudden change occurs, because the reacting member is then passing to the following space over a separating wall in th working member. Due to rotating members used, a relative circumferential movement of the partition wall in the worki space takes place always in the same direction as far as a certain process is concerned. In expansion use an increase of volume in the process space is accompanied by a corres¬ ponding diminishing of volume in the transferring space. Accordingly, during each cycle gas expanded during the previous cycle is forced away from the transferring space into the corresponding flow conduit. Correspondingly, when the machine is used as a compressor, during each cycle new gas is sucked into the transferring space from the corres¬ ponding flow conduit. During the next cycle the same gasjUK OΛ- amount is exposed to a compression process, being then pushed over the valve point into the flow conduit corres¬ ponding to the process space.The flow between the transferring space and the corres¬ ponding flow conduit may in practice occur through that opening in the body surrounding the rotation space of the working member, through which also the corresponding react¬ ing member is extending into the working space in question.One main advantage associated with the invented machine is that the reacting member does not require work for its rotation, but is rotating freely. To obtain this, the rotation of the reacting member is transversal in relation to the movement of the working member and working spaces moving therewith, and a higher pressure of the process space has effect only on a surface of the reacting member, which is a surface of revolution in relation to the rotation axis of the reacting member. The former aspect means that the movement of the reacting member .does not positively alter the volume of the process space. The latter aspect in turn means that a gas pressure difference cannot cause tangential forces upon the reacting membe± and thus no torque is created.In a preferred embodiment of the invented machine the rotation space of the working member has a cylinder-like general form. Working spaces are then circumferentially situating channels in the working member. One functional basic unit of a preferred embodiment is consisting of two working spaces one after another around the circumference of the working member, whence the said spaces are situating on the opposite sides of the working member symmetrically in relation to the middle axis. As the both side edges of the channel are at equal distances from the rotation axis of the working member, axial forces to the working member are avoided. One functional unit of the embodiment mentioned is provided correspondingly with two reacting members situ¬ ating on the opposite sides of the rotation space symmetri¬ cally in relation to the rotation axis of the working member. It is essential that in the invented machine it is possible to form the reacting member so strong that it is able to transmit outside the rotation space of the working member concrete forces caused by a pressure difference bet ween process and transferring spaces. Consequently, the machine may be used at high pressure level. It is possible to compensate reacting forces with a pressure effect pro¬ grammed to be properly temporally variable during the process cycle. The compensating force can be directed to an opposite surface of the reacting member, said surface being situated outside the rotation space of the working member. One object of this invention is to provide a pro¬ grammed compensation, in which in principle no energy is consumed. In one alternative embodiment there may be used several parallel working members with reacting members situated between them so that reacting forces compensate each other.In one preferred embodiment the reacting members can have end surfaces, which are surfaces of revolution in relation to. the rotation axis of the reacting member, one end surface serving as a surface to form a partition wall and the other serving as a surface for pressure compensati The reacting members would then be continuous strong bodie only somewhat thinner between said end surfaces and thus they could transmit reaction forces nearly in the directio of the rotation axis of the reacting member.The partition wall forming part of the reacting membe may be a plane surface, the normal of which is parallel to the rotation axis of the reacting member, or it may be a somewhat conical surface of revolution in relation to said axis. In a preferred embodiment of the invented machine th partition wall forming surface is provided with one tran¬ sition sector with a minimum distance of edge line to the rotation axis of the reacting member. This transition sect may cover about 1/4 of the whole angle. In the remaining sector, covering about 3/4 of the whole angle, the distanc of the edge line to the rotation axis of the reacting memb has a constant maximum value. The shape mentioned isOΛ.PI advantageous in several respects. Firstly, the distance of the edge line from the rotation axis being constant, the corresponding clearance between the working member and the reacting member does not alter in consequence of errors in synchronization between movem nts ' of said members. Thus, there are ideal conditions for maintaining the clearance small. In addition it is possible to form the clearance so long in a direction of leak that reduction of a velocity of leaking gas is possible. A small clearance and a reduced velocity together result in low gas leak through this leakage path. The only part of the mentioned edge line, the corres¬ ponding clearance of which depends on the synchronization of rotating members, is a short part situated quite radially in relation to the rotation axis of the reacting member and having as its countersurface in the working member the end surface of the process space. The direction of the edge mentioned- is advantageous for providing said edge with a relatively light sealing member capable to move slightly in relation to the body of the reacting member. Thus, one object of the present invention is to provide a sealing member, which by a slight turning movement in relation to the reacting member can compensate errors in synchronization between the working and reacting members. The movement of the sealing edge thus effected is practically identical with that caused by the rotation of the whole reacting member, whence theoretical possibilities even to an ideal sealing do exist.The sealing member can also be constructed so that centrifugal forces do not influence its movement. Accor¬ dingly, required movements can be effected with an insigni¬ ficant power consumption taking also in consideration the lightness of the member as well as a low absolute speed due to a small distance of movement needed. In the specification is also presented a method for measuring precisely a momen¬ tary error in synchronization between the working and reacting members. The possibility mentioned can be utilized when controlling movements of the sealing member in order to compensate errors in the said synchronization. One essential demand, which this type of machine performing compression or expansion with minimal losses must fulfill, is that valve function must be carried out so that a dead space in front of a valve must be small enough. In the invented machine the dead space may be negligible. Moreover, in the preferred embodiment of the invented machine the total area of the valve opening is of the same order as the maximal area of the partition wall corresponding to the area of a piston in a conventional piston machine. The invented machine might be characterized by saying that a speed of the piston is constant but the area of the piston is different in different phases of proc cycle. In the preferred embodiment the momentary areas of valve openings and the partition wall increase during the expansion cycle quite synchroneously beginning from value zero to certain maximal values of the same order. Accor¬ dingly, the velocity of gas in the valve opening need not rise essentially higher than the effective speed of the piston, thus resulting in small. losses in the valve opening Also during the closing period of the valve in expansion us only small losses result in the valve, since the closing action is rapid and the relative change of volume of the process space during said period is small.In a preferred embodiment of the invented machine periodical closing of openings belonging to the process spa is provided by means of rotating valve members mounted into the body structure so that a rotation axis of the valve is situated in a normal plane of the rotation axis of the working member, the plane of rotation being directed at lea approximately towards the said axis of the working member. In the case of the preferred embodiment there are two openings situated one after another in circumferential direction of the working member. Each of them is provided with a valve member, so constructed that it functionally corresponds to three true valve members one after another. the preferred embodiment the total opening of the valves ma be as large as on the whole is reasonable for diminishing pressure losses in said opening. Consequently, a circum¬ ferential speed of the working member is possible to keep as great as possible resulting in a minimum time of one process cycle and consequently in minimum leakage during one cycle.In another embodiment of the invented machine a use of actual valves may be avoided by basing the valve function upon the rotational movement of the working member. In that case the working member itself closes the opening, which is situated in the body of the machine. For this purpose that part of the reacting member which forms the partition wall has been shaped so that the edge line of the surface extends at one rotation sector farther off from the rotation axis of the reacting member, while the part of the working space corresponding to the mentioned sector extends so far in the direction of the rotation axis of the working member that only that portion extends to the position of the opening in the body of the machine. When said portion of the working space is turned to the position of -the opening, a connection between the process space and the corresponding flow channel is created. The pressure ratio attainable by this embodiment is small but it might be adequate just for the most important purposes.One embodiment of the invention may result in even a very great pressure 'ratio. In this embodiment the rotation space of the working member is provided with a projection portion surrounding the main portion of cylinderic form. The partition wall part of the reacting member is then formed to extend only into said projection part during those periods when the valves are open. On the other hand, when the valves are closed, the reacting member extends also into the main portion resulting in a large effective piston area and consequently in a great working volume.A further object of the invention is to present how heat losses into the walls of the machine may be reduced to a small value. Inner walls of the machine may be classified into two main categories. One group is characterized in that no precise dimensioning of wa.l Is is necessary and that gas passing by the said surfaces has not temperature variation during a process cycle. In the invented machine the surface mentioned may be provided with a heat insulation structure, the extreme surface of which is practically taking the temperature ofthe gas, whence heat exchange between gas and walls is small. The walls participating in the formation of the process space are characterized in that precise dimen¬ sioning is required and also the temperature of gas varies during the process cycle. Certainly, in the preferred embod ment quite a low pressure ratio is used, resulting conse¬ quently in quite a moderate temperature variation only. If t temperature of gas is not high in the application in question, those surfaces may be kept e.g. at the mean tempe rature of gas, thus resulting in a net heat exchange betwee gas and walls to be zero. During each process cycle some amount of heat exchange to and fro then takes place, the phenomenon being quantitatively unessential, however. If the temperature of the gas is high, walls of the process space may be cooled beneath the mean temperature of the gas e.g. to the temperature of the gas after expansion, or to a remarkably lower, value, even near ambient temperature witho an excessive rise in heat losses.One object of the invention is to present how also surfaces of the process space may be provided with an inter nal heat insulation layer and how even iron material may serve as an insulator. This kind of solution may become int question specially if very high gas temperatures were used. The surface of the insulation layer would then take some temperature between the mean temperature of gas and the internal temperature of structures surrounding the process space. The same construction may also be used if the tempe¬ rature of working gas is considerably under ambient tempe¬ rature.Because sealing lubrication is not used in the invente machine, corresponding friction losses occuring in conven¬ tional piston machines can be avoided. Losses in bearings'BUREOMPV . AΛ.-7' .. VVΛiit- may be kept negligible, especially if a high pressure level is used in a closed process and at the most weights of rotating members are loading the bearings. Forces loading reacting members as well mas valve members may be compen¬ sated by means of a pressure effect, which may be arranged in a way which in principle does not consume energy at all. Possible mechanisms synchronizing the rotations of the working and reacting members cannot involve great power losses, because reacting members do not require work for their rotation. Also heat exchange between working gas and surfaces can be maintained small or negligible. The remain¬ ing loss factors are gas leak and pressure losses involved with the flow of working gas. These two loss factors are most essential also in the sense that the machine being connected as a component of a process, effects of losses of these types are reflected to operating circumstances of other machines of the process.If principal loss factors are a gas leak and pressure losses, then relative losses in one machine can be expressed2 by an equation δ = A/v-, + B v_- , where v_. = circum speed of working member, to which also a speed of working gas is proportional. The first term denotes gas leak and the second pressure loss. The relative gas leak is proportional to the time of the process cycle and thus inversely proportional to circum speed. Derivation gives an optimal speed v-- , =1/3 ,opt(A/2B) . Consequently, the minimum of losses isS . - 21/V 3B1/3+ 0.5X21/3A2 3B1 3 = 1.5x21 3A2/V 3. mmAs the absolute pressure loss is proportional to density or in case of ideal gas to the factor Mp/T, and the capacity of a machine is proportional to pressure p, factor B may be presented in a form B = k~M/T, where M = molecular weight and T = absolute temperature.If a dominating gas leak takes place through a clear¬ ance having a great conductance, the velocity of leaking gas will be determined principally by characteristics of the gas, its temperature and the pressure ratio over the clear¬ ance. If factors taken explicitely into consideration are absolute temperature T, molecular weight M, absolute size s of the clearance and diameter D of the working member as a characteristic- easure of the machine, then by using proportionalities A.i sD., Vp D3, t ^ D and vgi, ^ (T/M)1/ where A_. = cross-section area of the leaking path, V = volume of working space, t = time of one process cycle and v -, = velocity of leaking gas, factor A may be pres ;ecnted in g 1 /2 the form A = k.. (s/D) (T/M) ' . Insertion of formu^^ and B gives the optimum circum .speedVR,opt = |<Vk2) (s/D)| 1 3(T/M)1 2and a proportionality for the minimum of losses δ /3 mm. ^ k„ 2 1 k 1/3 (s/D) 2/3. Conseq-__uently_., the minimum of losses would be independent of pressure, temperature and molecular weight. However, use of light gases would result in a higher optimum speed and consequently in greater spe¬ cific power., The minimum of losses would be proportional to power 2/3 of the size of the relative clearance.If the total length of the sealing point in the direction of gas leak is great enough, compared with the clearanc the leaking speed may be reduced by a labyrinth sealing including numerous throttling points one after another, because then the pressure ratio over each throttling point would become small. If L = total length of the sealing poin in the direction of gas leak, for the number of throttling points would be valid a proportionality n •- L/s, where s = an absolute size of the clearance. If the number of throttling points is great, a proportionality v , ^ n -1/2 is valid, resulting in a proportionality v . ■- L~1/2s1/2(T/M) /2, which may be applied to the equations presented earlier thus resulting in a proportio--1/3 -2/3 nality δmm. ^ L D s for the minimum of losses. The minimum value would then be proportional to the clearance. Even now the minimum would be independent of pressure, temperature and molecular weight. If, on the other, hand the machine includes continuous clearances having a considerable length in the direction of gas leak, a friction in the clearance may reduce the speed of leaking gas, if the clearance is narrow enough and the absolute pressure difference over the clearance small enough. If friction is a reducing factor, the propor-2 tionality v . ^ s Δp/yL is valid, where Δp = the absolute pressure difference and μ = dynamic viscosity of gas. -If a leak through this kind of clearance were dominant, a propor¬ tionality δmm. - would be valid.Then the minimum of losses would be proportional to the square of the clearance.In the foregoing there are presented three relation¬ ships for the minimum of losses. The relationships may be interpreted so that the power 2/3, 1 or 2 of the size of the clearance is a measure for the merit of the machine. However, several factors effecting losses are implicitely involved in the coefficients of the relationships presented and values of these factors may be different in different machines. These factors include aspects influencing quantitative pressure losses, such as shape of working space, relative size of valve opening and closing or opening time of valves. Factors effecting gas leak include in addition to size of clearance and speed of gas leak, also a relative length of the leaking line and time of process cycle, which is a fuction of the shape of the working space. The 2/3-power relationship derived may be applied also to some known machines, as to a screw-compressor not using sealing lubrication. Theoretical calculation as well as experience prove that losses are at least as great as in the best turbo- machines. The structure of the invented machine is so advan¬ tageous that there are reasons for using also the second or the third relationship presented for the minimum of losses for evaluating the merit of the machine. To maximize the advantage mentioned, one purpose of this invention is to set forth a machine, the clearances of which can be - controlled during running for maintaining them at minimum values. As to the merit of the machine, most essential is the clearance which exists through the dominant part of time during operation, short term deviations having no sig ficance from an energetic point of view. Thus, a machine having a possibility to control clearances is superior as compared with machines with fixed clearances, the dimen¬ sioning of which must be made by considering a possibility of jamming in the most unfavourable combination of circum¬ stances .If it is desired to accomplish an expansion machine o a compressor having losses of at most some percents, turbo machines using a kinetic way of action are excluded, becau then a very high gas velocity as well as narrow flow chann must be used. Losses depend on forming the channels and on friction, factor which can be influenced only by the smooth ness of surfaces. Compression and expansion efficiencies i the best turbo-machines are 0.85-0.90 and possibilities fo raising the efficiency are insignificant. Also positive di placement machines using sealing lubrication are excluded, because friction of oil is of significant order, in parti¬ cular if speeds used correspond at least to a tolerable specific power.In order to obtain minimum losses a machine of positi displacement type not using sealing lubrication should ful fill the following conditions: 1) the size of clearances should not depend on a mutual synchronization of moving members, 2) the structure of the machine should be of the kind that members having effect on clearances do not bend in consequence of unsymmetrical gas forces, 3) lengths of sealing points in the direction of gas leak should be so great that the speed of leakage can be reduced, 4) clear¬ ances of the machine should be controlled during operation for keeping them at minimum values, 5) a cross-section are of the flow channel in the point of a valve function shoul be of the same order as in other parts of the working spac 6) opening and closing operations of the valve fuction sho' _0MP ' be rapid enough and 7) geometry of the working space should be advantageous so as to have a great cross-section area and a relatively short length in the direction of gas flow.Condition 1 should be fulfilled before condition 4 could be applied because accomplishing a stable control system for regulating mutual movements of massive fast moving bodies with an extremely high precision is not possible.Known machines do not fulfill the conditions presented. For example, a screw-compressor does not fulfill conditions 1-3, neither conditions 6-7. Consequently, both theoretical calculations and experience reveal that losses in a screw- compressor not using sealing lubrication are at least as great as in the best turbo-machines. Also various constructions of Wankel- type are characterized by a great gas leak at the corners of the piston, due to need of synchronizing the rotations of the piston and the shaft by using inside gears.As a theoretical example of a machine, which would not fulfill condition 4, it may be mentioned a construction resembling a turbo-machine in the sense that if it were desirable to adjust the clearance between vanes and the body of the machine very narrow, the control action should be turned to each vane individually, which would be impossible already due to a large amount of vanes. In real turbo- machines a more dominant factor is that as the heat capacity of vanes is negligible as compared with that of the body, after starting the vanes are warming up rapidly, thus result¬ ing in a temporary narrowing of clearances.As in the known machines clearances are great, also possibilities to reduce speed of gas leak are poor, because a necessary length of the sealing point in the direction of gas leak in the case of a labyrinth seal is proportional to the clearance, and if a friction of leaking clearance is utilized, proportional to the square of the clearance.The preferred embodiment of the invented machine is accomplishing the conditions presented as well as it is on the whole possible. The reacting member of the machine includes a short portion of the edge line of the partition wall forming surface, the si.'e of the clearance corres¬ ponding to it is dependent on the synchronization of the working and reacting members, but the geometry of the machine is so advantageous that the edge mentioned can be provided with a light sealing member capable to move in so extent in relation to the body of the reacting, member. Thus, the problem of synchronization can be divided into two successive phases. Then for the rotation of the reacting member is required only a rough synchronization, and the actual sealing is accomplished by means of the sealing member, which need to move perhaps only a fraction of a millimetre in relation to the body of the reacting member. Thus , the frequency of the movement may be high and never theless the speed of movement as well as kinetic energy needed may remain low. Also the relative precision require for the movement is not high. Consequently, one possibilit is to base the movement of the member on a prediction made o the ground of a precise measurement of error in. synchroni¬ zation between working and reacting members. Alternatively, the movement of the sealing member might be limited to the counter-surface situating in the working member. To preven wearing a real mechanical touch may be avoided by using small gas streams conducted through the sealing member to some points of the sealing line. As the reacting member do not need work for its rotation, it is easy to maintain the speed of rotation usually perfectly constant. A possible unidentity between torque curves of the invented machine a a machine connected to it, as an electric generator or motor, may cause a minute fluctuation of the rotation spee of the working member, but it can be taken into account beforehand in designing the shape of the counter surface situating in the working member. Thus, in order to prevent energetic losses, movements of the sealing member are need only if additional disturbancies occur, the influence of wh cover a considerable part of the total operating time.In the invented machine the control of clearances, sizOMPI,A wfιτo of which do not depend on the mutual synchronization of moving parts, can be arranged to take place during operation, the machine being provided with temperature control systems for regulating temperatures of the mem¬ bers of the machine properly. Since the machine includes only a few members of quite unbroken masses, the tempera¬ ture control can be accomplished by quite a small amount of control units. It is presented later in the specifi¬ cation, how the temperature control can be arranged even into the rotating members of the machine. As coefficients of thermal expansion in the case of metals are of the order of 10 1/°C, a temperature change of 1°C means for a dis¬ tance of 0.5 m a change of 5 ,um in the corresponding clearance. Thus there are theoretical conditions to con¬ trol even remarkably smaller changes of distance than is necessary in this application, because temperatures may be measured and also controlled even remarkably more pre¬ cisely than 1 C. As thermal expansion is a slow phenomenon, there is no fear of instability in the temperature control systems. The control of clearances may surely be based on measuring temperatures of- respective parts, at least if slow changes are taken into account by checking measure¬ ments at times, and subsequent adjustment of the control system. Of course, it is also possible to use sensors measuring directly clearances as components of the control system. The control may be alternatively based on local control of a sealing construction proper at least for some clearances of the machine.The precision of the bearings of the machine is part¬ ly determining, how small clearances may be used. In the invented machine possibilities for using precise bearings are very good. No forces in excess of those originating from the weight of a rotating member need to be directed to the corresponding bearing. If desired, even those for¬ ces may be compensated by a pressure force elsewhere than in the bearings determining the position of the rotating member. All rotating members are so firm that bending of the corresponding shaft at the point of the member is im¬ possible and the bearings may be situated immediately on both sides of the member. A use of temperature control systems eliminates a formation of free play in bearings due to uncontrolled thermal expansion. In all applications the essential structures of the machine can be kept near ambient temperature, whence e.g. precise roller bearings can be applied. On the other hand, if aerostatic bearings were used, a free selection of temperature would be possibl A good temperature control would secure small clearances and thus also a low energy consumption in the bearings.As for the preferred embodiment of the invented machine, it is justified to use the second or the third relationship presented for the minimum of losses, according to which losses are proportional to the clearance or to the square of it at least so far that gas leak through other clearances of the machine has become small as com¬ pared with a short part of clearance corresponding to the radial-like edge of the reacting member provided with the sealing member. An efficient reduction of leaking speed in the clearance in question is unconvenient, but it is not necessary, since if the size of the said clearance is maintained small, sufficiently small losses for all prac¬ tical purposes are resulting.A relative gas leak is proportional to the product of three factors namely clearance, speed of gas leak and time of process cycle. By maintaining clearances small, also leaking speed can be reduced efficiently. The time of the process cycle is determined in the first hand by pressure losses in the valve, and also in this respect the invented machine is advantageous, because the cross-section of the valve opening is exceptionally large and opening as well as closing periods take place rapidly. Also the geometry of the working space is advantageous to result in a short time of process cycle. The valve opening being large, it is possible to use as great circum speed as the quality of gas and temperature allow without the kinetic energy of gas also in other parts of the channel becoming of relative significance.To make clear the profitabliness of the invented machine it is taught to be made a comparison between the invented machine and some hypothetical machine, which are similar in other respects, but in the invented machine clearance, leaking speed as well as the time of one process cycle at a certain pressure loss are one third of the corres¬ ponding values in the reference machine. If now pressure losses were kept identical, the amount of gas leak would be 27-fold in the reference machine, whereas at the opti¬ mal' working point both the gas leak and the pressure losses would be 9-fold. Because the final result is a product of several factors, a scale of variation may be very large. Consequently, by now losses in the known machines of posi¬ tive displacement type without sealing lubrication have been at least of the same order as in turbo-machines, ir¬ respective of the fact that there is no theoretical under- limit for losses.As the invented machine is compared with other machines, the most important aspect would be a quantitative compari¬ son of losses, because that kind of quantitative aspects are essentially determining the advantage offered by the invention over known machines. This is particularly true as far as an application to the invented process for stor¬ ing electric energy is concerned, because in the said pro¬ cess the influence of losses of machines to the total effi¬ ciency of the process is cumulative in a particularly great extent. Also in a heat power process using Brayton- cycle the influence of losses is significant, because in addition to an expansion machine, also a gas compressor is needed in the process.To minimize losses the invented machine should be used at some optimum circum speed, to which also the speed of working gas is proportional. A numerical value of the optimum speed is dependent on gas, its temperature as well as clearancies of the machine, as presented earlier. As light gases such as helium or hydrogen are used, the opti¬ mum gas speed at the ambient temperature would be of the order of 50-100 m/s. Although the speed would be so low that the relative significance of the kinetic energy of gas would be small, especially in the case of light gases, an optimum speed would be high enough to ensure quite a high volume flow. As besides this in connection with a closed process a high pressure level is used, a high specific power results. In addition, in some applications a higher speed than an optimum one may be used, thus resul_ ting in a still higher specific power.In the invented use of the machine for storing elec¬ tric or mechanical energy the machine is applied as a com¬ ponent in a reversible process, which is operating during charging period in such a direction that by means of the process mentioned heat is removed from a cold store mate¬ rial. For achieving this, mechanical work must be put into the process. During reversed operation, or discharg¬ ing period, heat is delivered- into the same cold store material and mechanical work is produced. Cold store mate¬ rial may be in solid or liquid form, or it may be air, which is liquefied during the charging period and corres¬ pondingly vaporized and released into atmosphere during the discharging period. in connection with the storing process it is advan¬ tageous to use also warm store, in which water is serving as a heat storing material. During the charging period water is warmed up e.g. to 90-100°C and stored. During the discharging period water is taken from the store and coole in the process e.g. near the ambient temperature.It is characteristic to the process described that during the discharging period it is possible to deliver heat into cold store material at the most the amount, whic has been removed therefrom during charging. Consequently, no heat can be accumulated into the cold store. According ly that portion of stored mechanical energy, which is not transformed back into mechanical energy, must remain as heat into the warm store or the surroundings.If the pro¬ cess is operating between two insulated heat stores, a net heat exchange with the surroundings is small. Con¬ sequently, there is a tendency that into the warm store is accumulating a heat amount, which is practically the difference between stored and recovered mechanical energy. Therefore, during a discharging period of the heat content of the warm store such a portion may be used for producing mechanical energy, which is necessary for discharging the capacity of the cold store. The remaining heat content of the warm store may be utilized as heat for certain low temperature purposes, as heating or water distillation. Due to exceptionally small losses of the invented machine, the efficiency of energy storing is good, especial¬ ly as also the heat energy component is taken into account. Due to the reversible character of the process, require¬ ments concerning small losses of 'machines are so severe that by using machines known before the efficiency attain¬ able would be far too low.Brief Description of the DrawingsFig. 1 is a perspective view illustrating a possible general structure of the invented machine;Fig. 2 is a cross-sectional view of the machine taken along the line and in the direction of the arrows 2-2 of Figs. 1 and 3;Fig. 3 is a partial sectional side view of the machine taken along the line and in the direction of the arrows 3-3 of Figs. 1, 2 and 4;Fig. 4 is illustrating the circumference of the work¬ ing member and the form of working spaces especially in the position of the separating wall and a location of valve openings in accordance with Figs. 2 and 3;Figs. 5-6 are illustrating possibilities to arrange one true valve member to correspond to three virtual val¬ ves; Fig. 7 is a cross-sectional view taken along the line and in the direction of the arrows 7-7 of Fig. 2 and de¬ scribing a valve member;Fig. 8 is a cross-sectional view describing a valve member taken along the line and in the direction of the arrows 8-8 of Fig. 7;Fig. 9 is a cross-sectional view illustrating a coun¬ ter-force part for arranging a pressure compensation onto the reacting member taken along the line and in the direc¬ tion of the arrows 9-9 of Fig. 2;Fig. 10 is a diagram describing a time course of pressure forces needed for a proper compensation of the reacting member;Fig. 11 is a cross-sectional view illustrating a de¬ vice for altering periodically a pressure level in a pressure compensation cavity;Fig. 12 is an enlarged cross-sectional view illustra¬ ting a piston part of Fig. 11;Fig. 13 is a cross-sectional view illustrating the piston taken along the line and in the direction of the arrows 13-13 of Fig. 12;Fig. 14 is a cross-sectional view describing an auxiliary device used for accomplishing a pressure com¬ pensation of the reacting member;Fig. 15 is a fragmentary view illustrating a pro¬ grammed shielding of a gas opening in the auxiliary de¬ vice of Fig. 14;Fig. 16 is a schematic side view of the machine illu¬ strating locations of pressure compensators in connection with one reacting member;Fig. 17 is a diagram describing a time course of pressure forces needed for a proper compensation of a valve member;Fig. 18 is a schematic end view of the machine illu¬ strating locations of pressure compensation in connection with valve members relating to one process space; Figs. 19-21 are illustrating a possibility to form the constant-radius-edge of the partition wall forming part of the reacting member so that the corresponding clearance has a considerable length in the direction of gas leak;Fig. 22 is illustrating a possibility to use a laby¬ rinth seal for reducing gas leak through the clearance in accordance with Figs. 19-21;Fig. 23 is a side view of a sealing member mounted to a radial-like edge of the partition wall forming sur¬ face of the reacting member taken along the line and in the direction of the arrows 23-23 of Fig. 24;Fig. 24 is a cross-sectional view of the sealing mem¬ ber taken along the line and in the direction of the arrows 24-24 of Fig. 23;Fig. 25 is a schematic view illustrating supplying high pressure gas into sealing members in the reacting member;Fig. 26 is a sectional side view of a. continuously controllable sealing member taken along the line and in the direction of the arrows 26-26 of Fig. 27 as well as of Fig. 28;Fig. 27 is a cross-sectional view of the sealing member taken along the line and in the direction of the arrows 27-27 of Fig . 26;Fig. 28 is a cross-sectional view of the sealing mem¬ ber taken along the line and in the direction of the arrows 28-28 of Fig. 26;Fig. 29 is illustrating a structure of a programmed plate in connection with an optiocal position defining system of the sealing member;Fig. 30 is illustrating a structure of a receiving device co-operating with the plate of Fig. 29;Fig. 31 is a block diagram illustrating a control of the sealing member;Fig. 32 is a cross-sectional view of a valve controlling a passage of high pressure gas for effecting turning of the sealing member taken along the line and in the direc¬ tion Of the arrows 32-32 of Fig. 33;Fig. 33 is a sectional side view of the valve controlling the sealing member taken along the line and in the direc¬ tion of the arrows 33-33 of Fig. 32;Fig. 34 is a fragmentary circumferential view illu¬ strating a control of an effective gas opening taken along the line and in the direction of the arrows 34-34 of Fig. 32;Figs. 35-36 are schematic views illustrating an opti¬ cal measurement of error in synchronization between the working member and the reacting member;Fig. 37 is an enlarged schematic view illustrating co-operating members of the measuring system taken along the line and in the direction of the arrows 37-37 of Fig. 35;Fig. 38 is an enlarged fragmentary view illustrating positions of supplying and receiving optic cables taken along the line and in the direction of the arrows 38-38 of Fig. 37;Fig. 39 is an enlarged fragmentary view illustrating the structure of the measuring system on the position of a light absorbing slit taken along the line and in the direction of the arrows 39-39 of Fig. 37;Fig. 40 is a sectional view illustrating the location of the active part of the system defining an error in syn¬ chronization between the working member and the reacting member taken along the line and in the direction of the arrows 40-40 of Fig. 41 ;Fig. 41 is a side view of the active member of an optical measurement system taken along the line and inthe direction of the arrows 41-41 of Fig. 40;Fig. 42 is illustrating schematically a possibility to use distant photo-detectors and light transmitting op¬ tic cables;Fig. 43 is illustrating an arrangement, according toOMPI fΛ , WIPO which light can be supplied into the reacting member from a stationary light source and electric contacts are arrang¬ ed through the shaft;Fig. 44 is a schematic view illustrating arrangements for the sealing members concerning supplying high pressure gas as well as electric and optic connections needed;Fig. 45 is a block diagram illustrating a temperature system, in which the member in question has been divided into several' parallel parts, which are individually con¬ trolled;Fig. 46 is a sectional view illustrating an arrange¬ ment for achieving heat exchange conduits near a surface of a member to be thermo-regulated;Fig. 47 is a sectional view illustrating a structure of a straight labyrinth seal;Fig. 48 is a diagram illustrating a decrease of gas leak as a function of a number of labyrinth grooves one after another;Fig. 49 is a sectional view illustrating a heat in¬ sulation structure suitable for surfaces of which precise dimensioning is not needed;Fig. 50 is a top view of a heat insulation structure suitable for surfaces requiring a precise dimensioning taken along the line and in the direction of the arrows 50-50 of Fig. 51 ;Fig. 51 is a sectional view of the heat insulation structure taken along the line and in the direction of the arrows 51-51 of Fig. 50;Fig. 52 is a fragmentary top view of a heat insulation structure suitable for use in connection with working gas under the ambient temperature;Fig. 53 is a schematic sectional side view of an alternative general structure of the invented machine;Fig. 54 is a graphical diagram illustrating a time course of various quantities in the invented machine during one process cycle;Fig. 55 is a block diagram indicating auxiliary devices associated with one machine unit;Fig. 56 is a partial sectional side view of one alte native embodiment of the invented machine;Fig. 57 is illustrating the circumference of the working member in the embodiment of Fig. 56 analogously to Fig. 4; Fig. 58 is a partial sectional side view of still another embodiment of the invented machine;Fig. 59 is illustrating the circumference of the working member in the embodiment of Fig. 58 analogously to Fig. 4;Fig. 60 is a schematic cross-sectional view of the machine in accordance with Figs. 58-59 as to parallel functional units are used in order to compensate re¬ acting forces;Fig. 61 is a process diagram illustrating the use of the invented machine as a component in a heat power proce using Brayton-cycle;Fig. 62 is a block diagram of a substitute model corresponding to a real expansion machine; Fig. 63 is a block diagram of a substitute model corresponding to a real compression machine; Fig. 64 is a graphical diagram illustrating the pro¬ cess efficiency of the process according to Fig. 61 as a function of the maximum gas temperature as various loss parameters have certain numerical values; Fig. 65 is a process diagram illustrating a charging period of an energy storing process, in which the invente machine is used as a component;Fig. 66 is a process diagram illustrating a discharg period of an energy storing process, in which the invente machine is used as a component;Fig. 67 is a process diagram illustrating a cold sto part of the energy storing process, if liquid cold store material is used;Fig. 68 is a process diagram illustrating an alternaOΛ'.PAι. WiP > '. tive cold store part of the energy storing process, as liquid cold store material is used;Fig. 69 is a process diagram of the energy storing process, if the cold -store side of the process is based on lique¬ fying air;Fig. 70 a partial process diagram illustrating a modification of the process shown in Fig . 69;Fig. 71 is a block diagram of a substitute model corresponding to a real ambient temperature machine in Fig. 65;Fig. 72 is a block diagram of a substitute model corresponding to a real low temperature machine in Fig. 65 ; andFig. 73 is a graphical diagram illustrating the pro¬ cess efficiency of the storing process of Figs. 65 and 66 as a function of a momentary cold store temperature, as various loss parameters have certain numerical values.Description of the Preferred EmbodimentsFig. 1 is illustrating a possible general structure of the invented machine. The machine includes a power shaft 2 connected to a working member situated inside the the body 4 of the machine. In this example it is thought that the machine includes two functional basic units 40 one after another in the direction of the shaft 2 on the positions of halves 4a and 4b of the body. As the units mentioned function in opposite phases, a torque of the whole machine may be fairly constant within each process cycle. Assembling of the machine may be carried out by pushing halves 4a and 4b of the body towards each other axially and by attaching them by means of projecting flanges 41. Each functional unit includes two reacting members situated at a transverse position in relation to the working member on opposite sides thereof. Shafts 9 of said members being shown in Fig. 1. To ensure syn¬ chronization of rotation of working and reacting members a synchronizing mechanism 42 may be used between corres- ponding shafts 2 and 9. The shafts 9 of the reacting mem¬ bers may be provided with small motors 43, whence a main energy exchange may occur between the motor and the. react¬ ing member, thus avoiding stresses and wear of the synchro nizing mechanism. It might even be possible to manage without said mechanism, if an elctronic control of motors 43 were safe enough. Valve members belonging to the machine are rotated by means of shafts 24 and 25. The rotation may be arranged by using motors 39 attached to the corresponding shaft. Moreover,- there are shown flow conduits 18 and 19, which have been branched for the both functional units 40. In expansion use gas enters the machine along conduit 18 leading to the valve members, and returns along conduit 19, the direction of circulation being reversed in compression use-An internal structure of the machine is illustrated in Figs. 2-3. The rotation space 3 of the working member 1 situated inside the body 4 of the machine has in the example the general form of a cylinder, the working mem¬ ber being attached directly to the power shaft. The work¬ ing member 1 is formed so that in the rotation space there are two working spaces 5 one after another in the direc¬ tion of the circumference of the working member, said spaces being situated symmetrically on opposite sides of the working member. The functional unit described also includes two reacting members 8, which situate transverse in relation to the working member and on oppo¬ site sides of it. As an expansion or compression process takes place in the same phase in the both working spaces of the functional unit, no transverse reacting forces are effecting the shaft of the working member. As the working spaces are channels in a cylindric body, both side edges of the working space are at the same distance from the ro¬ tation axis of the working member, whence no axial forces originated from gas pressure are created. Accordingly, the corresponding bearings are loaded only by the weight of the working member and the power shaft.The shafts 9 of the reacting members are located in the same plane to the rotation axis of the working member. Additionally, said members are located so that their rota¬ tion axes are situating outside the rotation space 3 of the working member. It would also be possible to use modi¬ fications where the shafts of the reacting members were mounted to deviate somewhat from the normal plane of the power shaft. In a general case one functional unit might include n reacting members, where n is any positive inte¬ ger. In that case the unit might include correspondingly n working spaces one after another circumferentially at intervals of the angle 360 /n. In principle, the number of working spaces might be alternatively m-fold as compared with the number of reacting members. Then only a fraction of 1 /m of all working spaces would be simultaneously on the points of reacting members and thus in active use.A partition wall 15 (indicated by a dotted line) formed bythe reacting member 8 divides the working space 5 into two parts,of which the process space 6 is connected to the corresponding flow conduit 18 through openings 26 in the body of the machine. The other partial space 7, named in the following a transferring space, is continuously in connection with the corresponding flow conduit 19 through an opening 52 in the body structure 4 surrounding the rotation space of the working member. Through the same opening also the reacting member 8 is extending into the working space 5 thus forming said partition wall 15. For sealing reasons the partition wall forming surface 10 of the reacting member must be a surface of revolution in relation to the rotation axis of the reacting member. Said surface may be a plane surface, the normal of which is parallel to the rotation axis of the reacting member or it may be a somewhat cone-like surface of revolution in relation to the said rotation axis for reasons ex¬ plained later. The shape of the edge line of the parti¬ tion wall forming surface 10 has been presented in Fig.3, said line having portions 44, 45, 46 and 47. The parti¬ tion wall forming part is thus provided with one tran¬ sition sector 77 having a sector angle ψ which in the example is about 90°. The partition wall 15 is formed by that changing part of the partition wall forming surface 10 which, in course of the rotation of the reacting member in turn is inside the rotation space 3 of the working member. If the axial co-ordinate z of cylinder co¬ ordinates is imagined to join the rotation axis of the reacting member, a general- form of the edge line of the partition wall forming surface 10 may be defined by means of the radial co-ordinate r and the co-ordinate - ψ r so that as the angular co-ordinate is varying beginning from ■ the sector 77, which is turned towards the working member the process cycle changes to a direction corresponding to the order of arrival of differentpoints of the said edge line in expansion use into the rotation space of the work¬ ing member, the radial co-ordinate is growing relatively steeply (segment 44) to a constant value r. , remaining at that value for the most part of the angle change corres ponding to the whole circle and returning finally (segment 46) to a low starting value rn - near the completion of the whole circle.The described general form may be superimposed by local deviations, as projections or grooves. Most essen¬ tial from functional point of view is that the distance of the edge line from the rotation axis of the reacting member is constant for the long segment 45 of the edge line. As working and reacting members rotate synchroπeous- ly, the clearance 14 corresponding to the said segment 45 remains constant irrespective of errors in synchronization Accordingly, it is possible to maintain said clearance 14 small. Faults in synchronization are harmful only as far as the segment 44 of the edge line is concerned. This segment 44 going quite radially is relatively short and is in the rotation space of the working member only for part of time, whence gas leak through the corresponding clearance 13 remains quite small. A radial-like direction of the last mentioned edge 44 is advantageous for providing said edge with a special sealing member, as presented later. The segment 46 of the edge line corresponding to the trans¬ ferring space end of the working space is not essential as to leakage, because there is no pressure difference between process and transferring spaces when said segment is inside the rotation space.In Fig. 3 also a location of valve members 23 is sketched. Shafts 24 and 25 of valve members are located in a certain normal plane of the rotation axis of the working member, this normal plane not being the same in which the shafts 9 of the reacting members are situated. The plane of rotation of each valve member may be directed at least approximately towards the rotation axis of the working member. To avoid dead space in front of the valves the rotation space of the working member may at the position of valve openings 26 deviate from a cylinderic general form in a way presented in Fig. 3. The rotation space includes a ring-shaped projection part 48 around the cylinderic main part, said part 48 being formed by a channel in the body of the machine. The bottom 49 of the channel is formed to corres¬ pond to the form of an unbroken circum surface 99 (Fig. 2) of the valve members- as well as it is possible, as presented later in detail. In Fig. 4 is presented a part of the circum surface of the working member by using as co-ordinates the rotation angle ^ of the working member and the axial distance zw in the direction of the rotation axis of the working member. The figure shows a separating wall 21 between two working spaces 5. One functional unit includes two separating walls 21 situated symmetrically on the opposite sides of the working member. When said wall is turned towards the corresponding reacting member, in said reacting member is correspondingly turned towards the working member a gap 77 formed in the position of the segment 47 of the edge line with a minimum radius rQ . In Fig. 4 are also presented locations of valve openings 26 at a moment when the partiti wall 15 in relation to the working space is in the position shown in figure corresponding also to the situation in Figs 2-3. The separating wall 21 is acting as a sealing wall between two working spaces one after another. For this purpose said wall is provided with a projection part 50 corresponding to the form of the cross-section of the channel 48. It is possible to form the projection part 50 o the same continuous material as the main body of the workin member, if the body 4 of the machine is provided with a . groo 51 situated in the inner wall of the body in the direction of the rotation axis of the working member and at a sector corresponding to the opening 52 for the reacting member. When the working member is.pushed axially inside the body during assembly, the projecting part 50 can be guided throu said groove 51. Alternatively, it is possible to install a separate projection part through opening 52 after installin of the working member.It might be favourable, although not absolutely necessary, to form the radial-like segments 44 and 46 of th edge line in the reacting member to correspond to the cross section of the bottom 49 of the channel 48 so that all part of said segments are entering or leaving simultaneously or nearly simultaneously the rotation space of the working member.In expansion use the working member rotates in directi 16 and the reacting member in direction 17. In the beginnin of a process cycle the front edge 44 of the reacting member starts to enter the rotation space of the working member on the point of the projection part 48. Consequently, the volume of the process space 6 starts to increase from value zero. When the gas openings 26 provided with valve members are just at the point of said projection part and one openi is extending close by the partition wall 15, access of gas from the conduit 18 into the process space is possible from the very first moment of the. process cycle in time with increasing of volume of the process space. To accomplish thi the gas openings in the body of the machine have thus to be located, as seen in the direction of the rotation axis of the working member, at the point corresponding to that side of the working spaces running circumferentially, on which the extreme end 20 of the process space 6 is situating, and as seen circumferentially on the process space side, at least one opening extending beside the point where the partition wall is formed. The valve members 23 start to open at a moment when the corresponding opening has been fully shielded by the separating wall 21 thus preventing gas •leak into the extreme end 22 of the transferring space of the adjacent working space. When the valves at a.certain moment close and the working member continues its rotation, the volume of the process space further grows and conse¬ quently the gas in the closed space expands. When the rotation of the working member has proceeded to the point p = 135° (315°) in the case of the example, the rear edge 46 of the reacting member enters the rotation space, thus resulting in a loss of sealing of the process space. Accor¬ dingly, expansion ends at that point, and in order to avoid losses, the end part 22 of the working member has been broadened to allow gas to flow past the reacting member. For the same reason it might be profitable to form also the edge of the opening 52 for the reacting member to correspond to the edge 78 of the working space at the process space end, whereby sealing is lost synchroneously also at the end • of the process space and, when the working member continues its rotation, the latter opening is steadily growing.Increasing the volume of the process space during expans ion cycle from zero to a certain maximum is accompanied by diminishing the volume of the transferring space, whence .gas expanded during the previous cycle is pushed away from the working space into the conduit 19 through the opening 52. The process cycle ends and the next cycle begins as the separating wall 21 in the working member reaches the point of the partition wall 15. During one cycle the reacting members rotate one revolution and the working member half a revolution. In compression use the directions of rotation of working and reacting members are reversed, as well as the direction of gas flow. Then gas is sucked from the conduit 19 into the transferring space 7, the volume of which increases to the maximal value. When the process cycle changes said space becomes the process space in consequenc of rotation of the working member, whence the gas amount sucked in is compressed and pushed through the valve openi 26 into the conduit 18 during the next cycle.It is possible to achieve a large total area of a val opening, if it is used several openings 26 one after anoth circumferentially, one of the openings extending close by the point of the partition wall, and each opening being provided with a real valve member, said valve members bein located fan-like so that their planes of rotation are directed at least approximately towards the rotation axis of the working member. The shafts of the valve members may be int connected by universal joints thus making it possible to rotate the whole chain of valves by means of one shaft connected to the last valve member. In the example it is succeeded to manage with two openings 26 and corresponding real valve men±jers 23, which have been formed so that they effectively correspond to three distinct openings, the virtual openings 27a, 27b and 27c thus formed being situat one after another circumferentially. During expansion proc the opening of the valve in the case of each virtual openi may be started when the corresponding virtual opening has come into the shield of the separating wall 21. As the width of said virtual openings is small in the direction o the 7 W-axis, it is possible to manage with a relatively narrow separating wall, whence more useful working space m be achieved. Opening of valves may take place in the shiel of said separating wall so that when extreme end 20 of the process space comes to the position of the opening in ques tion, it is already fully open. The use of virtual opening is advantageous, in addition to simplifying structures and increasing working volume, also because then it is possibl to manage with only one wall 38 betv.een the true opening.. As it is seen from Fig. 54, which is explained later, such a wall has a tendency to delay increasing of the total area of valve openings.In order to illustrate accomplishing of virtual openings possibilities are presented with the aid of Figs. 5-6 for selecting respective forms of an unbroken circum surface of a valve and on the other hand the bottom 49 of the channel 48 forming the projection part of the rotation space. Unbroken lines are presenting the form of the bottom of the channel and broken lines the form of the unbroken valve surface, the co-ordinates andjf presenting directions of circumferences of working and valve members, respectively. In Fig. 5 it is wanted to achieve indentical forms of sur¬ faces along lines A-B and C-D. To achieve this, it is thought that from the valve body are determined two circles situating in the positions of the lines mentioned, said circles being identical and situated in parallel planes symmetrically at equal distances on opposite sides of that normal plane of the rotation axis of the valve member, which is going through the rotation axis of the working member. Said circles being situated symmetrically completely determine the form of the bottom 49 of the channel. The remaining degree of freedom is to determine forms of revolution of the unbroken circum surface of the valve in other planes so that said surface at some angle J3 at the- most extends nearly to touch the bottom 49. Touching would happen between lines A-B and C-D firstly along line K-L, which is situating in that normal plane of the rotation axis of the working member which goes through the rotation axis of the valve member. Outside said lines touching would happen firstly along the sides, in a symmet¬ rical case at all lines A-G, B-H, C-I , and D-J. If the possibility offered by line K-L is not utlized, but said point is provided with a moderate clearance, then by utiliz¬ ing lines A-B and C-D as sealing lines it is possible to divide the true opening 26 into three virtual openings 27a, 27b and 27c one after another in- circumferential direction of the. working member. Sealing along the outer si s G-H, H-J, I-J and I-G is achieved by forming the projection par 50 of the separating wall to correspond to the cross- section of the channel 48. The forms of the bottom 49 and the unbroken circum surface of the valve correspond at all points to each other so well that dead space between them has no practical significance.In Fig. 6 the situation explained in the foregoing ha been turned 90 . In that case the sealing circles explaine belong to the working member, whence sealing lines A'-B' and C-D' in the direction of the circumference of the working member are achieved. The virtual openings 27a, 27b and 27c thus achieved are p carallel in the direction of rw- axis, but in series in the direction of 7 -axis. Also now an opening of the valve at the position of each virtual opening may be started in expansion use immediately after the virtual opening has been shielded by the separating wall. In the case of Fig. 6 equality in size of the virtua openings requires that the axis of the valve situates symmetrically in relation to the Opening in a direction of the rotation axis of the working member. In the example of Figs. 2-4, where an alternative presented in Fig. 5 is use the position of the valves is unsymmetrical so that the axes of the valves are located in the normal plane of the axis of the working member, which is approximately situatin at the position of the outer side edge 12 of the working member. Accordingly, it is easier for the shaft 24 of the valve to pass the reacting member. Also a symmetrical situ¬ ation would be possible, if the rotation of both valves would happen through the shaft 25 belonging to the latter valve, the shafts being connected with a double-joint.Figs. 2, 7 and 8 are illustrating a construction of rotating valve members 23. As to the general form they are bodies of revolution with the exception that from a certai sector material has been removed so that when this sector is turned towards the gas opening 26, a connection between the process space 6 and the corresponding conduit 18 is effected. As it is the purpose to open in expansion use virtual openings 27a-c in succession in time with their arrival at the position of the separating wall 21, opening times of the individual virtual openings are different from each other. To achieve this, the opening 28 in the valve is formed of three sections in the direction of the axis of the valve, said sections having individual opening angles3a, f>b, and f3 c as seen from the axis of the valve. As the valves in expansion use rotate in direction 31 , the indi¬ vidual edges 29 are acting as front edges, whereas the other edges 30 are all in the same line 'resulting in a simultaneous closing of all virtual openings in expansion use and correspondingly in a simultaneous opening in compression use. Simultaneous actions during said phases are advantageous in making the corresponding periods as short as possible for avoiding losses. The same point of view prefers a small visual angle α of the opening 26 in relation to the axis of the valve. In the example this is about 30 , whence losses during the periods mentioned are no more dominating. In the case of valves in accordance with the figures one revolution of the valve corresponds to one process cycle. In the example the valves have been provided with supporting parts 32 having the form of a body of revolution. It is possible to direct onto these parts a programmed pressure effect from cavities 33 for compensating the force induced by pressure difference between the process space 6 and the conduit 18. This can be accomplished in the same way as the compensation of forces effecting on the reacting member, which is discussed later. Alternatively, it is possible to conduct a pressure in the process space also to said cavities, in which case the area of the cavities must correspond to that of the opening 26. For making possible mounting of the valves the body of the machine may be provided in accordance with Fig. 7 with a loose part 34, which can be installed after the valve. If transverse forces are compen¬ sated, forces directed to bearings of shafts 24-25 are kept small. If desired, also considerably smaller axial unbalances nay be compensated. On the other hand, it is clear that especially if the pressure level used is not high, no pressure compensation is necessary.Fig. 7 also presents a possibility to use a shielding part 35 to reduce heat exchange between gas and the circum surface of the valve. Passage 36 of gas may take place e.g. in conformity with Fig. 8 past the valves along channels 3 in the body of the machine. The total cross-section area o those conduits is possible to dimension greater than the total area of gas openings 26, whence pressure losses in these conduits are not significant.The scope of the invention also includes an alternati in which the reacting members and/or valve members are formed so that one revolution of said members corresponds to two process cycles. In that case the members have two gaps 77 and 28, respectively, symmetrically on the opposit sides of the member in question. The advantage achieved is geometrical symmetry in> relation to the rotation axis, resul in an inherent balancing of the member. The drawback invol is greater losses than in the embodiment presented. As to the reacting member, also a considerably smaller working space is resulting. The balancing of said members in the preferred case may be accomplished by planning the members so that on the sides opposite to gaps 77 or 28 some materi is removed from suitable areas unessential from a function point of view. Radially going gaps 102 in Fig. 7 serve the purpose mentioned.The power shaft 2 may be composed of two parts, which are provided with a thicker portion 76 for mounting the shaft halves into the ends of the working member so that ev a very great torque can be transmitted. A connection may be arranged e.g. by using round locking means 79, as indicated in Fig. 2.The reacting members may be firm bodies as in Fig. 2 capable to transmit even very great forces caused by a pressure difference between the process space and the trans ferring space outside the rotating space of the working member. Reacting forces may be compensated by a programmed pressure effect which is directed onto a counter-surface 11 in the reacting member, said surface being situated outside the rotation space 3. Bearings 67 and 68 may take forces due to incomplete pressure compensation. The bearings can be dimensioned to bear for a short period the whole reacting force during a possible failure in pressure com¬ pensation. Mounting of the reacting member may happen so that the shaft 9 is pushed through a separate ring-like part 64 and screwed into its place and locked in tangential direction by using a Locking part 66. Axial forces on the bearing 67 are transmitted through the ring-like part 64, whereas axial forces to the bearing 68 are transmitted through the thread 65 and the shaft 9. In mounting a proper axial pre-stress may be used for avoiding an axial free play. For keeping this pre-stress within suitable limits, a thin flexible part between the bearing and a counter-part may be used or alternatively during running a control of temperatures. After mounting the reacting member the counter- force part 63 may be mounted into its place by pushing in circumferential direction. According to Fig. 9 this counter- force part is provided with three low cavities 53-55 for directing pressure forces onto the reacting member. In Fig. 9 the machine is looked in the direction of the shaft 9 and the location of the total cross-section area 60 of the working space is indicated by a dotted line. The.resultant of counter-forces can be kept every moment at the same line parallel to the axis of the reacting member as a momentary centre of gravity of the partition wall 15. As the locus 59 of the centre of gravity remains inside a triangle determined by the gravity centres 56-58 of the cavities, it is possible to arrange the resultant of forces to follow said locus.The cavities are surrounded by a broad seal margin 61 which may be provided with numerous grooves 62 forming a labyrinth seal for reducing the speed of gas leak. As the volume involved with the grooves is small, the pressure distribution within the seal is well corresponding the momentary pressure ineach cavity. Due to a gradual lowering of pressure within the seal about half of the seal area is effectively included in the cavities. Fig. 10 is illustrating a time course of counter-forces F^-F^c in corresponding cavities 53-55 in the case of Fig. 9 as a .function of the rotation angle ^ of the reacting member, the starting moment of an expansion cycle being at ψ = 0. As to curves of forces Y- . -Ε→ - , they are of periodic form deviating from a sinusoidal one mainly so that they have flattened portions at both tops of the curves, whereas the curve for F-., has one long flattened portion.A periodic variation of pressure may be accomplished by a periodic variation of volume by using a suitable apparatus in connection with each cavity. Accomplishing a back-and-forth variation of -volume does not in principle consume energy. If the volume of compensating cavities is of the order of 1% of the corresponding working volume of the machine, losses in actual compensating devices may be at the most some thousandth parts of the power of the machine.Taking into account wave forms presented in Fig. 10, a suitable apparatus to be used in connection with each cavity is shown in Fig. 11. The apparatus 70 includes a reciprocating piston 71 inside a tubular housing 82 and provided with support bearings 80, 81. The piston is moved by a conventional crankshaft 73 provided with a flywheel 7 and an electric motor 75. In front of the piston is a spac 72 in connection with the corresponding cavity 55. The wor done to the piston during expansion of the space 72 is sto into the flywheel and possibly also in electric form by using the electric machine 75 as a generator. Synchroni¬ zation with other moving parts of the machine is possible to arrange by using an electronic control of the motor 75. Flattened portions of the curves may be accomplished so that the piston 71 is provided with a circumferential groo 87 leading through conduits 89 into the interior 88 of the piston, as described in detail in Figs. 12-13. The inner surface of the body 82 is provided with circumferentialOMPI A W-PO spaces 83 and 84. As the piston during its reciprocation is situating so that the groove 87 is at the position of the space 83 or 84, a gas conduit is open from the space in question to the space 72 as well as tothe corresponding cavity. Thus, if said spaces are connected through conduits85 and 86 to , the corresponding pressure exists also in the cavity during those parts of the process cycle when the groove 87 is not between the spaces 83 and 84. The ratio of volumes of the cavity and the space 72 can be dimensioned so that the desired p eressure ratio prmax/p-mm. results. Pressure prmm. is that existing in the conduit 19 corresponding to the transferring space. Pressure p may be e.g. 1.3 p-, where p_, is the c 'max Λ ^ ^1 * ι pressure in the conduit 18 corresponding to the process space. A suitable pressure may be produced by using a con¬ ventional compressor as an auxiliary device.The apparatus described is suitable for achieving curve forms Fj-4 and F- - . For achieving curve F-, the space 83 may be omitted and the space 84 dimensioned to cover a dominant part of the process cycle.Gas leak from counter-force cavities as well as remain¬ ing unbalances may be compensated by using an auxiliary device described in Fig. 14. The device 90 includes a rotating valve member 91 provided with circumferential slots 97 and 98 at the position of openings 93 and 94 in the wall 92 of the device. The slots are designed properly to result in a desired time course of the size of openings between the hollow interior 100 of the valve member.and the corresponding conduits 95 and 96 having pressure p, . , and p, . Said interior is in connection with the cavity 55 in question. The rotating valve member 91 shuts in course with time a variable portion of the openings as described in Fig. 15.The rotation of the valve member 91 is synchronized with movements of other parts of the machine by controlling electro¬ nically the motor 101. The device described may he used so that more gas enters the cavity through the conduit 95 and the amount of gas is diminished through the conduit 96. Of course, the device can be used also so that there are sever pressure levels available to minimize energy consumption.Fig. 16 is illustrating locations of compensating devices as seen from outside of the machine in the directio of the shaft 9 of the reacting member. Locations of the counter-force part 63 as well as of cavities 53-55 are indicated by broken and dotted lines, respectively. Refe¬ rence signs are indicating positions of devices 70 and 90 described in Figs. 11-15. Each cavity is provided with one main device 70 and one auxiliary device 90. Possibly remain ing unbalanced forces load the bearings of the reacting member. These forces remain so small that even very great pressure levels may be used in a closed process. Mounting holes 69 for the main device 70 are shown in Fig. 2.Fig. 17 illustrates, a time course of radial gas forces effecting valve members 23 of the machine in expansion use, due to pressure difference between-the process space and the conduit 18, as a function of the rotation angle P of the valves, when the starting moment of the expansion cycle is ^f = 0. The curves are periodic having flattened portions at both tops. Thus, the forces may be approximately compen¬ sated by using devices 70 and 90 described above.Fig. 18 indicates positions of compensating devices fo the valve members as seen from outside the end side of the machine in the direction of the power shaft, the location of contours of valves 23 being indicated by dashed lines. Reference signs are those used in Figs. 11-14. 'Compensating devices are mounted into corresponding holes 108 and 109 indicated in Figs. 2 and 7.Figs. 19-21 illustrate a possibility to achieve for a leak path 14 corresponding to that segment of clearance between the working member and the reacting member which is independent of synchronization, so great length in the direction of leakage that speed of leak can be reduced. The best possibilities to accomplish this are present if the partition wall forming surface 10 is situated at the positi of that normal plane of the axis of the reacting member which extends through the axis of the working member, whence a tangent of. the bottom of the working space in circumferen¬ tial direction is parallel to the axis of the reacting member. The forms of said bottom and the edge of the reacting member cannot corrspond to each other perfectly in every place, but quite a satisfactory result is achieved, if the rim of the reacting member is formed to correspond to the form of the bottom of the working space in a situation where the rim point in question has turned about 1/4 or 3/4 of the total angle spent inside the rotation space of the working member. Fig. 20 illustrates the situation mentioned, - whereas Fig. 19 presents the situation in the middle of the working space and Fig. 21 on the extreme sides of said space. Due to a considerable length of leak path a pressure drop in the clearance is correspondingly distributed over the whole length. In order to avoid radial reaction forces into the reacting member, the end surface 10 may be a somewhat conical surface of revolution as described in Figs. 19-21 as well as in Fig. 2.Provided the pressure level used is so high that a laby¬ rinth seal results in a better reduction of speed of gas leak than the use of a continuous narrow clearance, the rim 45 of the reacting member may in accordance with Fig. 22 be provided with transverse grooves 62 forming a labyrinth seal structure 103. The grooves may be interrupted to avoid gas leak in the direction thereof. The general form of the rim may be that described in Figs. 19-21.Figs. 23-24 describe one embodiment for providing the radial-like edge of the reacting member with a sealing member 110 forming the true edge 44. The sealing member may turn in some extent in relation to axles 112 which are at least approximately parallel to the edge 44. The sealing member may be mounted so that axles 112 are pushed in their holes 113 axially into their places after insertion of the sealing member. The turning movement of the sealing member is restricted by an extension part 114 located in a cavity 115 of the body 111 of the reacting member. In this embodi- ment the sealing member is constructed somewhat unsymmet- rical so that a centrifugal force turns said member to its outmost position shown in the figure, whence the extreme edge 44 is situating at a surface 117 which is an extensio of the partition wall forming surface 10 of the reacting member. During normal operation the sealing member is at the position described. When necessary, the member may be turned inwards by applying gas pressure against the extens part 114 through a conduit 116. This may be done during starting and stopping of the machine as well as during special disturbances. Especially, if the machine is provid with means for detecting coming disturbances, the clearanc 13 between the edge 44 and the counter-surface 119 in the working member may be maintained quite small for a dominan part of time. For that purpose it may be used e.g. a metho for measuring errors in synchronization between the workin and reacting members, which is described later in Figs. 35-43. If such an arrangement is used that the reacting member is usually rotating exactly at an unchanged speed and a minute variation of speed of the working member due unidentical torques of the invented machine and a co¬ operating machine, a generator or motor, are taken into account by manufacturing the form of the counter-surface 119 properly, alterations in the clearance 13 are mainly caused by external disturbances through the co-operating machine. If the machine in question is a generator feeding a large number of consumers, rapid disturbances are small and the mode described might lead to quite a satisfactory result. Gas leak through a clearance 122 between the seali member 110 and the body 111 of the reacting member is negligible, because the clearance is formed between surfac 123 and 124, being surfaces of revolution, and the radius of the sealing member is small. According to 23 it is possible to use gas pressure to support the sealing member through cavities 120 during periods when the position of t sealing member is changed.High pressure gas needed in conduits 116 and 121 may supplied into the reaction member through the rotation axis as described in Fig. 25. Valves 125 and 126 controlling the gas flow may then be situated in connection with the statio¬ nary body of the machine. Opening and closing of valves may be timed so that gas support through cavities 120 is always effecting -during turning of the sealing member. As presented in Fig. 25, the total edge 44 may be provided with two sealing members 110 one after another, corresponding to two straight portions of said edge. In connection with the embo¬ diment of Figs. 23-24 it is alternatively possible to use a continuous curved form of the edge 44, the form being selected to correspond to the cross-section of the projection •part of the separating wall in the working member. In that case the radius of the sealing member is selected to be different in different positions along the direction of the axle 112 so that the desired form is resulting at an inter¬ section of the circum surface 123 and the surface 117.An alternative embodiment of the sealing member 110 is described in Figs. 26-28. Fig. 26 shows a sealing member corresponding to one straight portion of the edge 44. Now it is possible to use a continuous control of the clearance 13 by turning the sealing member in relation to axles 112 so that errors in synchronization between the working and reacting members are compensated. For this purpose the direction of axles 112 differs slightly from the direction of the sealing edge 44 so that the circum surface 123 of the sealing member is a cone-like surface of revolution in relation to the axle 112, said surface is a tangent surface to a surface 117 imagined as an extension of the partition wall forming surface 10 of the reacting member. The sealing line 44 as well as the clearance 13 between the sealing member 110 and the counter-surface 119 are formed approxi¬ mately at the point of the mentioned tangent line, because the sealing member is formed thinner on the side being out¬ wards from the reacting member so that the surface 118 beginning from the sealing edge is situating nearer the axle 112 than the cone surface 123. The degree of conical form is such that the distance R of each point of the sealing line from the axis of the sealing member is proportional to the distance R of the point in question from the rotation axis of the reacting member. If the turning angle £ of the sealing member remains small, the movement of the sealing edge 44 caused by the turning of the sealing member is identical to that achieved by a rotation of the whole reacti member. As forms of the cone surface 123 and the counter- surface 124 are identical, gas leak through a narrow and long clearance can be kept negligible.The sealing member may be formed symmetrical so that i centre of gravity is located exactly at the axis of rotatio whence a centrifugal force does not cause a torque to said member, even if the direction of axles 112 is different fro the radial direction of the reacting member. Alternatively the centre of gravity may be located slightly unsymmetrical so that the sealing member has a tendency to turn to the middle position described in Fig. 27.The turning of the sealing member may be achieved by using a projection part 127 serving as a piston and a cavit 128 serving as a cylinder. In the example the cavity is on the side of the body 111 of the reacting member. The ends- o the cavity are provided with gas conduits 129 and 130, thro which high pressure gas is effecting the piston and leaking away through clearances of the piston-cylinder construction For accomplishing a control system to regulate movements of the sealing member, a knowledge about the momentary positio of said member is needed. For this purpose the sealing memb is provided with a measuring projection 131 having a measur hole 132 provided with a plate 133 having properly designed openings for arranging an optical position determination in digital form. As the distance R of the measuring hole from the turning axis 112 is considerably greater than the dista R , a good resolution is achieved. Inside the hole 132 is a receiving unit 134 attached to the body 111 of the reacti member. A cable 172 connected to said unit may be an optic cable receiving light through the plate 133 and transmitting it to a detector situated near the axis of the reacting member, or the cable mentioned may be an electric cable leading to local photo-detectors within the receiving unit 134. An optic cable 135 is supplying light to the measuring point from a distant light source, which may be situated outside the rotating reacting member, as described later. The cable may consist of several fibres 173 arranged at the end of the cable properly for the purpose. Fig. 29 is illustrating one opening arrangement of the plate 133. In the example a momentary position of the sealing member is defined by using two digits. The less significant one is revealed by using round openings 136 and the more significant by using elongated openings 137. Correspondingly, the receiving unit 134 according to Fig. 30 is provided with receiving openings 138a-c for the less significant digit and openings 139a-d for the more significant digit. Members 140 behind the openings 138-139 may be the ends of optic cables or local photo-detectors. The dimensioning of openings being such that light is going at each moment through one or two openings 136 into the corresponding receiving means, a resolution of 41 positions is achieved. In the case of Fig. 29 light is going through openings 138a, 138b, 139b and 139c.Fig. 31 is a block diagram illustrating a regulation of movements of the sealing member. High pressure gas in the conduit 141 is distributed properly into the conduits 129 and 130 by using a valve member 142 controlled by an electronic control unit 143. Information about the momentary position of the sealing member is received from the measuring unit 144 described above in connection with Figs. 26-30. The unit 145 indicates a momentary error in synchronization between the working and reacting members, as described later in connection with Fiqs. 35-43.Figs. 32-34 describe one possible construction for the valve 142. The valve 142 is connected through an electric cable 175 to a central control unit and mounted into a space146 in the body of the reacting member near the piston- cylinder combination 127-128. The valve includes a moving part147 capable to turn in seme extent in relation to the axis 1 8, which is parallel to the direction 150 of a centrifugal force. The direction 149 of entering high pressure gas from the condu 141 is opposite to the centrifugal force and may be used f compensation of forces. Gas coming into a hollow interior 151 has an access through slots 152a-d in the circumferent wall 155 of the moving part 147 into conduits 129 and 130 through suitably formed openings 153a-d in the body 154 of the valve. Openings 153a and 153c situated at opposite sid are connected to the conduit 130 and correspondingly openin 153b and 153d to the conduit 129. The openings have triang formes described in Fig. 34. Triangles belonging to opposi conduits 129 or 130 are in opposite positions. Thus, as th member 147 is turned, an effective opening determined by t position of the slot 152 in relation to the corresponding triangular opening 153 leading to conduits 129 and 130 alt in opposite directions. Thus a distribution of gas flow through conduits can be controlled by turning the moving member 147 by any conventional electro-magnetic constructi involved in the valve 142. As the slots 152 are narrow, th effect of torque caused by gas forces is minimized. The us of two slots on the opposite sides results in a symmetrica construction for avoiding transversal forces.A precise and immediate determination of error in synchronization between working and reacting members may b based on the fact that a certain point in the constant- radius-edge 45 of the reacting member follows a certain tr on the bottom of the working space. Thus it is possible to define the error optically by using co-operating members situated at said edge 45 and at some point in the working member along said track. In Figs. 35-36 it is illustrated how by using an active measuring member 156 at the circum¬ ference of the reacting member it is arranged two measure¬ ments for each process cycle by using two co-operating members 157 being situated at the same distance from the axis of the working member. By using another measuring mem 156 on the opposite side of the edge 45 it would be possib to achieve e.g. four measurements for each rotation of the reacting member. In the example it is suggested that the co¬ operating member is a passive one which reflects back light coming from the member 156. The active member has effectively a multiplicity of light source - light detector pairs. The passive member is provided with a slit 158 which does not reflect light back to the active member 156. Thus it is possible to define which light source-detector pair is going on the position of said slit. The direction of the slit has an angle of tf in relation to _ expressing the direction of the circumferential movement of the_member 157. Correspondingly, the member 156 moves in direction y . The angle V .is selected so that the relationship tg/x/ = v /v is valid, where v and v are corresponding circum speeds. Thus the same source-detector pair remains on the point of the slit all the time the co-operating members cross each other. As the slit is formed to have a considerable length, the time of light pulse is long enough to ensure a response in other detectors in spite of great circum speeds and small dimensions of detectors. A precision corresponding to a fraction of a space between adjacent measuring points can be achieved if also relative light intensities are measured in ach -detector. A precision of 20-30% in intensity measurement would already mean an essential improvement. In the example it is suggested that true light sources or deterctors are not in the measuring member 156 itself, but light enters and leaves said member through optic cables 161 and 162. A real light source may be situated outside the reacting member, as explained later in connection with fig. 43. The location of the detector unit may be near the rotation axis of the reacting member. Figs. 38-41 illustrate a structure of the measuring member 156. The ends of light cables 161 and 162 are mounted at positions of holes 159 and 160. As it is seen from Fig. 39, light entering the slit 158 is practically absorbed. The width of the slit may be made very small if the reflecting member 157 is manufactured of two pieces attached together. As it is seen from Figs. 40-41, the measuring member may have a collar oart 164, by means of which centri- fugal forces are transmitted into the body of the reacting member. The measuring member may be mounted through an opening 163 in the partition wall forming surface 10. Afte mounting said opening is closed by a corresponding cover. Light cables 161-162 are extending in a cavity inside the reacting member to a vicinity of the axis of the reacting member, where the corresponding light dectectors 165 may b situated, as described in Fig. 42. According to Fig. 43 a light source unit 167 may be situated in connection with the stationary body of the machine and light is transmitte through a cable 166, the other end of which is situating coaxially at the end of the shaft 9 of the reacting member It is also presented how, by using three sliders 168 and a corresponding electric cable 169, it is possible to arrange an electric supply to devices inside the reacting member a further to transmit control orders and other information between the rotating member and the stationary body. By utilizing known electric methods three sliders are suffici for purposes mentioned, although a transmission of a multi channel information is concerned.In Fig. 44 is shown how through an axial conduit 174 high pressure gas from the stationary body may be supplied into conduits 121 and 141 for purposes of sealing members 110. Light from an optic main cable 166 may be distributed into cables 135 and 161 presented in Fig. 26 and Fig. 38, respectively. It is also presented, how electronic circuit needed may.be concernated into an electronic unit 170 situ ating near the rotation axis of the reacting member. The unit 170 may be mounted into its place through a channel 1 situated radially in the body of the reacting member. If t wall of the gas conduit 19 is provided with a small door ( shown), the mounting may happen handy. Electric connection to cables 169 and 175 may be arranged by using suitable contact plugs. Optic detectors relating to light cables 16 and 172 may also be situated in the electronic unit 170.Temperature control of members of the invented machin would ensure maintaining of minimal clearances. Because he-BΪJREAO PI exchange takes place through surfaces of members, at least a considerable part of heat exchange conduits for circu¬ lating cooling or heating gas would be situated near the surfaces of the members. In Fig. 3 is shown, how the working member is provided with a network 176 for circulating heat exchange gas . The circulation takes place through a conduit 177 leading to the end space 178 and a conduit 179 connected to the space 180 at the circumference of the working member. The mounting channel 51 may be closed after mounting of the working member by a suitable part 181. In Fig. 3 is also shown, how by using conduits 182 as well as spaces 183, a heat exchange circulation through the reacting member may be arranged, the end surface 10 of said member being provided with several holes, which are situated at certain intervals at a constant distance from the axis of the reacting member. As gas pressure in the temperature control circuit is main¬ tained the same as that in the working gas surrounding the reacting member, gas leak can be kept small. Spaces 183 in the wall of the stationary body of the machine may be surrounded by local labyrinth seal. An arrangement of heat exchange circulation into valve members is illustrated in Figs. 3 and 18. The pressure level in conduits 184 may be the same as that of working gas in the valve space, whence gas leak can be kept small.Main conduits leading to each member are' distributed into several branches. By careful planning a distribution of heat exchange may be made proper for resulting in a suffi¬ ciently uniform temperature within the body of each member. Temperature level may then be controlled e.g. by regulating total mass flow circulating through each member. The regu¬ lation may be based on temperature measurements with electric sensors located within the member in question. From a rotating member measurement information may be transmitted into a stationary control unit e.g. as described in connect¬ ion with Fig. 43.The state of the art in electronics and control technics further permits even orovidinσ each member with several branches which are individually controlled. This ha been illustrated schematically in Fig. 45. Parts being situated inside a rectangle 185 are within a rotating memb In the stationary part of the machinery is located a pump 186 for gas circulation as well as a heat exchanger 187. T flow- conduit 188 is divided inside the rotating body into branches 189. The amount of average gas flow is controlled valve means 190. A circuit connected to each valve consists of at least one temperature sensor 191 and an electronic control circuit 192. The state of the art permits a use of small and unexpensive control components, whence even numerous control circuits may be used in each part of the machine. Neither a high temperature of structures would be a hindrance, because in that case the control unit may be situated inside a thermally insulated casing, inside which part of cooling circulation is conducted. Besides, the structures may be kept at a low temperature level even if working gas is used, as discussed later.Supplying energy into a rotating member may be arrang also otherwise than by feeding along the corresponding shaft. It is possible to use a winding inside a rotating member, which is passing through a magnetic field created by means being situated in the stationary body of the machine. It is also possible to use circulating heat excha gas for rotating a small generator. For transmitting infor mation also wireless methods may be used, e.g. optical technics.A total dimensioning of the machine may be such that during running the temperatures of the rotating members ar maintained somewhat higher than that of the stationary bod of the machine. Thus during running smaller clearances app than in an isothermal case.The heat exchange network needed in each member may b arranged e.g. in connection with casting procedure. If the member in question is composed of several parts united by welding technics, the conduits needed can be easily arrang If it is desired to use conduits going very near the surfa an arrangement described in Fig. 46 may be used. The surfa of a body 193 of a member in question is provided with grooves 194 forming a heat exchange network. The grooved surface is covered by a thin plate 195, which may be fastened here and there by screws or by welding. If the pressure in the temperature control circuit is kept some¬ what lower than that of the working gas, a compression against the body results, even though applied to the rotating member.As stated earlier, the possibility of reducing the speed of gas leak is one important advantage of the invented machine. As the pressure level is high, the use of a laby¬ rinth seal is advantageous, because then the speed of gas leak is depending on the pressure ratio over an individual throttle line and not on an absolute pressure difference. A straight labyrinth seal may be arranged by using numerous grooves at least in another surface forming the clearance in question. The grooves are transversal in relation to the direction of gas leak and they may be interrupted here and there in cases where there is a possibility for leak also in the direction of the grooves. Especially in compressor use it is advantageous to use grooves at the circum surface of the edge 45, as described in Fig. 22. Similarly, the circum surface of the working member may be provided with a seal structure 104 extending through the separating wall 21 and thus surrounding the process space, as described in Fig. 4. In expansion use it may be more desirable to use a seal structure at the bottom of the working space and at the inner surface of the stationary body of the machine. In expansion use namely, a gas leak takes place in the direction of the movement of the partition wall in relation to the working space and correspondigly in the direction of the movement of the separating wall 21 iri relation to the stationary body. Because the speed of gas leak is reduced to some value in relation to the labyrinth seal structure, the effective speed is now a difference between the gas speed and the speed of the wall in question both taken in relation to the seal' structure. Thus, by using an effecient seal structure and a sufficiently high wall speed, gas leak would be in princip even totally prevented, provided that the volume involved with grooves is negligible as compared with the volume of the working space.Figs. 2-3 are indicating other surfaces to be provide with a straight labyrinth seal, namely in the stationary body of the machine the surface 105 opposite to the end surface 10 of the reacting member as well as surfaces 106 and 107 surrounding the valve openings 26. In addition, a labyrinth seal is used in connection with pressure compen¬ sations, as indicated in Fig. 9 as to the compensation wit the reacting member. In connection with a compensation' of valves, the grooves may be partly arranged at the bottom o the mounting piece 34 presented in Fig. 7.The profile of a labyrinth seal may be e.g. that pre¬ sented in Fig. 47. The profile is formed by grooves 62 be ween ridges 196. Tooth spacing S may be5s-10s, where s = clearance. If a clearance of 0.1-0.2 mm is maintained, a tooth spacing S = 1 mm might be suitable. Fig. 48 is pre¬ senting a relative reduction of gas leak IT . / . as a funct t of the number N, of throttle lines one after another. Curv for tooth spacings S = 5s, S = 10s and S = 20s are achieved by a theoretical extrapolation based on an experimental study o air indicated by circles. It is concluded that if the toot spacing were 1 mm or less, a reduction factor 0.1-0.2 is possible to achieve as to major part of clearances occurin in the machine. As to the clearance 14, a reduction factor of 0.3-0.5 is well achievable.A heat exchange of working gas with inner surfaces of the machine may be reduced by using an internal heat insu¬ lation. Surfaces, into which it is easy to arrange an insulation layer, include stationary surfaces of the valve spaces, side surfaces of the valves, stationary surfaces surrounding the reacting member, the circum surface of the reacting member as well as the bottom surface of the worki space in the position of the end portion 22. The surfaces mentioned are characterized in that no precise dimensionin is required. In addition, the temperature of working gas near the surfaces remains unchanged during each process cycle. The surfaces mentioned may be shielded in accordance with Fig. 49 with an insulation layer 198 between a base structure 197 and a covering metal plate 199, which may settle down to .-a temperature near that of working gas . The heat insulation layer may be composed of some sheets 200 in series. The said sheets may be separated from each other by supports 201 of wire type. Supports next to each other may go crosswise whence the structure may bear pressing forces of some magnitude. A pressure level in the insulation space may be maintained as the- same as the pressure of the working gas or somewhat smaller. In the latter case the structure may be used also at surfaces of rotating members, because the centrifugal force is overcome by the pressure difference. Because the insulation layer is thin, only a small pressure difference is needed. A suitable pressure level may be arranged by connecting the insulation spaces into a tempera¬ ture control circuit of the member in question. A possibility for thermal expansion or contraction of the covering plate 199 may be arranged by using foldings 202 in both directions at suitable intervals. A basic fastening into the base structure may be secured by fastening elements 203. The effeciency of the insulation structure presented in Fig. 49 may be based on several surfaces in series. The lack of forced convection would result in a poor heat exchange coefficient at each surface and thus in a sufficient insulation. Besides, sheets in series would serve as a shield against radiant losses.It is to be noted that requirements as to heat insulation are quite low. If the thickness of insulation is d, k is the effective conductivity in insulation layer and <_3T is the temperature difference, a heat flow density q = k_ T/d is resulting. If k = 0.1 /m°C, ΔT = 400°C and d = 2 mm, then q = 20kW/m , which is so a low value that the quantative heat loss is insignificant as compared with the useful work done by the machine.Surfaces surrounding the process space are characterized in that a precise demensioning is required. When the machi is applied as an engine in a heat power process, said sur¬ faces need not to be at a higher temperature than that of working gas after expansion. It might be still more advant geous to manage with a further lower temperature. Therefor in the following a calculation is made concerning the heat loss which might then result. If surfaces not requiring a precise dimensioning are insulated as illustrated above, t total area exposed to the hot working gas for each process2 space would be about A = 2D in one process space. The he loss during one process cycle may be calculated from the equationQw where T = temperature of wall, T~ = temperature of gas af expansion, T.. = temperature of gas before expansion, p1 = pressure before expansion, p2 = gas pressure after expansi R = universal gas constant, c = heat capacity of working in constant pressure, h = heat exchange coefficient, A = area of heat exchange surface and t = time of process cyc In the equation a reducing coefficient 0.25 is used for a part exceeding temperature T_, because a higher temperatur occurs only for a part of time. Into the equation nay be inserted area A = 2D 2 as well as cy —' w Jcle time tc = //D/2vR--, where D = the diameter of the working member and v- R-, = the circum speed of the working member. Most uncertainty is relating to the heat exchange coefficient h. As working ga is supposed to be helium, in the following is used a formu h = 20 (_p v )°'8/D0-2 (W/M2oC) , as [ ?v ] = kgm2s and [D] in.which gas sp ceed is vg = 0.5vnR. It is to be noted that abou a half of the walls of the process space are stationary, whereas the other half is moving in the direction of gas fAdditionally, a typical circumferential speed of the centr of area of the partition wall is vg = 0.8vR-- . As the Reynol number is very high, the entrance section effect is probab quite small. Density is calculated at the mean temperat of the boundary layer. Heat Oss is compared with the work done by gas during one process cycle, namely-R/cW- (cp/R) Pi V1 - (P1/P2)3 where V_. = 0.1D is the maximum volume of one process space before expansion. By using numerical values D = 0.75 m,VR = 120 m/s, p_. = 50 bar and p2 - 25 bar the ratios Q /WQ as well as heat flow densities q presented in the following table are obtained with various wall temperatures T , as expansion of gas is thought to happen within the temperature range 850K - 650K (577°C - 377°C) :T 100 Q /W_ q w w 0 ^350K { 77°C) 4% 400kW/m2500K (227°C) 2% 200 650K (377°C) 0.5% 50 According to the calculation the walls may be even near the ambient temperature without resulting in a great relative heat loss. Neither is the heat flow density too great as far as thermal stresses are concerned, if a cooling circulation is arranged near the surfaces in question. Consequently, in connection with the invented machine even very high gas temperatures may be used and still essential parts of the machine be maintained at moderate temperatures . It may be concluded from the formulae presented that the significance of working gas as well as the size of the machine to the relative heat loss is of minor importance.Figs. 50-51 present a heat insulation structure which may be used even to shield surfaces surrounding the process space. If the shield were used at least to a remarkable portion of said surfaces, the heat loss would then be reduced correspondigly. The most suitable surfaces appear to be the stationary surfaces of the body, especially the cylinderic portion, and the bottom portion of the surface in the working member. According to Figs. 50-51 the surface in question would be covered by plates. 204, which are fastened into a base structure 197 centrally so that thermal expansion o contraction takes place symmetrically in all directions, t middle line 0 of each plate remaining fixed. The plates 20 are supported by a series of co-axial cyliners 205 made of thin material. Said cylinders are installed into corres¬ ponding grooves 206 and 207 in the base structure and the covering plate. The idea involved is that a cylinder-symme rical structure with thin walls may undergo a thermal expansion or contraction due to a temperature gradient in the direction of the central line 0 without excessive thermal stresses in the material being induced. The plates 204 are warmed or cooled isothermally and a temperature change appears at the supports 205, which thus becomes som what conical. The use of cyliner-symmetrical supporting structures would result in an essentially greater rigidnes against force components transversal to the line 0 than th use of many separate thin supports. The supports 205 may b fastened into the base structure 197 e.g. by welding. Also fastening to the plates may be done by welding at the position of projection portions 208 extending through the plate in holes made therein. Thus, the structure may resis also pulling stresses and is thus suitable to be used in rotating members. Certainly, if the pressure level used is high, forces caused by pressure difference are considerabl greater than the centrifugal force effecting a relatively thin plate, whence a pulling stress may be avoided. Altern tively, the fastening of the plates into the base structur may be effected by using bolts, which would preferably be thermal contact with the supports 205.If the total cross-section area of the supports were of the area of the plate, the pressure in the underlying space 211 were the minimum pressure of working gas, and if the pressure range used v/ould be as high as 100bar - 50bar2 then a maximum stress of 5kN/cm v/ould effect on the suppoIf the supports were of iron material with a thermal condu tivity of 50W/m C, the free hight of the supports were 2 cm and the temperature difference 400 C, then a mean heat flow2 density of 100kW/m would result. As compared with the table presented above, this would correspond to a relative loss of 1%.A sufficient seal between the process space and the underlying space 211 may be arranged by using a seal 209 with a round cross-section permitting a slight movement in direction of a thermal expansion or contraction. When used in a machine using hot working gas the plates can be dimen¬ sioned so that at a high running temperature the slots between the plates are reduced to zero. In a machine using cold working gas this is not possible. In that case an arrangement described in Fig. 52 is possible for preventing gas leak through remaining slots 213. The example is thought to refer to the covering of the surface of the working member. To prevent gas leak under the circumferential edge 45 of the reacting member, those sides of the plate not parallel to said edge are formed to be of zik-zak character having portions 212 and 213. The slot '212 does- not change during cooling of the plates, whereas the slot 213 grov/s . Because the slots 213 are so short that they do not extend over the edge 45, a continuous gas leak is prevented. The gas volume involved with the slots remains negligible as compared v/ith the volume of the working space-.If an expansion machine is concerned, the surface of the plates may be provided with a labyrinth seal structure 210, as sketched in Fig. 51.The use of an internal heat insulation as described above makes it possible in connection with every application of the invented machine to maintain the temperature of the stationary body as well as of the essential parts of moving members near the ambient temperature. Thus, favourable conditions for using precise roller bearings in every appli¬ cation are guaranteed. Bearings with a negligible free play offer a good basis for utilizing temperature regulation for maintaining clearances of the machine at a minimum. Alter¬ natively, the use of gas bearings would permit a free selec- tion of the bearing temperature.In Fig. 53 an alternative total construction of the machine is sketched. In contrast to Fig. 1 the body 4 pf the machine is of one piece, whereas one machine unit consists of two working members 1a and 1b mounted on a uniform power shaft 2. End walls 214 mounted after the working members increase the rigidness of the body.Fig. 54 presents graphically various quantities asso¬ ciated with the machine in accordance with Figs 2-3 as a function of rotation angle of the working member, the origin of j -axis corresponding to the situation, where the extreme end of the process space is at the position of the partition wall, corresponding to the starting moment o an expansion cycle. Curves presented include a time course of the total area A of the valve opening as well as the area Apr of the p^artition wall r•educed to a distance D/2(Fig. 3) of the circumference of the working member. As the centre of gravity of said reduced area is thought to b located at the distance mentioned, true values for the working volume as well as for ttie torque may be calculated by using this constant distance D/2. In expansion use the process proceeds in the direction of the positive w-axisAreas A and A grow quite equally in time from the ver beginning of the cycle. In the example closing of the valv starts at ^w = 90° and ends at _f = 105°. During the clo period the reacting members as well as valve members rotat an angle of 30 . Expansion ends at f = 135 . In the figu is also presented the time course of gas speed v in the opening of the valve, provided that the circum speed of the working member is 80 m/s, the working gas being helium at temperature of 370K (97°C) before expansion. Within ψ = 0-90 , where areas A and A are of the same order, the speed is fairly proportional to the ratio A /A . During the closing period the sizes of the valve opening and the effective piston area do not correspond to each other, whence a rise of gas speed results. The quantitative signi ficance of losses induced during the closing period is not dominating, however, being partly due to that closing is happening rapidly because of a small visual angle α (Fig. 7) of the valve opening, partly to that in consequence of the low pressure ratio used, the volume of the process space at the moment of the beginning of the closing period is great, resulting in a relatively small change of volume ratio during the short closing period, whence also a formation of pressure ratio between opposite sides of the valve opening is remaining small, said pressure ratio being a necessary presupposition for a rise of gas speed. Accordingly, gas speed v in expansion use during the closing period is rising remarkably more slowly than ratio 'A /A .In compression use the process proceeds in the direction of the negative ϊr Vv-axis. If the opening of the valves is started at ^w = 105 , it may result in a course of gas speed v presented in the figure during the opening period. However, in compression use it is possible to manage v/ith smaller losses, if a small advance in the opening of valves is used, resulting in that gas is first flowing backwards. In the example in accordance with Fig. 54 the kinetic energy of the amount of helium gas flowing through the valve opening of one working space during one expansion cycle may ' be calculated from the equationwgv Vfc) [vgv(t)] 3 dt' • and correspondingly the work done by the same gas amount during .one expansion cycle from the equation where subscript 1 is referring to the state of gas before expansion and subcript 2 to the state after expansion, v_ = circum speed of the working member, D = diameter of the working member, V. = maximum volume of working space before expansion and p_. = gas pressure before espansion. By using3 pressure ratio P../P-, = 1.80 and the relationship V. = 0.1D which is approximately valid in the example, it may be concluded that the kinetic energy Wgv is about 1 % of the work Wfi done. The kinetic energy is corresponding to a constant gas speed v - 90 m/s. As by using this mean velocity the relative pressure drop in the valve opening_2 is calculated from the formula 0.5 J _1. v gv/p*.! , a numeric value of 0.006 is obtained in the case of helium at the temperature presupposed above.The calculation presented may roughly indicate pressu losses in the machine, because the working space correspon to quite a short and wide flow conduit with low friction losses, taking also into account that one side wall is stationary and the other is moving in the direction of gas flow and that a typical circumferential speed of the cent of gravity of the partition wall is about 0.8vα. In additi all kinetic energy calculated above does not necessarily mean loss.In Fig. 54 it is still presented a course of torque M as it is supposed that two functional basic units are used in opposite phases in accordance with Fig. 1. Fluctuations in the torque curve are of so high frequency that the iner of rotating masses is sufficient to maintain the speed of rotation practically constant even at high pressures . In Fig. 30 a timing of different phases is certainly such tha it would be possible to use on the same shaft three comple machine units in accordance with Fig. 1 at a phase shift of 5 = 30 , whence a practically ideal torque could be gainThe moment of the valve action presented in Fig. 54 results in a pressure ratio of the order of 1.8:1, if one- atomic gas is used. By selecting the time interval of valv action otherwise it is yet possible to reach different pressure ratios. If the closing of valves were started in expansion use already at y W = 70°, it would be possible t achieve even with two-atomic gas pressure ratios more than 2.5:1. The structure of the invented machine makes it possible to regulate at least to some extent the pressure ratio by altering the phase angle of the rotation of valveOΛ.P - - ' • Then it would be advantageous to have an additional width in the separating wall 21 so that opening of each virtual valve in expansion use and correspondingly closing in compression use would happen totally in the shield of said separating wall within the whole regulating range.At the best operating point of the machine the best compromise is achieved between pressure losses and gas leak. To illustrate quantitatively the order of minimal losses, also a relative gas leak is evaluated by using the example of Fig. 54, where working gas is helium at the temperature of 370K (97 C) before expansion, circum speed of the working member being vR = 80 m/s. Leaking clearances of the machine may be classified as follows: 1) clearance 13, corresponding to edge 44, 2) clearance 14, corresponding to rim 45, 3) other clearances associatedwith the process space, including clearances surrounding the valve openings, and 4) clearances associated with pressure compensations. When as a characte¬ ristic measure of the machine is used the diameter D of the working. member, then as reduce lengths of leaking clearances for one working space may be used values l→ = 0.1D, 12 = 0.5D, 13 = 2D and 1. = 1D. These reduced lengths give a correct gas leak as it is thought that leakage takes place during the v/hole process cycle and a maximal pressure ratio is present over each clearance. The volume leakage during one cycle is reduced to -a state of maximum pressure, because it is then readily comparable with the maximal volume of the process space before expansion. Said maximal volume is in the example about V.. = 0.1D , which is the volume of one process space when the partition wall is at _ψ = 90 . Gas leak through clearance 13 is supposed to happen with a velocity of sound. As this velocity is reduced to the maximum pressure state, the relationship is obtained, subscript 1 referring to the maximum pressure state and L to the Laval state. As numerical values c /c p v 1.67, f - I → = 0.650 and Ty /T = 0.750 of one-atomic gas and molecular weight M = 4 kg/kmol of helium are inserted, a numerical value v.. = 0.726 (RT../M)0.726{8314x370/4) ° 5 = 640 m/s is obtained. The relative gas leak can be obtained from the equationV1/V1 = (7?O/2vR) (0.1D s1 v_j + 0.5D s2 v2 + 2D s3 v3 +1D s4 v4) / 0.1D3,where clearances have been divided into four groups listed above. In the following table numerical values of relative gas leak have been presented in cases 1-4, in which variou values for mean clearances s1 - s, as well as reduced speeds v_. - v. have been presumed.case 1 case 2 case 3 case 4S1 0.25 mm 0.25 mm 0.5 mm 0.5 mmS2 0.05 mm 0.1 mm 0.2 mm 0.3 mm0.05 mm 0.153 mm 0.2 mm 0.3 mm54- 0.05 mm 0.1 mm 0.1 mm 0.2 mmV1 640 m/s B40 m/s 640 m/s 640 m/sV2 180 m/s 250 m/s 350 m/s 430 m/sV3 75 m/s- 100 m/s 150 m/s 200 m/sV4 75 m/s 100 m/s 100 m/s 150 m/s relationship 0.006 0.012 0.028 0.05 for gas leak D D Dgas leak, if 0.6% 1.2% 2.8% 5% D = 1 mThe clearances supposed are mean values, e.g. clearan s_. may vary within 0-2s_. in ordinary use. It is found on t basis of the calculation that a relative gas leak of 0.5-5 is possible to reach at an operating point where pressure losses are of the order of 1%. As proved earlier, the temp rature level or the quality of gas does not effect on the result. If air were used insted of helium, an optimal speed v„ at T. = 370K (97°C) might be under 30 m/s.Fig. 55 is presenting a total block diagram including main parts of the invented machine as well as external devices needed for accomplishing control functions presented earlier. External devices include a synchronization control unit 236 for synchronization of the other members with the rotation of the working member. A synchronization sensor circuit 215 may utilize some conventional method, e.g. an optical one. Figs. 35-43 are presenting one way as to the reacting member. Precision requirements are considerably lower in the case of the valve members as well as pressure compensators. A temperature control unit 216 regulates mass flow through pumps 186 on the basis of temperature measure¬ ments with temperature sensor circuits 217. The pressure level in each thermostat circuit is maintained suitable by means of compressors 218. The diagram includes chambers 219-221 for high pressure gas to be supplied to the sealing members in the reacting members and to pressure compensators presented in Figs. 11 and 14. Pressures needed are produced by compressors 222-224. Conduits for p, and p .. may be connected directly to the conduit 19, if the temperature of the working gas is near the ambient temperature. In the case of an expansion mach'ine of a heat power process, a connection may be made into the corresponding conduit 19 of the com¬ pressor of the Brayton-cycle. Also is presented means for controlling pressures in the conduits 18 and 19 when a closed process is used. Said means consists of chambers 225-228, valves 229-232, a control unit 233 for regulating said valves so that, when needed, either more gas is entering the process circuit from high pressure chambers 225-226 or part of the gas is removed from the process circuit into low pressure chambers 227-228. Compressors 234-235 are pumping gas from low pressure chambers back into the corresponding high pressure chamber.The presentation of the embodiment accordinσ to ^igs. 1-55 is so detailed that a person skilled in the art can understand as well as accomplish the invented machine. Auxiliary devices presented in Fig. 55 are conventional. As to the two alternatives concerning the sealing member, a selection between them depends on the application in question. If an emphasis is put on structural simplicity and if disturbances caused by a machine connected to the invented machine are small, the former alternative present in Figs. 23-24 is adequate.Figs. 56-57 illustrate another kind of modification o the invented machine. By this modification it can be achie in principle an arbitrarily great pressure ratio, which in addition may be regulative. '.Fig. 56 presents the machine a the section corresponding to Fig. 3, whereas Fig. 57 corre ponds to Fig. 4. The rotation space of the working member includes an extension part 48 surrounding the cylindrical main part, the separating wall 21 of the working member be provided with a projection part 50 corresponding to the cross-section of the channel 48 in the body of the machine The partition wall forming part 10 is provided with one transition sector 77. The edge line of the partition wall forming part 10 is now of such general form that when the angle co-ordinate varies starting from the sector, whi is turned towards the working member when process cycle changes and the separating wall 21 between working spaces is correspondingly turned towards the reacting member, to direction corresponding to the order of arrival of various points of said edge line in expansion use into the rotatio space of the working member, the radial co-ordinate increa from the minimum value r0 at first to an intermediate val r_. , v/hence the reacting member is extending into the mentioned projection part 48, but not yet into the main pa of the rotation space of the working member, and in the second phase to the maximum value r.., , whence the reactin member now extends also into the main part of the rotation space, and at last said co-ordinate decreases to the start value rQ near the completion of the whole circle. The forTURH of the working space corresponds to said form of the reacting member. A process phase corresponding to an open valve is restricted to the projection part 48 resulting in a small cross-section of the partition wall, whereas during the process phase corresponding to the closed valve also the main part of the rotation space is in use, resulting in a great cross-section area of the corresponding partition wall. Consequently, a great volume ratio can be achieved. The valve of the machine may be of the same kind as was presented in connection with the preferred embodiment of the invention. Because the cross-section area of the projection part is small, it is possible to manage with one true valve member, by means of which three virtual openings may be formed as presented earlier. If the projection part 48 is located symmetrically in relation to the reacting member, it is possible to interconnect the shafts of said members by means of a universal joint, whence the rotation of the valve member may happen through the reacting member.Hov/ever, by using an independent mechanism for rotating the valve member, it would be possible to use a greater valve member and thus achieve a faster closing or opening. Additio¬ nally, it would then be possible to regulate the pressure ratio by altering the phase angle of the valve in relation to the other rotating parts . It would thereby be advantageous to have an additional width in the separating wall in such extent that closing of the valve in compression use as well as opening in expansion use would happen completely in the shield of said separating wall within the whole regulating range.Figs. 58-59 illustrate still another modification of the invented machine. In this modification no true valves are needed. Fig. 58 is corresponding to Fig. 3 and Fig. 59 to Fig. 4. Again, the partition wall forming part 10 has one transition sector 77. The edge line of the partition wall forming part 10 of the reacting member has now such general form that as the angle co-ordinate _P is varying starting from the sector, which is turned towards the working member, when the process cycle changes and the separating wall 21 between working spaces 5 is turned correspondingly, towards the reacting member, to a direction corresponding to the. order of arrival of various points of said edge line in expansion use into the rotation space of the working membe the radial co-ordinate is increasing from the minimum valu r„ to the maximum value r→ , decreasing after this to an in mediate value r„, and finally to the starting value r„ nea the completion of the whole circle. Fig. 59 is presenting the form of the working space 5 as a function of the rotat angle w of the working member and of the co-ordinate z in the direction of the rotation axis of the working membe It is characteristic of the working space that a section 2 at the process space end, corresponding to the maximum radius r→ of the reacting member, is extending further sid wise in direction of the rotation axis of the working memb than any other part of the working space. Then the gas opening 26 may be located in- the body of the machine so th in direction of the circumference of the working member it located on the process space side of the partition wall 15 and extends close by said wall so far in direction of the rotation axis of the working member that only the mentione section 237 extends to the position of said opening. Accor dingly, the valve operation may be based on the rotation o the working member. The opening 26 is closed by the unbrok part 238 of the circum surface of the working member. Thus expansion use the valve starts to open, when the process space end of the working space and thus also the section 2 is passing the position of the partition wall 15, and the valve is closing as the section 237 has proceeded over the opening 26.Fig. 60 illustrates a possibility to combine two functi units 40 in parallel so that reacting forces induced are compensating each other. It would be easiest to utilize th possibility in connection with the embodiment in accordanc with Figs. 58-59, because then the valves are not in the w To the reacting member 8a situated between working members a compressive stress is induced, whereas to the shaft 9 between reacting members 8b a tensile stress. By using a force pair F-F it would be possible to arrange a compen¬ sating moment whence a bending moment to the shaft 9 can be avoided.Industrial ApplicabilityIn order to illustrate possibilities of applying the invented machine in a heat power process it is examined in the following a two-stage Brayton cycle according to Fig. 61 including two expansion machines M one after another with corresponding heat exchangers E, in front of each machine, and correspondingly two compression machines M one after another with corresponding heat exchangers E, in front of each machine. In addition, the process includes heat exchan¬ ger E between hot and cold sides. Incoming heat flow Q. is transformed partly into mechanical work. Engines M deliver power P , whereas compressors M consume power P . As is well known, an ideal Brayton cycle consists of isentropic phases in engines as well as in compressors and isobaric phases in heat exchangers . In order to analyse the cycle mathematically each real expansion machine is replaced by a substitute model in accordance with Fig. 62, and correspondingly the com¬ pressors are replaced by a substitute model in accordance with Fig. 63. The substitute models have an ideal expansion __ξ_ or compression machine M' or M with a parallel block 239 denoting relative gas leak a, and a serial block 240 denoting relative pressure change b especially in the valve opening. If the pressure ratio in the real expansion machine is p3/p4, appears the pressure ratio (1-b)p,/p, over the ideal expansion machine, resulting in a temperature fall of working gasV 4 = < 1 (1-b) T- in isentropic expansion, temperature notations being those expressed in Figs. 61-63. As gas leak is supposed to happen isothermally for a dominating part (after transformation of kinetic energy of leaking gas into heat) , temperature fall of gas in the real expansion machine is-R/c 3T4 = (1-a) { 1 - (1-b) (p3/p4) Vτ3 = fE(a,b,p3/p4)Correspondingly, over the ideal compression machine appear the pressure ratio (1+c) (1+b) (p3/p4) . where term c is taki into account pressure losses in the heat exchangers of the process circuit. Thus, it is obtained for the rise of work gas temperature in the ideal compression machine the equatR/cT -τs (1+c) (1+b) (p 1 0 ■ [ ,/P4>] Tin isentropic compression. If the dominating gas leak take place isothermally, then by applying the realtionship TQ = (1+a)T - aT1 obtainable from the joint point 241 for a temperature rise in the real compression machine is obtain the equation(1+a)| [(1+c) (1+b) (p3/p4)] Pj- 1T -T TQ = gc( a,b,c,p3/p 1 ~ o 1 - a [(1+c) (1+b) (p3/p4)] p|- 1In the equations presented there have been at the sam time defined functions f and g for expressing generally th size of temperature change in isentropic expansion or com¬ pression, as f-function is multiplied by the maximum tempe rature of the temperature range in question and correspond ly g-function by the minimum temperature, subscript E denoting expansion and subscript C compression.For process effeciency or the ratio of the difference of powers of expansion and compression machines to the hea flow coming into the process is then obtained equations- P (τ3-τ4) - (τrτ0) - 9 l . in (T. - (T t T2)/N LΛ f T + E 3 (1-e) (T4 where N = the number of stages one after another (in Fig. 61 N = 2) , e = (T„-T ) / (T . -T . ) is the temperature effeciency of the heat exchanger E , and coefficient m. is taking into account heat losses into walls of hot spaces.Fig. 64 presents graphically the process efficiency m as a function of the maximum temperature T-. of gas with various values of loss parameters a,b,c and e, when the minimum temperature of gas is T_ = 30OK (27 C) , working gas is one-atomic, e.g. helium, the pressure ratio p3/p4 = 1.80:1, number of stages N = 2 and T). = 0.97. Dotted curves present theoretical upper limits of the effeciency. It is noted that, for example, in case of the combination a ='0.02, b = 0.01, c = 0.02 and e = 0.95, the effect of losses is quite small. When a closed high-pressure process with helium as working gas is used, the temperature efficiency e = 0.95 used in calculations is fully realistic.As it was stated earlier, losses within the machine in principle do not depend on the working gas used. Therefore, also the use of air as working gas may come into question. As then the speed of rotation would be lower, it would be possible to use a smaller machine with an electric generator producing the frequency of a general electric network.As it may be concluded from Fig. 61 , waste heat flow Q can be removed from the process in a profitable form from the secondary side E.. of the counter-current heat exchanger E, . If the pressure ratio in the machines of the process were of the order 1.8:1, a rise of temperature in the compressor and also on the secondary side of the heat exchanger would be of the order of 80°C . By selecting the pressure ratio properly the process may be planned for various uses of waste heat.In evaluating the over-all electric effeciency of a power plant also losses of electric generators and in fuel- fired power plants also in a burning process must naturally be taken into account.To prove that the specific power of the invented machine is high enough, it is presented in the following table the quantity p , , which is the difference of powers of the expansion machine M and the compressor M as well as the quantity (m +m ) /P u. > which is the sum of weights of. the both machines divided by Pout, , as a function of the diametD of the working member of the expansion machine and of pressure p_. before expansion:Each expansion and compression machine has been thoug to comprise two functional units in accordance with Fig. 1 Working gas is supposed to be helium and the circum speed the working member of the expansion machine v-- = 120 m/s. The maximum temperature of working gas is supposed to be about 80OK (about 530 C) . If air were used as working gas instead of helium, power attainable would be about half of that indicated in the table due to a lower speed of rotati Most of weight is in the stationary body of the machine, which may be lightened somewhat e.g. by radially extending cavities, whence individual material thicknesses are not s great thinking about manufacturing e.g. by using casting technique. If the body is composed of several parts by usi welding technique, possibilities for a considerable lighte are good.As a typical weight of a condensing turbine is about 5-10 kg/kW, the invented machine should be fully competiti It can also be proved that weights of heat exchangers need in the Brayton-process are only of moderate order, when a closed high pressure process is used, especially with a light-weighted working gas. Besides, heat exchangers are needed also in a Rankine-cycle. Weights of non-condensing turbines may be of the order of 1 kg/kW, but the effecienc as to mechanical or electric energy is essentially lower. One interesting reference would be slowly running diesel- engines, e.g. in large ships or for a power plant use, which may have a weight of 40 kg/kW, for example. In addition to the high weight of the engine drawbacks include that only expensive oil can be utilized as energy source and that life time is not the best possible.In the use of the invented machine for energy storing said machines are used as components performing expansion and compression in a reversible storing process.Figs. 65-66 present process diagrams of the energy storing process especially when a solid cold store is used, Fig. 65 corresponding to a charging period and Fig. 66 to a discharging period. The process cycle 251 is a Brayton-cycle provided with a heat exchanger E between warm and cold parts of the circuit. The cycle includes a machine M, working near or above the ambient temperature and a machine M-, working below the ambient temperature. During a charging period the machine M, functions as a compressor, v/hereas the machine M, operating on a lower temperature level funtions as an expansion machine. Consequently, mechanical work must be fed to the process during the charging period. During said period the working gas is warmed in the compressor M, from temperature Tl to temperature T' . Then the gas is cooled in a counter-current heat exchanger E, to temperature T ' , in other words approximately to the temperature before compression. Water taken from a cold water store S or from an open water supply is circulated by means of a pump P, in the circuit 253 so that the temperature of the water rises in the heat exchanger E, e.g. to 90-100 C, whereafter the water is stored in a hot water store S, . Then the working gas is further cooled in the heat exchanger E to temperature T' and after that in the expansion machine M.. to temperature T' The gas is then warmed up in the counter-current heat exchanger E to temperature T', thus making it possible to remove heat from the cold store S, . Then the working eas is heated in the heat exchanger E to the temperature T' mentioned earlier, at which the process cycle has become completed.The maximum temperature Ti of the gas may naturally be permitted to exceed +100 C by an amount corresponding to a temperature difference needed in the heat exchanger E, . Additionally, the minimum temperature of water may be even under 0 C, if salty water is used.In the cold store circuit 252 some fluid, e.g. air is circulated with the aid of pump means P, . The cold store S, being of solid material it may be provided with a multi¬ plicity of parallel flow conduits, so that the store may be used as a regenerator having a very great time constant. Thus, during a charging period the temperature of the cold store decreases slowly. To achieve as reversible operation possible, a temperature gradient is permitted o be create in the storing material in the direction of conduits so th the temperature difference between the ends of the store is of the same order as the change of gas temperature in the machine M_. working at a lower temperature- level.During a discharging period the process is used in t opposite direction. Then the machine M, working at a highe temperature level is used as an expansion machine, whereas the machine M, working at a lower level is used as a com¬ pressor. Consequently, the process is capable of producing mechanical work. From the store S, is taken hot water, whic is cooled down in the process before going into the cold water store S or to the open surroundings. As working gas cooled in the heat exchanger E, from temperature T- to temp rature T0, the corresponding heat amount is got into the cold store S, , the temperature of which thus slowly rises.In practice the process may include both on the warm and cold sides several machine heat exchanger pairs (M, -E, , M,-E,) in series, resulting in smaller losses cause by the heat exchanger E having a certain temperature effi¬ ciency.The process diagram presented may be modified so that the cold stores is directly a part of the circuit 251,O.V.P* 1 ' whereby working gas would circulate through the cold store, the heat exchanger E. as well as the pump means P, being omitted. On the other hand, an additional liquid-form circuit between the cold store S, and the process circuit 251 may be used for transmitting the cold capacity over a conside¬ rable distance.The change of water temperature in the storing process may be of the order of 40-100 C, whereby the corresponding change of gas temperature in the cold machine M, may be 10-60 C, depending partly on the temperature level at which the cold machine f nctions at each moment.Figs. 67-68 present partial process diagrams for a charging period, when liquid material is used in the cold store. If the material is in a liquid form over a wide tempe¬ rature range, e.g. between -40 C - -180°C, the whole range may not be utilized in one process stage. Then it is possible to use arrangements according to Figs. 67-68. In the both cases two cold store units are used, the sto •re un-it Sl,a containing colder liquid and the unit S_, warmer liquid. In Fig. 67 the temperature of liquid in the store S,, is at an upper limit of the temperature range used and during a charging period liquid taken from the said store unit is circulated by the pump P.. through several heat .exchangers E_. , the cold store 'sides of which are connected in series and being thus cooled down to the lower limit of the total tempe¬ rature range used before transferring into the store unit S. , which thus receives liquid having a minimum temperature. The opposite sides E_. of corresponding heat exchangers are each connected to corresponding process cycles, which are in parallel, but the lower temperatures of which are stepped so that temperature ranges in cold machines of the various circuits together cover the temperature range used for cold liquid. The parallel circuits mentioned may be wholly sepa¬ rate, or they may have the machine M, and the heat exchanger E, in common. In Fig. 68 only one process cycle is needed. Cold liquid is transferred by the pump P, during charging period from a warmer store unit into a colder one, until the- BURE U first-mentioned store is empty. Then the direction of circulation is reversed by using valve means V.. and V„ so that liquid is transferred from the full store into the empty one and is still cooled because direction of circu¬ lation remains unchanged regarding the heat exchanger E, . After each reversion of curculation the working temperatur level of the cold machine M, is lowered. The described manner of proceeding may be repeated until the whole tempe rature range has been utilized.The cold store side of the process may be also based liquefying of air. Because air cannot be stored in a gas form in great quantities, during the charging period air taken from the atmosphere must be cooled at least to the boiling point of air in addition to liquefying. Then the process machinery needed may be more complicated than in t case of a store having material continuously in a solid o liquid form. On the other hand, specific capacity is increased if also the capacity involved in cooling and heating of air is utilized. One difficulty associating with the use of air is that the invented machine fits well with a Brayton-cycle having isentropic work phases, whereas in utilizing heat involved in liquefying and boiling, iso¬ thermal work phases would be natural for achieving a reversible process. In the process diagram presented in Fig. 69 the problem -mentioned has been solved. Moreover, moisture of air can be separated. In said process a major part of the energy is going through the circuit 251 connec as a Brayton-cycle, and being analogous to that in Figs. 6 66. By means of said circuit it is possible to remove from air a heat amount released during liquefying and to pump said heat into the warm reservoir S,n. The cold machine M1, operates e.g. within a temperature range of 20-25°C, in th case of the example so that the normal boiling point of ai(about 80K or -193°C) constitutes a lower limit. Liquefyi during charging period as well as boiling during dischargi period has been distributed evenly over the whole temperat range of the cold machine so that air passes through the■iUR O,V_ heat exchanger E. in several parallel conduits C.-C , the pressures in various conduits being stepped gradually so that the boiling points are distributed over the whole temperature range of the cold machine. During the dis¬ charging period liquid air taken from the cold store S, is pumped by machines P....-P, to pressures needed in each flow conduit. Thus, the operation of the heat exchanger E, can be arranged to be wholly reversible in principle.Since the partial pressure of oxygen is about 20% of the total pressure of air, the boiling points of oxygen and nitrogen in air are quite near each other, whence boiling of air takes place within quite a narrow temperature range, which as a.rough approximation can be called the boiling point of air in the total pressure in question. The tempe¬ rature of air at each joining point i.,-i of the corres¬ ponding flow conduit C..-C to the heat exchanger E, is arranged to correspond to the boiling point or. strictly speaking to the upper limite of the boiling range at the pressure in question. In a charging period combinations of pressure and temperature corresponding to the vapour pressure curve are arranged in the following way. Adapting of pressure is accomplished so that in each flow branch C_.-C __. expansion machines are used Mr,1,-Mr(,n-_1, ,) having^ an individual p cressure ratio selected to result in the wanted pressure after expansion. Adapting 'of temperature as a correct one is accomplished so that air passes through the heat exchanger E' , which is cooling air during the charging period. The air side of said exchanger is provided with joining points Jl~jn for parallel air conduits C_.-C , the joining points being situated so that the temperature of air at each joining point is suitable for the conduit in question.During charging the input point 256 of air leads to a chain of machines M..-M, functioning as compressors for compressing air into a high pressure. The chain includes heat exchangers E.-E, for cooling air warmed up to about 100 C back near the temperature of cold water. Thus, on the opposite sides of the heat exchangers water going into the warm water store S, can be heated. During isobaric cooling of air in said heat exchangers the moisture of air is condensed and can be separated. From the last machine M, of the chain the high pressure air during charging period goes into the expansion machine M Q, in which air is cooled considerably due to expansion, e.g. to a temperature of the order of 150K (about -120°C), after which the air goes to the input jn of the heat exchanger E'- .In the process diagram of Fig. 69 parallel air stream arrive during charging period to the cold side heat exchan of Brayton-cycle at individual points i..-i in the directi of the flow of working gas so that the temperature of work gas at each point approximately corresponds to the boiling point of air at a pressure corresponding to each flow cond C_.-C so that in each flow circuit is firstly accomplished liquefying of air within the section 257 of the flow condu which is transversal in relation to the flow direction 259 of working gas, and subsequently cooling of liquid within the section 258, in which the direction of flow is opposit to that of working gas, at least to the normal boiling poi of air. Alternatively, it is possible to join all parallel branches to the heat exchanger at the maximum temperature end, whence air ought to be cooled in a gaseous state at first. Temperatures at input points of various branches wo be the same, whence a need for compensating temperature falls occuring in- expansion machines M .M . _→ . would be greater than in Fig. 69.For removing heat from the cooling air in the heat exchanger E' working gas of Brayton-cycle flows on the opposite side of said exchanger. Due to branching of air flow the heat capacity of the flow is also different at various points of the exchanger. To achieve a reversible operation, the working gas flow must be made to vary corre pondingly by using in the exchanger E' several working ga circuits E' -E' situated geometrically in parallel, the lower temperature ends u.-u of which being drawn away fro the exchanger at points corresponding to joining points j_.-j of the air flow. Each working gas circuit E' -El functions as a cold side heat exchanger of a Brayton-cycle .- with a corresponding cold machine M' -M' . The temperature change on the air side of E' within the section E' _. adjacent to the machine M . may be of the order of 10-20 C, v/hence a moderately great temperature variation results in the first cold machine M' . On the other hand, within other sections E' -E' temperature ranges may be small, the size of the temperature range growing gradually from one cold machine to another. If the number of parallel branchesC..-C is very great, it is possible without essential losses to use a more rough division on the v/orking gas side so that one working gas circuit corresponds to two or several branches for air flow.Branches consisting of heat exchange circuits E' -E' and cold machines M 1, .1-MIin can be joined to form cold side- circuits of parallel Brayton-cycles having approximately the same pressure ratio, so that the sum of temperature ranges of cold machines in each process is approximately the same, and the total pressure ratio is divided on the warm side of the process over several compression machines in series so that the temperature rise of working gas during charging period is suitable for warming up water going into the warm store S, . In Fig. 69 it has been presented how components E' _. and M' _. of the first circuit have been combined with corresponding components Ei , Mi and M' , of the last circuit. The Brayton-cycle thus formed includes on the warm side machines M' -M' and heat exchangers E - E' and between the warm and the cold side the heat exchanger E' . As presented in Fig. 69, in circuits extending near the lower temperature end of the heat exchanger E' there may be used two machines (M' , M' ) in series to cover the tempe¬ rature range needed. By using circuits presented in Fig. 69, it is possible to achieve in principle a fully reversible operation of heat exhanger E' as well as on the cold sides of Brayton-cycles. Possible unfitnesses of quantitative dimensioning may be shifted to the warmer side, whence only a slight lowering of efficiency of use of waste heat of the process is resulting.In the process presented hot water going into the war store may be produced in three parallel circuits, namely i the phase change circuit 251 , in the temperature change circuit 254 and in the pressure change circuit 255. The tw circuits mentioned first are closed Brayton-cycle circuits in which helium or hydrogen may be used as working gas. The third circuit is an open air circuit, which includes machin M..-M, working above or near the ambient temperature as wel as machines M Q-M , __., working under the ambient tempera¬ ture. During discharging period the process is run in an opposite direction. Liquid air is then taken from the cold store S, , and gaseous air is released into the atmosphere from the point 256. Hot water taken from the the warm storSh, is cooled and transferred into the cold water store Ss to the surroundings The total process is reversible in principle, whence possibilities to a good efficiency are existing. Most of energy goes through the circuit 251 , whi is analogous to the circuits in Figs. 65-66. As in the hea exchanger E, liquefying and boiling of air take place the heat exchange coefficient is good during charging as well as discharging periods . Although a pressure of 1 bar is us at the low temperature end of E, , the temperature at the l temperature end of E would be about 10OK (-170°C) or more whence in case of helium as a working gas the pressure depe dancy of the specific heat of the working gas would yet be so small that conditions for a theoretically ideal heat exchanger E between the warm and cold sides of the Brayto cycle still exist.The process diagram presented may be modified e.g. so that the temperature range of the heat exchanger E, is shifted to a higher temperature level, e.g. within a range100K-120K (-170°C 150°C) and to a correspondingly highe pressure range. Then below E, would be situated one heat exchanger connected to the corresponding Brayton-cycle for reversibly altering the temperature of liquefied air.Most of the machines presented in Fig. 69 possess suc a pressure ratio that the preferred embodiment of the invented machine is well suitable. Machine M - may have quite a high pressure ratio, but a use of 2-3 machines in series would result in the proper ratio. Alternatively, . the embodiment presented in Figs.56-57 may be used. At the low pressure end of the chain M..-M, some turbo-machines may be used without a considerable increase of losses of the process .Fig. 70 presents a partial process diagram relating to that presented in Fig. 69. The modification of Fig. 70 aims at simplifying the temperature change circuit 254 of Fig. 69.Now, suitable combinations of pressure and temperature for parallel flow conduits C..-C of the heat exchanger E, are achieved by permitting, during the charging period, a small fraction of cooling air liquefy in some expansion machinesM _.-M . _ A> \ r whence an amount of heat needed for keeping the temperature of air at the boiling point at the pressure in question is released. In Fig. 70 a numerical value n = 10 has been p fresumed, whence machines Mr„1-Mr9„ are needed. Said machines are divided into four groups, each of which includes 1-3 machines. Pressure ratios in machines M _. , M . and M _ are designed to result in a suitable combination of pressure and temperature at the corresponding input points i1 etc., whereas in the other machines a few percents of air is liquefied for reaching the proper combination. In the heat exchanger E' only four branching points j-ι~j4are needed. Consequently, cooling of air may be accomplished by using .only one Brayton-cycle circuit 254 having in the example three cold machines M' -M' in series. During discharging period a certain fraction of liquid air is conducted by pump means (P - etc.) past the boiling sections 257 of the conduits 2, 3, 5, 6, 8 and 9. Said liquid may be sprayed into gaseous air stream, whence it is boiling during the com¬ pression process in the corresponding machines M „, M -., M ,-Mro c , MroD and Mry„ . Thus, also this modification is a rever- sible process. In other respects the diagram would be the same as in Fig. 69. Diagrams presented in Figs. 69-70 are additionally serving as an example when using the invented machine generally for liquefying air or other gases with a good efficiency.In order to give evidence of utility of the storing process in the following is derived a formula for the effi ciency of the process in question. The derivation is perfo ed on the basis of Figs. 65-66. To accomplish this, the machines of the process are replace by substitute models, Figs. 71-72 describing them in case of a charging period.Each substitute model includes an ideal machineMh, or M 1, , a parallel block 239 denoting relative gas leak a and a serial block 249 denoting relative pressure change b especially in the valve opening. As working gas is consi¬ dered to be ideal gas, the temperature fall of the working gas in the ideal expansion machine may be expressed by the equation- -R/c ( ,R/c ■ m 1 rπ^1 x0 = <1 - [«i:b)7 '] p = Ud-b.if] p - y T*'in isentropic expansion, where i ' is denoting pressure rat in the real expansion machine, temperature notations being those indicated in Fig. 72. By using the relationship Ti. = a T| + (1-a) TQ* obtainable from joint point 241 of Fig. 7 as gas leak is thought to happen dominantly isothermally (transformation of kinetic energy of leaking gas into heat being taken into account) , the temperature fall in the rea expansion machine may be expressed in forms=OM Correspondingly, the temperature rise of working gas in the ideal compression machine may be expressed in the formT3 T4' = 11 ~ fπ+c) (l+bjlf'l pf T^ =_ -, R/c ){ [(1+c) M+bJrf'J p - 1J T*'in isentropic compression, where / ' is denoting pressure ratio in the real expansionmachine of the process and c is denoting relative pressure losses in heat exchangers of the process circuit. Supposing that gas leak takes place dominantly isothermally, it may be obtained the relationship T4f = [~1/(1+a.)l T^ + [a/(1+a)l T» from joint point 241 of Fig. 71. Then the temperature rise of working gas in the real compression machine may be expressed in forms = (1+a) i 1 - [(1+c) (1+b)TΪ ] P f T3 : gc(a, b, c, if'.T^.In the equations presented there have been at the same time defined functions f and g for expressing generally the size of temperature change in isentropic expansion or compression, as f-function is multiplied by the maximum temperature of the temperature range in question and corres¬ pondingly g-function by the minimum temperature, subscript E denoting expansion and subscript C compression.In the storing process a heat balance in the cold store must be fulfilled, in other words, during the discharging period heat can be delivered into the cold store at the most up to the amount, which has been removed from it during the charging period. The equality of heat amounts results in the relationship m1 N (Tjj-T ) - m'-dT' = N (T^TQ) + m^3T where N = number of stages one after another in the pro (in Figs. 65-66 N = 1) , masses m1 and of working gas denoting integral quantitiesm' = J V m'dt , m = J t m dt , where t' = charging time 0 0 and t = discharging time. Temperature notations used ar the same as in Figs. 65-66. Especially temperature diff rencies __1T' and _3T are denoting differences between t opposite sides of the heat exchanger E due to an imper temperature efficiency of said exchanger. If the cold s had a perfect heat insulation, for the ratio of integra working gas masses during discharging and charging peri is obtained the relationshipsm (T1'-T -o'l' ^T'/N gE( ')τέ - (1-e) _ 2'- /N m,/i (T-I-TQ) + T/ gc(ir')T0 + (1-e) (T4-T1)/NIn the latter form the loss caused by the exchanger E been expressed by means of temperature efficiency -e of said exchanger, defined by relationships Tλ-T' = e (T' or 4-T5 = e (T4-T1) .For the process efficiency defined as the ratio of amount of mechanical energy produced during the dischar period to the amount of mechanical energy consumed duri the charging period can be obtained the equations^ wm ^1- i (T3~ - ( ϊ-τό} gE(7i )T - (1-e) (T^-T^)/N f£ (~t ) 3' - gc CϊT ) Q7ι ' gc T) 0 + (1-e) (T4-T1)/N fcrjr')T - gEcτ,)τ()where factor /??, is taking into account additional loss such as thermal leakage from the surroundings into- the store.-B Fig. 73 presents graphically the calculated efficiency i as a function of the minimum temperature T' of working gas in the charging process at some values of loss para¬ meters a, b and c. Working gas is supposed to be helium (c /R = 2.5) and pressure ratio '// = // ' = 1.80:1. Besides, numerical values T^ = 375K, T3 = 365K, T.Q = T^+5K, η = 0.95, e = 0.96 and N = 2 have been used. Temperature diffe- rencies T.-T. and T'-T' have been calculated from relation¬ ships 4-T1 = (T3-TQ) - (T3-T4) - (T,-T0) and Ti,-T = [(T3-TJ) - ( 3- ) - (T_|-TJ)J/(2e-1) . For example, the temperature Ti = 130K (-143°C) and loss parameters a = 0.02, b = 0.01 and c = 0.02 are resulting in efficiencym - o gς 33.0 - 2.8 74.6 - 38.6 L ~ υ'y 38.6 + 2.3 83.6 - 33.0 Ul -The range of water temperature v/ould be then about 80 C. The two dotted curves in Fig. 73 correspond to pressure ratio It = U ' = 2:1. As to the upper curve, in' addition exceptional values N = 3 and e = 0.97 have been used. Pressure ratio 2 is corresponding to a water temperature range of over 90°C. By using a closed water circuit the mentioned range is well applicable.If the energy to be stored is originated from the sun, the efficiency of 50% may already be considred quite satis¬ factory, because part of the energy may be transmitted directly to consumers without storing. Additionally, the characteristic of the invented storing process is that the part of stored energy, which is not reversible to mechanical energy, remains in form of heat in the hot water store and, thus, in a form profitable for low temperature purposes. As seen from Fig. 73, theoretical possibilities even for a considerably higher efficiency exist. The best efficiency may be achieved in short-term storage and by using liquid as a cold store material. Then temperature differences Ti-T-. and TQ-T would be at the minimum as well as thermal leakage into the cold store. The equation derived may also be applied to circuits 251 and 254 in Figs. 69-70. The efficiency of-BTrTtl _0MPI_ the circuit 255, in which the store air is directly flowin is expected to be high.The efficiency of the process may be altered in some extent by using different pressure ratios during charging and discharging periods . A moderate control range of press ratio is easy to arrange in the invented machine.If a solid cold store or a store with a material bein continuously in liquid form is used, then on the basis of Fig. 73 the total range of the temporal temperature variat may be about 70-80 C without the mean efficiency being rem kably lower than the maximum one. Then if a solid store we used, the temperature range of the colder end of the store might be within 100K-180K (about -170°C - -90°C) , for examWhen to this is added 50oC-2__T..-T at the warmer end of the1 o store, the store temperatures would be approximately withi 100K - 230K (about -170°C - -40°C) , in which both temporal and local variations have been taken into account.Fig. 73 reveals, how strongly the efficiency of the storing process is decreased by losses of machines. Thus, is clear that turbo-machines are not competitive in this application, neither other known machines. | Claims:1. A machine for the expansion or compression of gases or vapours in closing spaces, the volumes of which vary periodically, including a body structure (4) defining at least one rotation space (3) therein, and a working mem¬ ber (1) being rotatably mounted within said rotation space (3) , one portion of the working member facing the surround¬ ing body forming, together with the surrounding body, at least one working space (5) moving with said member cir¬ cumferentially, and another portion of the working member being provided with at least one separating wall (21) ex¬ tending close to the wall of the rotation space (3) , flow conduits (18, 19) in the body structure of the machine for the inlet and outlet of gas or vapour, and means for syn¬ chronizing moving parts of the machine, c h a r a c ¬ t e r i z e d in that one functional basic unit of the machine is including,^ n rotating reacting members (8) equally distributed around the periphery of the rotation space in such a way that each reacting member is rotatable around its own axis which is essentially perpendicular to the rotation axis of the working member and preferably situating totally outside the rotation space of the working member, the number of aforesaid working spaces (5) situated one after another in circumferential direction being equal to the number of said reacting members or to an integral multiple thereof, and each reacting member extending partially into the rotation space (5) of the working member and having a part (10) , which forms a transversal partition wall (15) dividing the working space in question into two parts , a process space (6) and a transferring space (7) , respective¬ ly, the volumes of which vary periodically according to rotation of the working member, said partition wall form¬ ing part (10) being shaped to have one, at the most two transition sectors (77) , in which the distance of the outer edge line to the rotation axis of the reacting mem¬ ber (8) has a minimum value, at least one first opening (26) located in the body part (4) surrounding the rotation space on the process space side of the partition wall (15), for providing connection between the process space (6) and the corres¬ ponding flow conduit (18); at least one second opening (52) positioned in said body part (4) on the transferring space (7) side of the partition wall (15) for providing connection between the transferring space and the corresponding flow conduit (19) and means (23, 238) for closing periodically said first opening (26) , means (42) for synchronizing the working member and said closing means so that the connection between the pro¬ cess space (6) and the corresponding flow conduit (18) is established during such a part of the process cycle, durin which the working space (5) moves circumferentially over a certain distance, at one end of which the partition wall (15) is in the process space end of the working space, the working member and the reacting member being syn¬ chronized so that once for each process cycle a passage of one separating wall (21) of the working member through one transition sector (77) in the partition wall forming part (10) of the reacting member is established.2. The machine as defined in claim 1, c h a r a c t e ¬ r i z e d in that the partition wall part (10) is pro¬ vided with only one transition sector (77) , one revolution of the reacting member corresponding to one process cycle, and one revolution of the working member (1) corresponding to the number of cycles equal to the number of working spa (5) one after another in the circumferential direction of the working member.3. The machine as defined in claim 1 , c h a r a c t e ¬ r i z e d in that one functional basic unit of the machine comprises two reacting members (8) on the opposite sides of the rotation space (3) of the working member (1)Oft'PI• ' and correspondingly two working spaces (5) one after an¬ other in the circumferential direction of the working mem¬ ber.4. The machine as defined in claim 1, c h a r a c t e ¬ r i z e d in that each reacting member (8) is a massive rotating body, extending into the rotation space (3) of the working member (1) so that its end surfaced0) , which is a part of an imagined surface of revolution in relation to the rotation axis of the reacting member, is situating at least near that normal plane of the rotation axis of the reacting member, which extends through the rotation axis of the working member, the partition wall (15) of the working space (5) being formed by that part of said end surface (10), which in turn is inside the rotation space of the working member, the massive form of the re¬ acting member making -possible to transmit reacting forces outside the rotation space of the reacting member nearly in the direction of the rotation axis of the reacting mem¬ ber.5. The machine as defined in claim 1, c h a r a c t e ¬ r i z e in that periodical closing of the openings (26) between the process space (6) and the corresponding flow conduit (18) is performed by a rotating valve member (23) mounted into the body (4) of the machine in front of the opening (26) in question, the rotation axis of the valve member being situated in a normal plane of the rotation axis of the working member (1) , and the plane of rotation of the valve member being at least approximately directed towards the rotation axis of the working member.6. The machine as defined in claim 5, c h a r a c t e ¬ r i z e d in that it is provided with a few openings be¬ tween the process space (6) and the corresponding flow conduit (18), said openings (26) being situated in the body (4) of the machine one after another in a circum¬ ferential direction of the working member (1) , each open¬ ing being provided with a rotating valve member (23) bein situated fan-like so that the rotation plane of each valv member is at least approximately directed towards the rotation axis of the working member.7. The machine as defined in claim 1, c h a r a c t e ¬ r i z e d in that the edge line of the partition wall forming surface (10), which is a part of an imagined sur¬ face of revolution in relation to the rotation axis of the reacting member, has such general form, as defined by means of the radial co-ordinate and the angular co-ordinat of cylinder co-ordinateswhen the corresponding axial co¬ ordinate is imagined to join with the rotation axis of the reacting member, that when the angular co-ordinate varies in the direction corresponding to the order of arrival of various points ofsaid edge linein expansion use into the rotation space member and starting from the sec¬ tor (77) , which is turned towards the working member when the process cycle is changing, said radial co-ordinate grows relatively steeply to a constant value (r..), and remains at that value for the major part of the angular variation corresponding to the whole circle, and returns finally to a low starting value (r ) near the end of the whole circle, the openings (26) connected to the closing process space (6) being situated in the body (4) of the machine so that they in the direction of the rotation axis of the working member are on that side of the cir¬ cumferential working space (5) , which is including the extreme end (20) of the process space (6), and in the di¬ rection of the circumference of the working member on the process space side so that at least one opening is extend¬ ing near the position of the partition wall (15).8. The machine as defined in claim 1, c h a r a c t e --_0_,.P1 v.'.po r i z e d in that it includes two functional basic units (40) in series in the direction of the rotation axis of the working member (1) , said units working in opposite phases for producing a relatively uniform torque, the corresponding working spaces (5) being situated within one working member (1) , the body (4) of the machine being composed of two halves (4a, 4b) in series corresponding to the respective two functional units, said halves having a rotation space for the working member on one side of the body so that the machine may be assembled by pushing the halves together in the direction of the rotation axis of the working member the sides of the rotation space faced towards each other.9. The machine as defined in claim 5, c h a r a c t e ¬ r i z e d in that the rotation space (3) of the working member (1) is at the .position of the working spaces of cylindrical form except for the position of the openings (26) of the process space, where the rotation space has a projection part (48) outside the cylindrical main part, formed by a channel in the body of the machine., the bottom surface (49) of said channel corresponding as well as possible to the form of an unbroken circum surface (99) of the valve member (23) , whence dead space in front of the valve is negligible, the separating wall (21) of the working member being provided with a projection part (50) corresponding to the cross-section form of said channel (48).10. The machine as defined in claim 9, c h a r a c t e - r i z e d in that the unbroken circum surface (99) of the valve member (23) is tangential to the bottom surface (49) of the projection channel (48) along two lines (A-B and C-D) , which are at intersections of said bottom sur¬ face and on the other hand oftwo parallel fictive planes situated symmetrically on the opposite sides of that normal plane of the rotation axis of the valve member , which extends through the rotation axis of the working member (1), the positions of said lines (A-B and C-D) forming sealing lines between said unbroken circum sur¬ face and the projection part (50) of the separating wall (21), the true opening (26) of the process space (6) be¬ coming thus divided into three parts one after another, which are performing as virtual openings (27a-c) , whereby the corresponding opening operation in expansion use for part of each virtual opening can be started as soon as the separating wall has shielded the virtual opening in question.11. The machine as defined in claim 9, c h a r a c t e ¬ r i z e d in that the unbroken circum surface (99) of the valve member (23) is a tangent to the bottom surface (49) of the projecting channel (48) along two lines (A'-B' and C'-D1). which are at -intersections of the unbroken cir¬ cum surface of the valve member and on the other hand of two parallel fictive planes situated symmetrically on the opposite sides of that normal plane of the rotation axis of the working member (1) , which extends through the rotation axis of the valve member, the positions of said lines forming sealing lines between said unbroken circum surface and the projection part (50) of the separating wall (21) the true opening (26) of the process space (6) being thus divided into three parts one after another in the direction of the circumference of the valve member, said parts performing as virtual openings (27a-c) , where¬ by the corresponding opening operation in expansion use can be started as soon as the separating wall has shielded 'the virtual opening in question.12. The machine as defined in claim 10, c h a r a c t e ¬ r i z e d in that the process space (6) has been provided with two true openings (26) situated one after another in the direction of the circumference of the working member'BUREAOMPI 1P0 (1) , each opening being provided with a true valve member (23) , whence six virtual openings (27) one after another are formed in the direction of the circumference of the working member.13. The machine as defined in claim 11, c h a r a c t e ¬ r i z e d in that the process space (6) has been provided with two true openings (26) situated one after another in the direction of the circumference of the working member(1) , each opening being provided with a true valve member (23) , by means of which are achieved six virtual openings (27) forming two groups in the direction of the working member, each group having three virtual openings in the direction of the circumference of the valve member.14. . The machine as defined in claim 9, c h a r a c t e ¬ r i z e d in that the total cross-section area of the openings (26) of the process space (6) is of the same or¬ der as the maximal area of the partition wall (15) formed by the reacting member (8) .15. The machine as defined in claim 10, c h a r a c t e ¬ r i z e d in that the circum part of the valve member (23) has been provided with a gap (28) extending over a certain rotation sector (β 3., βJ, , 3C) individual to each virtual opening (27) , a connection between the process space and the corresponding flow conduit (18) being creat¬ ed when said gap is turned towards the opening (26) of the process space (6) , the other edges (30) of the gap (28) in the valve being at equal positions, whence closing the valve in expansion use as well as opening in compression use takes place at the same time for part of each virtual opening, whereas the other edges (29) are at individual positions, so that the starting moment of opening of each virtual opening (27) in expansion use as well as the ending moment of closing of each virtual opening in compression use is timed so that at that moment the virtual opening in question is in the shield of the separating wall (21) of the working member (1 ) .16. The machine as defined in claim 5, c h a r a c t e ¬ r i z e d in that the visual angle ( α ) of the opening (26) of the process space (6) in relation to the rotation axis of the valve member (23) is of the order of 30 .17. The machine as defined in claim 1, c h a r a c t e ¬ r i z e d in that it is provided with means for directing a programmed pressure effect onto the counter-surface (11) of the reacting member (8) for achieving a periodically varying force effect for compensating at least approximate ly reacting forces caused by a pressure difference between the opposite sides of the partition wall (15) .18. The machine as defined in claim 16, c h a r a c t e - r i z e d in that the machine is provided with threee counter-pressure spaces (53-55) for directing a compensat¬ ing pressure effect onto the counter-surface (11) of the reacting member and corresponding means for varying the pressure in said spaces so that the resultant of forces at each moment is directed on a straight line parallel to the rotation axis of the reacting member, which ex¬ tends through the centre of gravity of the partition wall (15) of the working space (5) .19. The machine as defined in claim 17, c h a r a c e ¬ r i z e d in that a pressure effect is directed onto the reacting member from counter-pressure spaces, each of which is provided with a device (70) for altering periodi¬ cally the volume of said space, the device including a reciprocating piston (71) for achieving a desired volume variation, the circum surface of said piston being pro¬ vided with a circumferential groove (87) , in connection through the interior of the piston with the counter- pressure space in question, the inner wall of the de¬ vice being provided with circumferential enlarged spaces (83,84) , which are in connection with spaces having a pressure needed in the compensation spaces during periods of constant counter-forces, the positions of the enlarged spaces in the wall being selected so that the groove (87) in the piston at either or both ends of the reciprocation moves a certain distance at the position of said enlarged space, whereby a periodical pressure variation of the counter-pressure space caused by a periodical volume variation a constant pressure period results in another or both extreme ends of the pressure range used.20. The machine as defined in claim 17, c h a r a c t e ¬ r i z e d in that a pressure effect is directed onto the reacting member through counter-pressure spaces, each of which is provided with a compensating device (90) includ¬ ing a rotating valve member (91) provided with one or a few circumferential slots (97,98) , the width of which is different in different parts of the slot, whence the valve during its rotation partly shuts the corresponding opening (93,94) in the wall of the device in a suitably programmed way, said opening being in connection with a space having a certain pressure (p, . , , p-, ) , whence the gas content of the counter-pressure space can be varied in a program¬ med manner.21. The machine as defined in claim 5, c h a r a c t e ¬ r i z e d in that the valve member (23) is provided with the pressure compensation parts (32) , situating co-axially on both sides of the valve member.22. The machine as defined in claim 7, c h a r a c t e ¬ r i z e d in that in the- partition wall forming part (10) of the reacting member (8) the edge (45) being at constant distance from the rotation axis of the reacting member has been formed in the direction of said axis so that a sealing clearance (14) between the working member and the reacting member has a considerable length in the directio of gas leak, said form corresponding exactly to the form of the bottom of the working space in a situation, where each point of the edge has moved inside the rotation space about a quarter of the total angle, which said poin spends inside the rotation space of the working member.23. The machine as defined in claim 1, c h a r a c t e ¬ r i z e d in that clearances, the size of which does not depend on mutual synchronization of moving members, are provided with a labyrinth seal for reducing gas leak.24. The machine as defined in claim 7, c h a r a c t e ¬ r i z e d in that in the reacting member (8) that radial like edge ,(44) of the partition wall forming part (10), which corresponds to the process space end (20) of the working space (5) , has been provided with a sealing mem¬ ber (110) capable of moving to some extent in relation to the body of the reacting member.25. The machine as -defined in claim 24, c h a r a c t e r i z e d in that the sealing member is formed so that the centrifugal force tends to turn it to one extreme position and the machine is provided with means for turn¬ ing said member to the opposite extreme position.26. The machine as defined in claim 24, c h a r a c t e r i z e d in that the radial-like edge (44) of the par¬ tition wall forming part (10) consists of one or a few straight parts, each of which is provided with a sealing member (80) , which may turn to some extent in relation to the body of the reacting member around its turning axle (112), the direction of said axle deviating somewhat from'BU EA O PI the direction of the corresponding edge section so that in the sealing member a circum surface (123) facing the body of the reacting member, which comprises a conical surface of revolution in relation to said turning axle, is tangenting an imagined surface (117) forming an ex¬ tension to the partition wall forming surface (10) , the sealing edge (44) being thus formed approximately at the point of the corresponding tangent line, the sealing mem¬ ber being formed thinner on the side (118) outside from the body of the reacting member and the conical form of said surface of revolution being such that the perpendi¬ cular distance (R ) of each point of the sealing edge from the turning axis of the sealing member is proportion¬ al to the perpendicular distance (R ) of the same point from the rotation axis of the reacting member, whence follows that when the turning angle (£) of the sealing member is small, the movement of the sealing edge caused by turning the sealing member corresponds to that caused by the rotation of the whole reacting member.27. The machine as defined in claim 26, c h a r a c t e ¬ r i z e d in that it is provided with control means for turning the sealing member (110) in relation to the re¬ acting member (8) so that errors in synchronization be¬ tween the working member (1 ) and the body (111) of the reacting member are compensated.28. The machine as defined in claim 27, c h a r a c t e ¬ r i z e d in that it includes means for defining an error in synchronization between the working member (1) and the body (111) of the reacting member (8) and means for de¬ fining the position of the sealing member (110) in re¬ lation to the body of the reacting member, said means being parts of the control means for turning the sealing mem¬ ber. sioning and in which the gas flow has no temperature variation during the process cycle, are provided with a thermal insulation structure (198), the surface of which is settling down near the temperature of gas.33. The machine as defined in claim 1, c h a r a c t e ¬ r i z e d in that surfaces participating to a formation of the process space (6) are provided with heat exchange conduits in superficial layers of said walls for deviating the temperature of said surfaces from gas temperature to¬ wards the ambient temperature.34. The machine as defined in claim 1, c h a r a c t e ¬ r i z e d in that at least a part of the surfaces, parti¬ cipating to the formation of the process space, are pro¬ vided with a heat insulation structure including several parallel plates (204)~, which form the precise surface needed, said plates being supported in the base structure(197) of the member in question by using co-axial cylinders (205) with thin walls between each plate and the base structure, said cylinders serving as a heat insulator and being able to expand or contract without excessive thermal stresses resulting.35. The machine as defined in claim 1, c h a r a c t e ¬ r i z e d in that the rotation space (3) of the working member (1) includes a projection part (48) surrounding the main part of the cylinder form, the edge line of the partition wall forming part (10) having such general form as defined by means of a radial co-ordinate and an angular co-ordinate of cylinder co-ordinates, the corresponding axial co-ordinate being joined with the axis of rotation of the reacting member that when the angular co-ordinate changes to a direction corresponding to the order of arrival of various points of said edge line, in expansion use, into the rotation space of the working member, and vided with a gas opening (26) situating in the direction of the circumference of the working member on the side of the process space and extending beneath the partition wall (15) and so far in the direction of the axis of rotation of the working member that only the portion (237) mentioned of the working space can extend to the position of said opening.37. A use of the machine of claim 1 for energy storing, c h a r a c t e r i z e d in that the low-loss machines are used as components in a reversible .process, which is run during charging period in such a direction that by con¬ suming mechanical energy heat can be removed from a cold store material, and during discharging period in the oppo¬ site direction, whereby heat is delivered into the cold store material and mechanical energy is produced. | NILSSON P; TAKALO K | TAKALO K |
WO-1979000654-A1 | 1,979,000,654 | WO | A1 | EN | 19,790,906 | 1,979 | 20,090,507 | new | A01N9 | C09D5 | A01N25, A01N37, C09D5 | A01N 37/34+M, C09D 5/14 | TETRACHLOROISOPHTHALONITRILE DISPERSION | Finely divided tetrachloroisophthalonitrile powder is dispersed in a vehicle which is a mixture of calcium alkyl aryle sulfonate, nonionic surfactant, fatty acid or other ester, coupling agent and optionally lecithin. The vehicle provides a water and organic solvent compatible tetrachloroisophthalonitrile dispersion having a pourable and pumpable viscosity as well as settling resistance which is useful as an antimicrobial agent in both water-based and solvent-based protective coatings such as paints. | TETRACHLOROISOPHTHALONITRILE DISPERSIONBACKGROUND OF THE INVENTION1* Field of the InventionThis invention relates to a dispersion of an antimicrobial agent for use in water-based and solvent-based protective coatings such as paints. 2. Description of the Prior Art Antimicrobial agents such as 2,Ψ,5,6-tetrachloroisophthaJonitrile are used in water-based and solvent-based protective coatings such as paints. These agents are almost insoluble in water and are sparingly soluble in organic solvents. For example, 2, ,5,6-tetrachloroisophthalonitrile is soluble to the extent of about 0.6 ppm in water at 25°C and is soluble at 25°C in xylene 8% (wt/wt), cyciohexane 3%, acetone 2% and kerosene at less than 1%. Since solutions of this agent are too dilute for most purposes, concentrated formulations are prepared using the solid agent in the form of finely divided powder. Convention¬ ally, this agent is formulated as wettable powders and aqueous suspensions for use in aqueous systems in agriculture. U.S. Patent 3,948,636 - Marks, issued April 6, 1976, describes preparation of fiowable aqueous compositions of water-insoluble pesticides such as tetrachloroisophthalonitrile. These fiowable aqueous compositions are for use in aqueous systems in agriculture.Because of insolubility of tetrachloroisophthalonitrile and difficulties involved in its formulation, in protective coatings, improved methods fo incorporating this agent in protective coatings are required. Further, ne governmental regulations impose additional restrictions on the handling, formu lating and use of the solid form of this biocidal agent so there is a need fo dispersible formulations which can be directly added to protective coatings. /00654- 2 -SUMMARY OF THE INVENTIONA tetrachloroisophthalonitrile dispersion is prepared by dispers finely divided tetrachloroisophthalonitrile powder in a vehicle which is a mixt of calcium alkyl aryl suifonate, nonionic surfactant, ester, coupling agent optionally lecithin. The vehicle provides a water and organic solvent compati dispersion having pourable and pumpable viscosities as well as settling resistan The resulting dispersion is an antimicrobial agent for use in both water-based solvent-based protective coating such as paints.DESCRIPTION OF THE PREFERRED EMBODIMENTSUseful tetrachloroisophthalonitrile dispersions may contain the ran of indicated and preferred ingredients shown below: Indicated Preferred parts by weight parts by weight tetrachloroisophthalonitrile 10 - 70 0 - 60 calcium alkyl aryl suifonate 5 - 50 25 - 30 nonionic surfactant 5 - 50 15 - 20 ester 5 - 50 20 - 30 coupling agent 5 - 50 10 - 20 lecithin 0 - 10 2 - 5The tetrachloroisophthalonitrile is 2,4,5,6-tetrachloroisophth nitrile, also known as 2, ,5,6-tetrachloro-l,3-benzenedicarbonitrile or 1 dicyano-2,4,5,6-tetrachIorobenzene. It is available under the registered tr names of Nopcocide ® N-96, Daconil ® 2787, Termil® and Forturf ® . It the structural formula: and forms colorless crystals which melt at 250° to 251 °C. This tetrachloro¬ isophthalonitrile is a broad spectrum foliage and fruit protectant fungicide as well as an industrial antimicrobial agent. It may be prepared by the process described in U.S. Patent 3,290,353 - Battershell and Bluestone, December 6, 1966, wherein halogenated aromatic nitriles are prepared from the corresponding ring-chlorinated acid chlorides. The acid chloride is converted to the corresponding amide by dissolving the_acid chloride in a suitable organic solvent and introducing ammonia to form the amide. Either anhydrous or aqueous ammonia is employed. The ring-chlorinated aromatic amide is dried and then reacted with a dehydrating agent such as phosphorus pentoxide or phosphorus oxychioride to obtain the nitrile. Details on its preparation and properties- are given in U.S. Patent 3,331,745 - Battershell and Bluestone, July 18, 1967.The calcium alkyl aryl suifonate used in the vehicle may be Witco Chemical Corp. Emcol ® D-24-25 (25% ethanol) or Witconate® 605-T (25% xylene type solvent), calcium dodecyl benzene suifonate, alkaline earth petro¬ leum sulfonates and lead alkyl aryl sulfonates. The alkyl aryl sulfonates may have from 6 to 18 carbon atom alkyl groups.Useful nonionic surfactants for the vehicle include nonylphenol ethoxylated with 4 moles ethylene oxide, castor oil ethoxylated with 43 moles ethylene oxide, octylphenol plus 15 moles ethylene oxide, ethoxylated alcohols, e.g., tridecyl alcohol with 10 moles ethylene oxide, dinonylphenol with 1.5 moles ethylene oxide and ethoxylated blown oil. It is to be understood that ethoxyiates containing from about 1 to about 150 moles of ethylene oxide based on the above may be used. Esters which may be used include isodecyl oleate, methyl oleate, butyl oleate, propyl stearate, 2-ethylhexyl tallate, isopropyl myristate, phosphate esters (triethyl phosphate, tributoxyethyl phosphate, tricresyl phosphate) and plasticizers (dioctyl phthalate, butyibenzyl phthlate, glyceryl trioleate, sebacic acid esters, diisodecyl adipate, epoxidized soya oils, tributyl citrate, octylene glycol dibenzoate and polyesters). The coupling agents in the vehicle may be butyl Carbitol, butyl Cellosolve® (2-butoxyethanol), Carbitol (diethylene glycol monoethyl ether), Cellosolve® , hexyl Cellosolve® , butoxytriglycol, butyl Carbitol (diethylene glycol monobutyl ether), l-butoxy-ethoxy-2-propanol, phenyl glycol ether, poly- glycols, dibutyl Carbitol, butyl Cellosolve® acetate, Carbitol acetate, hexylene glycol diacetate and Tergitol ® XD (polyalkylene glycol ether). - 4 - Useful lecithin products for the vehicle include soya lecith alkoxylated lecithin, fractionated lecithin, hydrolyzed lecithin, hydroxylat lecithin, halogenated lecithin, sulfonated lecithin, coacervated lecithin a bleached lecithin. The vehicle may be prepared by blending the above ingredients in t desired proportions at room temperature, heating if necessary, to obtain homogeneous mixture and then cooling to room temperature. The tetrachloroisophthalonitrile is then added to the vehicle a mixed until a uniform dispersion is obtained. The antimicrobial agent is usual added slowly and dispersed by mixing from about 15 to about 60 minutes. For 50% active dispersion, the consistency or viscosity of the dispersion after mixi is about 15000 to about 30000 cps. If a lower viscosity is desired, higher she dispersing equipment must be utilized, e.g., homogenizer or 3-roll mill. T equipment will reduce the viscosity to about 7000 to about 10000 cps. T viscosity will also vary depending on- the concentration of tetrachloroisophthal nitrile present.The tetrachloroisophthalonitrile dispersion may be added to eith water-based or solvent-based protective coating formulations. From about 2 about 100 lbs of the dispersion per 100 gallons of formulation is required. T dispersion may be added to the finished protective coating formulation or may incorporated as one of the components during manufacture of the protecti coating formulation.The dispersion is useful in water-based protective coatings such acrylic, polyvinyl-acetate and vinyl-acrylic emulsions for the trade-sal coatings industry.Further, the dispersion may be used in solvent-based protecti coatings such as long oil alkyds, medium oil alkyds, short oil alkyds and linse oil based systems for the trade-sales coatings industry. Additional details both types of coatings are given on pages 500 and 501 of Volume 13 of t Encyclopedia of Polymer Science and Technology (Interscience Publishers, N York, N.Y. 1970).Because of the diverse nature of protective coatings systems, t products of this invention may be varied to increase water and/or solvent, e. polypropylene, mineral spirits, xylene dispersibility of Nopcocide N— 6. example, increasing the ' ethoxylated castor oil content will increase t dispersibility of Nopcocide N— 6 in water but will decrease the mineral spir dispersibility. Propoxylated or low (1-5 moles) ethoxylated alcohols will improve mineral spirits dispersibility, whereas ethoxylated alcohols with 15-60 moles ethylene oxide will improve water dispersibility.The stability of Nopcocide N-96 dispersions was determined by 5 placing 4 ounce samples in capped glass jars in a circulating air oven at 120° to140°F for one month. No hard sediments, which could not be redispersed by simple stirring, formed.For a fuller understanding of the nature of this invention, reference may be made to the following examples which are given merely to illustrate the 10 invention and are not to be construed in a limiting sense. All weights, proportions and percentages are on a weight basis unless otherwise indicated. Likewise, all temperatures are °C unless otherwise indicated.EXAMPLE I A Nopcocide N— 96 vehicle was prepared using the following com- 15 ponents: parts by weight33 Emcol D-24-25 (calcium alkylbenzene suifonate. 75% active in ethanol). 19 nonionic surfactant (nonylphenol plus 5 moles ethylene oxide).20 30 fatty acid ester (Isodecyl oleate).16 coupling agent (butyl Cartibol).2 lecithin (soya).Total 100The above quantities of the component were blended at room 25 temperature to obtain a homogeneous vehicle.A 50%, by weight, dispersion of Nopcocide N— 96 was prepared using 50 parts, by weight, of the vehicle and 50 parts of Nopcocide N— 96 by adding the biocide into the vehicle slowly and disperse for 30 minutes using a laboratory stirrer. Dispersion consistency at this stage was 17000 cps. After homogenizing 30 in a laboratory hand homogenizer, the viscosity decreased to 8150 cps (Brookfield LVF model).After aging for six weeks at 120°F, the fluid dispersion did not develop a hard, difficult to redisperse Nopcocide N— 96 sediment. EXAMPLE II50%, by weight, Nopcocide N-96 dispersions were prepared using t quantities of ingredients shown in Table I and I (continued). These dispersio were prepared following the procedure in Example I and are designated as 5 through Q in the table. TABLE I NOPCOCIDE N-95 DISPERSIONSNopcocide® N-96 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0Emcol® D-2'l-25 11.8 11.8 11.8 11.8 15.0 . 11.8 11.8 11.8 15.0Water 5.0 5.0 5-0 5.0 5.0 5.0 5.0 5.0 •Ethoxylated (43) castor oil 11.8 11.8 11.8 11.8Ethoxylated (1) nonylphenol 3.7 3.7 3-7 3.7 .17.0 13.9 9.5 7.0 7.5Tergitol® XD 3.7 3.7 3.7 3.7 5.0 9.0 .1.5 7-0 7.0Butyl Cellosolve® 8.0Butyl Carbitol 8.0 8.0 8.0 7.3 7.2 7.2 8.0Carbitol 8.0Butyl oleate . 9.0Dloctyl phthalate 9.0Methyl oleate 7.5Tributyl phosphate 5.0Propeller blade vie. cpβ 31,000 20,000 16,500 28,500 21,800 24,600 22,600 31,650 26,0003-roll milled via. cps' 8,600 7,800 7,800 15,500 7,600 9,150 9,250 13,150 16,000 TABLE I(Continued)NOPCOCIDE N- -96 DISPI ..RSIONS •J K L M . N 0 PNopcocide® N-96 50.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0Emcol® D-21-25 16.5 16.5 16.5 16.5 16.5 16.5 10.0Witconate® 605-T 16.5Water 2.5 2.5 2.5 •Ethoxylated (4) nonylphenol 9.5 9,5 9.5 9.5 13.0 15.0 . 18.5 9.5Butyl Carbitol 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0'Propoxylated (90) butanol 12.5Iaodecyl oleate 12.5 15.0 10.0 8.0 11.0 15.0Lecithin 1.0 1.0 1.0 1.0 ?.5 2.5 2.5 1.0UCON LB385 12.5Propeller blade via. cps 39,000 15,750 35,000 26,750 30,000 21,500 11,5003-roll milled vis, . cps 31,000 10,000 25,500 •Homogenized vie. < :ps 8,150 16,500 16,000 11,750 8,600 EXAMPLE III in Table I was n acrylic (50% eight of paint. affected by the .Results of theNcocide spersion0TABLE IIPHYSICAL AND OPTICAL PROPERTIES OF 50* NOPCOCIDE N-96 DISPERSIONS IN POLYVINYL-ACEΓΛTE FORMULATIONPHOTO VISCOSITY (KU) PH OPACITY DISCOLORATION SENSI50* BIOCIDE DISPERSION LEVEL TIVITY ODOR INITIAL WK 120°F INITIAL IWK 120°F INITIAL WK 120°F INITIAL WK 120°FControl (Blank) OK OK 90 91 7.2 7-5 OK OK OK OKNopcocide® N-96 1.0* OK OK 90 90- 7-3 .7.5 OK OK OK OKNopcocide® N-96 2.0* OK OK 90 90 7.2 ' 7.6 OK OK OK OKNopcocide® N-96 2.0* OK OK 90 95 7.1 7.2 ' OK OK OK OKEXAMPLE VThe 50% Nopcocide N— 96 dispersion designated as Q in Table I was evaluated in a water-based protective coating formulation, a vinyl-acrylic (55% solids) system at a level of 2.0% (total weight of paint). No problems incorporating the dispersion in the formulation were encountered and no changes in film appearance of the dried coating were observed.EXAMPLE VIThe 50% Nopcocide N-96 dispersion designated as Q in Table I was evaluated in a linseed-oil house paint system at a ϊewei of 2.0% (total weight of paint).. No problems incorporating the dispersion in the formulation were encountered and no changes in film appearance of the dried coating were observed.EXAMPLE VIIThe 50% Nopcocide N— 6 dispersion designated as Q in Table I was evaluated in a solvent-based protective coating formulation, a linseed-oil primer paint system at a level of 2.0% (total weight of paint). No problems incorporating the dispersion in the formulation were encountered and no changes in the appearance of the dried film were noted.EXAMPLE VIII The 50% Nopcocide N— 6 dispersion designated as Q in Table I was evaluated in a solvent-based protective coating formulation, an alkyd house paint system at a level of 2.0% (total weight of paint). No problems incorporating the dispersion in the formulation were noted and no changes in film appearance of the dried coating were observed. While the invention has been described with reference to certain specific embodiments thereof, it is understood that it is not to be so limited since alterations and changes may be made therein which are within the full and intended scope of the appended claims.- | - 12 -WHAT IS CLAIMED IS:1. A tetrachloroisophthalonitrile dispersion for use as an ant2 microbial agent for protective coating formulations comprising:3 (a) tetrachloroisophthalonitrile,4 (b) calcium alkyl aryl suifonate,5 (c) nonionic surfactant,6 (d) an ester,7 (e) coupling agent, and8 (f ) optionally, lecithin.2. The dispersion of claim 1 wherein there is present2 (a) from about 10 to about 70 parts, by weight, of tetr3 chloroisophthalonitrile,H (b) from about 5 to about 50 parts, by weight, of calciu5 alkyl aryl sulphonate,6 (c) from about 5 to about 50 parts, by weight, of nonioni7 surfactant,8 (d) from about 5 to about 50 parts, by weight, of an ester,9 (e) from about 5 to about 50 parts, by weight, of couplin10 agent, and11 (f) from 0 to about 10 parts, by weight, of lecithin.3. The dispersion of claim 1 wherein the nonionic surfactant2 selected from the group consisting of nonylphenol ethoxylated with 5 moles3 -ethylene oxide, castor oil ethoxylated with 43 moles ethylene oxide, octyl phen Lf. ethoxylated with 15 moles ethylene oxide, ethoxylated aliphatic alcohol5 dinonylphenol ethoxylated with 1.5 moles ethylene oxide and ethoxylated blow6 oil.4. The dispersion of claim 1 wherein the ester is selected fro2 the group consisting of isodecyl oleate, methyl oleate, butyl oleate, prop3 stearate, 2-ethylhexyl tallate, isopropyl myristate, dioctyi phthalate, butylbenz4 phthalate, glyceryl trioieate, sebacic acid ester, diisodecyl adipate, epoxidiz5 soya oil, tributyl citrate,' octylene glycol dibenzoate, polyester, trieth6 phosphate, tributoxy ethyl phosphate and tricresyl phosphate. 5. The dispersion of claim 1 wherein the coupling agent is2 selected from the group consisting of butylglycol monoethyl ether, 2-butoxy-3 ethanol, diethylene glycol monoethyl ether, butoxytriglycol, diethylene glycol -. monobutyl ether, l-butoxy-ethoxy-2-propanol, phenyl glycol ether, polyglycol,5 hexylene glycol diacetate, polyalkylene glycol ether, diethylene glycol ihexyl6 ether, diethylene glycol dibutyl ether, ethylene glycol monoethyl ether, ethylene7 glycol monohexyl ether, ethylene glycol monoethyl ether acetate, diethylene8 glycol monoethyl ether acetate and ethylene glycol monobutyl ether acetate.6. The dispersion of claim 1 wherein there is present about 332 parts, by weight, of calcium alkylbenzene suifonate, 19 parts, by weight, of3 nonylphenol condensed with 5 moles of ethylene oxide, 30 parts, by weight, of if. isodecyl oleate, 16 parts, by weight, of diethylene glycol butyl ether, 2 parts, by 5 weight, of soya lecithin and 100 parts, by weight, of tetrachloroisophthalonitrile.7. A process of preparing a water-based protective coating2 formulation containing tetrachloroisophthalonitrile as an antimicrobial agent3 comprising adding to the formulation or adding as a component during ij. manufacture of the formulation the dispersion of claim 1, the amount added 5 providing for an effective amount of the tetrachloroisophthalonitrile.8. A process of preparing a solvent-based protective coating2 formulation containing tetrachloroisophthalonitrile as an antimicrobial agent3 comprising adding to the formulation or adding as a component during4 manufacture of the formulation the dispersion of claim 1, the amount added5 providing for an effective amount of the tetrachloroisophthalonitrile.9. The process of claim 7 wherein the dispersion is added to the 2 protective coating formulation.10. The process of claim 8 wherein the dispersion is added to the 2 protective coating formulation.11. A water-based protective coating formulation containing2 tetrachloroisophthalonitrile as an antimicrobial agent, there being present the3 dispersion of claim 1, the amount of the dispersion present providing for an effective amount of the tetrachloroisophthalonitrile. - 1412. A solvent-based protective coating formulation contain tetrachloroisophthalonitrile as an antimicrobial agent, there being present t dispersion of claim I, the amount of the dispersion present providing for effective amount of the tetrachloroisophthalonitrile. | DIAMOND SHAMROCK CORP | ALDERMAN J; IHDE F; MAKAR P |
WO-1979000660-A1 | 1,979,000,660 | WO | A1 | XX | 19,790,906 | 1,979 | 20,090,507 | new | H02H3 | null | H01T1 | H01T 1/14 | CLIP-ON PROTECTOR | Protective devices for use with conventional over-voltage protectors, especially applicable for use in protection of communication equipment. The device of this invention overcomes the prior art problems of lack of reliability, excessive size and cost, installation and maintenance difficulties, and various other problems more fully understood in the specification. The apparatus in the preferred embodiment features a small, cylindrical housing (10, 11, 12), connectors (13, 14) designed to attach simply to the electrodes of a standard over-voltage protector (23, 23A, 23B), and dual grounding paths for increased reliability and activated upon heat transfer upon sustained overload from the over-voltage protector. These paths are described as from ground-connected plates (16) to normally tensioned springs (17) to plungers (18) to electrical transfer plates (13), effected when fusible elements (19) are fused by heat conducted from the over-voltage protector (23) through heat transfer plate (14). | CLIP-ON PROTECTORThis invention relates to equipment and methods for protecting apparatus from over-voltage conditions and is particularly directed to over-voltage sensitive devices attached to electrical conductors serving various types of apparatus such as used for communication. An example of the protection device's application is the device pro¬ tecting apparatus from the effects of excessive voltage such as might occur because of lightning, a fault, contact by a high tension line and the like.Of the various types of equipment presently employed for accomplishing the foregoing, each suffers from one or more disadvantages including excessive cost and size, lack of adaptability to existing protector terminals, maintenance difficulties, hazardous conditions during servicing, loss of function in the presence of sustained overload, lack of safety provision thereby permitting the apparatus supposedly under protection to function withou a protector, and less-than- optimum reliability.It is an object of this invention to overcome or substantially reduce the foregoing shortcomings and to this end the invention provides improvements in performance, utilization and construction leading to reductions in size and cost, adaptability to existing mounting locations, reduction in hazards, an assurance that the over-voltage protector is installed, ability to utilize the device in a densely packaged area, simplication and safety in servicing and an increase in reliability. Moreover, in the invention techniques, additional protection features are attained without significantly impairing the essential simplicity of the construction.The invention consists of the novel methods, processes, parts, steps, combinations and improvements herein shown and described.Serving to illustrate exemplary embodiments of the invention are the drawings of which:FIGURE 1 is an isometric view illustrating the invention;FIGURE 2 is the detail view of components taken in FIGURE 1; FIGURE 3 is a sectional view taken along the line 3-3 of FIGURE 1 and looking in the direction of the arrows to reveal the components of the device of FIGURE 1;FIGURE 4- is a diagrammatic illustration of the inventive device in combination with an over-voltage protector.Referring to the embodiment of FIGURES 1-3, the arrangement therein illustrated comprises a housing consisting of a center 10 with two identical ends 11, all shown as hollow cylinders, and two identical cylindrical end caps 12. Each of these is constructed of a nonconducting material illustratively shown to be Bakelite, although end caps 12 may be metal, and may be assembled by such means as glue or threaded intern¬ ally and externally, as shown and hereinafter described, in order to allow ease in assembly and disassembly.Mounted in and located on the housing in aligned relationship are two identical electrical transfer plates 13, one heat transfer plate 14, and two identical safety contactors 15. Each of these five parts may be made of any suitable material; phosphor bronze, beryllium, copper or spring brass are satisfactory. The electrical transfer plates 13 are placed at the ends of housing center 10, positioned by such means as having the center shaped to accept these parts and secured tightly when housing ends 11 are screwed into the center. Heat transfer plate 1 is mounted through slots in the housing center and held in place by suitable means such as a spring clip 14c shown to be formed from a protrusion of the heat transfer plate. Each safety contactor 15 is held in position by a groove on the outside of center 10 and by extension arms 15c, 15d which rest against the heat transfer plate and an adjacent electrical transfer plate at their spaced blades, described hereinafter.Electrical transfer plate 13 and heat transfer plate 14 each has a pair of spaced blades 13a, 13b and 14a, 14b respectively. Each pair of associated blades comprise a holding clip. The holding clips are aligned to receive and hold the over-voltage protector 23. In the embodiment illustrated in FIGURES 3-4- this over-voltage protector is of known con¬ struction; examples of which are an AEI type 16 gas tube protector, a TII-16 type surge arrester, a Siemens type TI-6350 surge voltage arrester. A cartridge of this type comprises a gas filled housing having a pair of opposed, spaced electrodes each of which makes electrical contact with one of the cartridge end terminals 23A and 23B. In the presence of an excessive voltage the gas between the electrodes is ionized thereby effectively shorting the end terminals and connecting them to the case of the protector and to external ground as described below. The lines and apparatus connected to these electrodes via the electrical transfer plates are thus short-circuited to thereby prevent the over-voltage con¬ dition from causing excessive current flow in the protected apparatus.The two end plates 16 are identical and are made of any suitable material; copper or brass is satisfactory. These plates are held in place at the distal ends of housing ends 11 by such means as having the housing ends shaped to accept these parts and secured tightly when end caps 12 are screwed into housing ends. The end caps have slots in their ends to accommodate a screw driver if necessary for tightening.In the application of this device each of the end plates 16 is connected to external ground. This is illustratively accomplished by such means as a crimp type wire connector 16a shown to be formed from a protrusion of the end plate, which allows one end of wire 22 to be electrically and mechanically connected to the end plate with soldering assistance while the other end of the wire is connected to external ground by suitable means,Within housing center 10 and ends 11 are two identical springs 17, two identical plungers 18, each with a large diameter head 18a and shaft 18b, and two identical fusible spacers 19 described hereinafter. Mounted symmetrically within each half of the housing (see FIGURE 3), in spaced relationship, is one spring, one plunger and one fusible spacer. The springs are made of any suitable material, phosphor bronze, spring brass, beryllium copper or spring steel are suitable. The plungers may be made of any suitable material; copper, brass or steel is satisfactory. The fusible spacer may be lead, solder, babbit or other appropriate material in accordance with ratings and installation requirements of the protector 23, the fusible spacer being designed to melt when the current rating of the over-voltage protector is exceeded. Each spring acts between an end plate and plunger head in such a way that it tends to urge its associated plunger shaft against a fusible spacer. Movement of the fusible spacer and plunger shaft is resisted by the heat transfer plate 14..Around a portion of each plunger shaft is electrical insulation, illustratively shown as electrical insulation sleeving 20, which assures that plunger shaft 18b will not come into electrical contact with electrical transfer plate 13 as it passes through an opening in that plate. The fusible spacer 19 is cylindrical with a small guide hole 19a in the center of one face which is used to locate and guide plunger shaft 18b. In the assembled position the distance 'x' between the end of the plunger shaft 18b and the heat transfer plate 14 is larger than the distance 'y1 existing between the underside of the plunger head 18a and the electrical transfer plate 13, illus¬ tratively shown to be three times larger in FIGURE 3.Each line terminal is connected to the device through a different wire 21 which mechanically and electrically connects to one of the electrical transfer plates 13 by means illustratively shown as crimp type connector 13c, formed from a protrusion of the electrical transfer plate.In FIGURE 4 there is illustrated the combination of an over-voltage protector with the device. If an excessive voltage pulse exists at the line terminals 100 or 101 the current developed will be conducted to ground through the path consisting of its associated wire 21 to its associated electrical transfer plate 13, to its associated protector end terminal, then through the protector 23 which will ionize, to the pro¬ tector case, through the heat transfer plate 14 and then through two parallel paths,thus using' redundancy to provide an extra measure of reliability, each path to ground consisting of a fusible spacer 19, plunger 18, spring 17, end plate 16 and wire 22.In the case of a prolonged over-voltage condition there is a pos¬ sibility that the gas tube or other protective element will fail. If the element becomes an open circuit the apparatus and lines connected thereto are no longer protected. To eliminate this possibility the embodiment of FIGURE 3 includes a shorting arrangement which provides an extra measure of safety and reliability as described hereinafter.In event of a sustained excessive voltage the heat generated in the protector will be conducted by spaced blades 14a, 14b of the heat transfer plate 14- to the two fusible spacers 19. As excessive heat melts a fusible spacer, its plunger 18 is forced to move because of its spring 17. During this movement electrical contact is maintained between plunger shaft 18b and the fusible spacer. Eventually, when movement is large enough, and before the end of plunger shaft 18b touches heat transfer plate 14, the underside of plunger head 18a contacts electrical transfer plate 13, thus connecting line terminal 100 or 101 to ground through the path of its associated wire 21, electrical transfer plateOiVi> iP 13, plunger head 18a, spring 17, end plate 16 and wire 22. In the illustrated use of this device there are two fusible spacers, each pro¬ viding similar heat sensitive means and similar grounding means for said excessive voltage.An important aspect of this device is its adaptability to existing terminals of presently utilized protectors, which- may be removed from operation due to one or more undesirable deficiencies and may be replaced by this device without major installation costs. This device may be operated across existing circuit terminals which presently utilize an air gap type protector such as made by Cook Electric Company, Western Electric Company or Reliance Electric, with the air gap pro¬ tector removed, since safety during prolonged overload is provided by its own fusible element and is not dependent upon the fusible element backup accompanying the air gap protector. This small mobile holder for the gas-filled over-voltage protector may be encapsulated with a protector using a potting material, Stycast 2651-40 or RTV-21 are suitable examples, with wires for its connection left exposed, and may be maneuvered and positioned into place so that it is quickly and easily connected to existing circuit terminals. Another important feature of this small device is its adaptability to existing home office equipment presently utilizing densely packaged gas-filled over-voltage protectors which operate without the use of any fusible safety elements, such as in the Til 700 block. Only a minor modification, consisting of removal of the existing block ground connection at each protector case, is necessary.An important feature providing additional safety in the use of the device is the optional use of two safety contactors 15 to prevent any electrical impulses from entering the apparatus unless an over-voltage protector ϊs employed. When the protector is removed from the device the spaced blades 15a, 15b on each safety contractor, which are aligned to separate by the entrance of the over-voltage protector 23, will con¬ tract allowing extension arms 15c, 15 to connect the grounded plate 14- to an adjacent live electrical transfer plate 13 thereby shorting all plates to ground as described above along with line terminals 100, 101 connected to the electrical transfer plates. Thus shorted to ground the protected apparatus cannot function and no electrical impulses will enter the apparatus until the short is removed by placing a protector completely into the device. This arrangement is particularly important when it is recalled that some presently used over-voltage protector devices allow the circuit which is supposed to be protected to function although the protector is not installed in the device. This line grounding arrangement also provides an additional important feature of safety and ease of maintenance in the replacement of the over-voltage protector since the protector may be placed into the device's holding clips without fear of shock from a 'hot' line. Also, it is this feature which provides safety when replacement of the device is required such as when excessive voltage has caused melting of a fusible spacer. After the protector has been removed from the device by grasping the case on the protector and the heat transfer plate on the device, both of which are grounded at all times, the safety contactors ground all line terminals and the device may be disconnected without danger.The safety contactor 15 performs the function of shorting the electrical transfer plate and heat transfer plate because of its physical configuration. The ends of the spaced blades 15a, 15b on the safety contactor are formed with a smaller distance between them than between the ends of the spaced blades 13a, 13b and 14a, 14b on the electrical transfer plate and heat transfer plate respectively. Also the lengths of the spaced blades on the safety contactor are shorter than the lengths of the spaced blades on the electrical transfer plate and the heat transfer plate. When the over-voltage protector is installed, the safety contactor's spaced blades 15a, 15b'being short, touch the over-voltage protector on opposite ends of the protector dia¬ meter, and therefore the blades' ends are moved further apart than are the ends of the longer spaced blades 13a, 13b and 14a, 14b on the electrical transfer plate and heat transfer plate respectively, which touch the over-voltage protector below the protector's diameter. For these reasons the ends of the spaced blades on the safety contactor move a greater total distance from their contracted positions to their expanded positions than do the spaced blades on the electrical transfer plate or on the heat transfer plate. Because of this greater total outward movement of the spaced blades on the safety contactor, the extension arms 15c, 15d make contact with the electrical transfer plate's blades and the heat transfer plate's blades when the over-voltage* protector is not in place and break contact with the blades on these plates during normal operation.OΛIPI μ * It is possible that the device may be removed from the existing terminals and not be replaced. To assure replacement of the device, existing wiring should have been previously modified by removing from each of the two existing line terminal posts only the wire going to the apparatus and connecting this wire directly to a different electrical transfer plate 13. Connection of the apparatus wire may be accomplished by such means as direct connection to the unused crimp type wire connector 13c, or via such means as an electrical wire nut, to the end of a wire previously connected to the crimp type wire connector 13c. Through this rewiring additional safety is obtained since the device becomes a series element rather than a parallel element in the use of apparatus and it becomes impossible for the apparatus to function without the device and the protector in their proper places.While only one embodiment of the present invention has been shown, and described, it is to be understood that many changes and modifica¬ tions can be made hereto without departing from the spirit and scope hereof. | What is claimed is:1. A clip-on protection device for use with an over-voltage protector comprising a housing, electrical contact means disposed in insulated spaced array in said housing, heat conduction means disposed in said housing and electrically insulated and spaced from said contact means, each of said contact means and conduction means including means extending from said housing and adapted detachably to engage the respective electrodes of the protector such that said conduction means is in thermal communication with the common or grounded electrode of the protector and each of said contact means is in respective electrical communication with a line-electrode of the protector, and movable means disposed in said housing and adapted electrically to ground a respective one of said contact means, said movable means including fusible means in thermal contact with said conduction means such that said movable means is normally electrically insulated from said contact means until a sustained overload condition causes said fusible means to fuse whereupon said movable means engages said contact means electrically to short same to ground.2. The device of claim 1, each of said means extending from said housing being substantially complementary to the external periphery of the protector thereby allowing the device detachably to engage the protector.3. The device of claim 2, each of said means extending from said housing being in the form of a pair of spaced blades having an arcuate or bowed portion allowing same to clip-on to a respective electrode of the protector.4.. The device of claim 1, said housing having a longitudinal length that is less than the longitudinal length of the protector onto which it clips.5. The device of claim 1, safety contactor means adapted to short said contact means to ground when the device is disengaged or detached from the protector.6. The device of claim 5, said safety contactor means adapted detachably to engage to the external periphery of said housing, the last-mentioned means resiliently biased to engage said contact means when the protector is removed from the device and disengage said contact means when the protector is inserted into the device.OMPA . IPO 7. The device of claim 1, said contact means including two electrical transfer plates disposed in said housing, said movable means including two plungers, biasing means urging each of said plungers into a pressured engagement with said fusible means, each of said plungers adapted to contact a respective one of said transfer plates, the dimensions of said fusible means being such as normally to space each of said plungers from contact with a respective one of said transfer plates until a sustained overload fuses said fusible means whereupon said biasing means drives an associated one of said plungers into contact with a respective one of said transfer plates shorting same to ground.8. The device of claim 7, two end plate means disposed in said housing, each of said end plate means being in electrical communication with a respective one of said plungers and being formed with means for connecting same to a circuit ground lead, each of said transfer plates being formed with means for connecting same to a respective circuit line.9. The device of claim 7, each of said transfer plates including an opening, each one of said plungers being configured so that a portion thereof is disposed through a respective one of said openings, said plunger portion being maintained from electrical contact with a respec¬ tive one of said openings such that said plungers are driven into electrical contact with a respective one of said transfer plates only upon the fusing of said fusible means.10. Supplementary protection means for preventing the burn out of an over-voltage protector and the apparatus protected by same and wherein the over-voltage protector has a casing and spaced electrodes, comprising plungers with shafts substantially parallel to the axis of the protector to conserve space, each of said plungers connected to ground and oriented to potentially ground a different spaced electrode of said protector, resilient means urging said plungers towards a condition of electrical contact with said electrodes, heat conduction means from said protector case to fusible means during sustained overload, said fusible means com¬ prising a fusible element in pressure engagement with said plunger, said fusible means located at a place remote from the protector but oriented to maintain said plungers and said electrodes in insulating relationship except during a condition of sustained overload threatening to burn out said protector which condition causes said fusible means to fuse where¬ upon said grounded plungers are urged into electrical contact with said electrodes, and grounding means for grounding said plungers whereupon fusing of said fusible means causes said electrodes to be 11. Protection means as defined in claim 10 including spring means resiliently urging said plunger towards electrical contact with said electrodes of said over-voltage protector.12. Protection means as defined in claim 10 in which heat con¬ ducting means comprise a plate having a holding clip for releasably holding said protector while conducting heat threatening to burn out said protector during sustained overload to said fusible means which fuse allowing said grounded plungers to make electrical contact with said protector electrodes grounding same and the voltage overload.13. Protection equipment for protecting a two wire circuit from sustained and transient over-voltage conditions comprising a housing in which is mounted two end plates, one heat transfer plate and two electrical transfer plates, said heat transfer plate and said electrical transfer plates each having a portion external to said housing shaped to form a pair of spaced holding clips for receiving and releasably holding a generally longitudinally shaped over-voltage protector having electrodes and a casing, said electrical transfer plates providing a connection from said circuit to said electrodes and said heat transfer plate providing two identical electrical paths from said casing through plungers, springs and end plates to ground, said plungers being resil¬ iently urged towards contact with said electrical transfer plates, fusible means responsive to heating of said protector and located to insulate said plungers from said electrical transfer plates except when said protector is subjected to overload.14. Protection means as described in claim 13 in which an additional wire from each of the two electrical transfer plates of said housing connects to a different apparatus wire which has been removed from its existing air gap protector terminal, thus placing the device in series with the apparatus and power line thereby providing assurance that the device and protector are installed.15. Protection means as described in claim 13 for application with existing densely packaged home protection office equipment operating without fusible backup means in which the existing equipment ground con¬ nection at the case of each three terminal protector is removed so that the protector is grounded through fusible means in the device when the device is clipped onto the existing protector.16. A clip-on protection device for use with an over-voltage pro¬ tector comprising a housing, electrical contacts disposed in insulated/-BU O spaced array in said housing, heat conduction means disposed in said housing and electrically insulated and spaced from said contacts, each of said contacts and conduction means including means extending from said housing and adapted detachably to engage the respective electrodes of the protector such that said conduction means is in thermal com¬ munication with the common or grounded electrode of the protector and each of said contacts is in respective electrical commuiiication with a line-electrode of the protector, said housing having a longitudinal length that is less than the longitudinal length of the protector, and means movable in said housing adapted electrically to ground a respective one of said contacts, said movable means including fusible means in thermal communication with said conduction means such that said movable means is normally electrically insulated from said contacts until a sustained overload condition causes said fusible means to fuse whereupon said movable means engages said contacts electrically to short same to ground.17. The device of claim 16, that part of said heat conduction means which is disposed in said housing being in the form of a plate, said fusible means being disposed in opposed back-to-back pressure engagement against a respective face of said plate thereby causing said fusible means to share a common heat source. | COREN G | COREN G |
WO-1979000662-A1 | 1,979,000,662 | WO | A1 | XX | 19,790,906 | 1,979 | 20,090,507 | new | A47H15 | E05D13 | A47H1, A47H15, E05D15 | A47H 15/02, E05D 15/06B1, P01B 202/02B | CANTED WHEELS CARRIER | An object carrier utilizing a pair of canted wheels, both wheels being always engaged with the underlying track to provide a low friction smooth riding non jammable carrier. In one embodiment the wheels are continuously engaged with and drive one another. In another embodiment each wheel is engaged with a separate rolling bearing carried by the carrier wheels axles support block. The canted wheels arrangement causes the carrier to move in a straight line along the direction of pull without crab walking. The carrier (27) includes a carrier block (78) from which divergingly upwardly extend in a common plane a pair of axles (79) which are orthogonal to each other and oriented forty-five degrees to the horizontal and vertical directions. Wheels (81) mounted on the axles (79) engage one another at their upper ends so that as one wheel rotates in a given direction its frictional engagement with the other wheel drives the other wheel in the same direction which prevents twisting or cocking of the carrier (27) within the track. Depending from the carrier block (78) is a stem (83) which carries at its lower end a support chain (85). In a modified carrier, the upper bearing for the carrier wheels (81) is provided by a ballbearing (88) seated in a socket formed in the carrier block (78) proximate to its upper edge. The ball bearings (88) engage the inside surfaces of the wheels (81) and ride within a circular groove (89) formed on the wheels inside surfaces. | CANTED WHEELS CARRIER Technical FieldThis invention relates to carriers of objects sus¬ pended from track systems for moving such objects along the track, and more specifically relates to curtain carriers for a privacy curtain system such as is used in hospitals and other facilities requiring privacy cubicles.Background ArtPrior art wheeled carriers have been either single wheeled or have been multiple wheeled with each wheel func¬ tioning independently of the others. Disclosure of InventionThe novel carrier according to the present invention utilizes a pair of canted wheels, both wheels being always engaged with the track to provide a low friction smooth rid¬ ing non-jammable carrier. In one embodiment the wheels are continuously engaged with and drive one another. In another embodiment each wheel is engaged with a separate rolling bearing carried by the carrier wheels axles support block'. The canted wheels arrangement causes the carrier to move in a straight line along the direction of pull without crab walking.The object of the invention is to provide a novel dual canted wheels non-jammable curtain carrier. Brief Description of DrawingsFigure 1 is a vertical sectional view through a portion of a track section within which is seated the novel dual canted wheel curtain carrier, one wheel of the carrier being also sectioned; Figures 2, 3 and 4 are respectively side, top and bottom views of the carrier shown in end elevation and par¬ tial section in Figure 1; andFigure 5 is a view similar to that of Figure 1 but for a modified form of dual canted wheel curtain carrier. Best Mode For Carrying Out The. InventionTurning now to the showing of Figure 1, the carrier 27 is seen to include a carrier block 78 from which diverg- ingly upwardly extend in a common plane a pair of axles 79 which latter terminate in a frusto-conical end formation80 having the larger conical base closest to the carrier block 78 and of larger diameter than the axles 79. The axles 79 are orthogonal to each other and oriented forty- five degrees to the horizontal and vertical directions. Wheels 81 are mounted on the axles 79 with the axle re¬ ceiving bores 82 being of frusto-conical cross-section wit the opening closest to the carrier block 78 being of large cross-sectional area than the axles 79 and converging to the size of the axle just inward of the frusto-conical axl end formations 80.The wheels 81 are forced onto the axles 79 by pres¬ sing them inward past the end formations 80, which latter then restrain the wheels 81 from moving outward on the axle 79. The thickness of the wheels 81 is such that when moun¬ ted upon the shaft 79 there is a clearance between the car¬ rier block 78 and the inner surface of the wheel 81. Addi¬ tionally, the wheels 81 engage one another at their upper ends so that as one wheel rotates in a given direction its frictional engagement with the other wheel drives the other wheel in the same direction. Accordingly, each of the whee drives the other which prevents twisting or cocking of the carrier 27 within the track. The outer surfaces of the lower ends of the wheels81 are spaced slightly away from the inside surfaces of the track walls 57, and the inside surfaces of the wheels 81 do not engage the inner edges of the tracks 56. As a conse¬ quence of this construction, the wheels 81 ride on the hor- izontal surfaces 56 of the track with freedom to move sligh ly laterally, and therefore never laterally bind within the track structure. Depending from the carrier block 78 is a stem 83 which terminates at its lower end in a chain holder 84 within which is replaceably secured a support chain 85. Figures 2, 3 and 4 are respectively side, top and bottom views of the carrier shown in end elevation and partial section in Figure 1.OMPI y_ WIPO A slightly modified carrier 27' is illustrated in Figure 5, the parts being identical to those of carrier 27 except for two differences. In the showing of Figure 5, the upper bearing for the carrier wheels 81 is not provided by having the wheels engage one another, but is provided by having the inside surfaces of each wheel bear against a ball¬ bearing 88 seated in a socket formed in the carrier block 78 proximate to its upper edge. The ball bearings 88 engage the inside surfaces of the wheels 81 and ride within a cir- cular groove 89 formed on the wheel inside surfaces. In both cases, the double bearing supports for the wheels 81 provide a mechanically strong and stable structure.While the axles 79 are shown in Figures 1 and 5 as being orthogonal to one another, it is not absolutely manda- tory that the angle between the axles be precisely ninety degrees. Other angles could be used if desired. However, significantly smaller angles increase the bearings loads and widen the track with no apparent offsetting benefit, while significantly larger angles can increase the required- track height and decrease the upper bearings loads which in extreme cases could cause the wheels in the embodiment of Figure 1 to slip relatively to one another. | CLAIMS1. A dual wheel carrier for use in conjunction with a car rier track consisting of a pair of parallel longitudinally extending spaced apart tracks, said carrier being charact- erized by, a) an axles support from which extend divergingly upwar a pair of axles, and from which depends means for at¬ taching an item to be carried, and b) a wheel mounted on each of said axles for rotation, the lowest points of said wheels being spaced apart th proper distance so that each wheel is seatable on and rideable along a different one of the spaced apart tra of the aforesaid carrier track, said wheels converging toward one another at their upper edges.2. A dual wheel carrier as described in claim 1 further including a rolling bearing for each said wheel, said bear ings being positioned at locations closer to each other th are the locations of the bearings of the wheels on the axl and than are the contacts of the wheels with the underlyin tracks.3. A dual wheel carrier as described in claims 1 or 2 whe in said axles are non-rotatably fixed to said axles suppor and said wheels are centrally apertured to receive said ' axles therethrough, said central wheel apertures being of frusto-conical shape with the smaller base being of substa tially the same diameter as said axle and located proximat to the outer face of the wheel while said wheel aperture larger base is larger than the axle diameter and located at the inner face of the wheel.4. A dual wheel carrier as described in claim 1 or 2 wher in each said axle is provided on its outer end with a resi iently deformable wheel retainer formation of larger dia¬ meter than the axle, and each said wheel is forced onto sa axle until said wheel retainer passes the outer end of sai wheel central aperture. 5. A dual wheel carrier as described in claim 1 wherein said pair of axles are orthogonal to each other and in use are oriented at forty five degrees to the horizontal plane of the tracks on which the wheels of said carrier are ride- able.6. A dual wheel carrier as described in claim 2 or 3 where¬ in said wheels are of such diameter that when mounted on said axles they converge at their upper edges into engage¬ ment with one another, said engagement constituting said rolling bearing.7. A dual wheel carrier as described in claim 2 wherein said rolling bearing comprises a ball bearing journalled in said axles support and engaged with the wheel face clos¬ est to said axles support.8. A dual wheel' carrier as described in claim 2 wherein said rolling bearing comprises a ball bearing journalled in said axles support and engaged with the wheel face clos¬ est to said axles support, which wheel face is circularly annularly grooved to receive therein a portion of said ball bearing surface.9. A dual wheel carrier as described in claim 3 wherein said axles are co-planer and said rolling bearing comprises a ball bearing' journalled in said axles support and engaged with the wheel face closest to said axles support.■BURE-Q;_O PI■ W1P | TODER E | TODER E |
WO-1979000667-A1 | 1,979,000,667 | WO | A1 | XX | 19,790,906 | 1,979 | 20,090,507 | new | E01B25 | A47H1 | A47H1, A47H15, E05D15 | A47H 15/02, E05D 15/06B1, P01B 202/02B | TRACK SWITCH | A hospital curtain track system utilizing a track switch (25) which permits the use of a single privacy curtain (28) selectively for one of two or more adjacent bed cubicles. One track switch unit (25) between each two bed environment splices directly with the cubicle track (23, 24, 26) and eliminates extra connecting parts including the elimination of one complete track leg, resulting in minimal installation time and expense. The switch utilizes a pull-chains actuated toggle for shifting a horizontally shiftable switch section (37) for aligning a common track (26) with the desired curtain track. | TRACK SWITCH Technical FieldThis invention relates to privacy curtain track systems and more particularly to a hospital track system utilizing a track switch which permits the use of a single privacy curtain selectively for each of a pair of adjacent bed cubicles. Background ArtHospital privacy curtain systems in the past util- ized a separate track system for each hospital bed with a separate curtain for each track system thus requiring more track and more curtains. Disclosure of InventionThe privacy curtain system is adaptable to multiple bed hospital environments and requires fewer curtains while providing maximum privacy. One curtain may be used for two or more beds. Self splicing cubicle tracks of various lengths and shapes provide easy assembly and versatility in space planning. The track switch unit connects a com- mon track between each two bed environment directly with either of the discrete cubicle tracks which enclose the other sides of each bed and eliminates extra connecting parts, including one complete track leg and resulting in minimal installation time and expense. The switch utilizes a pull-chain actuated toggle for shifting a horizontally shiftable switch section for aligning the common track with the desired discrete cubicle curtain track.The switch and tracks are of two types, one type being a recessed system installable flush with the under- side of and as an integral part of an original ceiling in¬ stallation, and another type being surface mounted instal¬ lable upward against the underside of an existing ceiling. The system can of course be used also in residential and commercial drapery installations. A primary object of the invention is to provide a novel curtain track system which requires only one curtain to provide privacy for a plurality of hospital beds. Another object of the invention is to provide a novel curtain track system as aforesaid which utilizes a manually actuatable track switch to selectively direct a privacy curtain from one track to another. Brief Description of DrawingsFigure 1 is an isometric view of the novel ceiling recessed curtain track system according to the invention;Figure 2 is a fragmentary isometric view of the curtain track system in the region of the track switch; Figure 3 is an exploded isometric view of the track switch;Figure 4 is a vertical sectional view through the track switch as would be seen when viewed along lines 4-4 of Figure 2; and Figure 5 is a horizontal sectional view through the track switch as would be seen when viewed along lines 5-5 of Figure 4. Best Mode for Carrying Out ~the InventionReferring now to the drawings, and first to Figures 1 and 2, there is observed a room, which typically could be a hospital room, having a suspended ceiling 20 consisting of a plurality of the usual T-bar supports, designated gen¬ erally as 21, which support a plurality of ceiling panels 22. In place of one of the T-bars 21 are a pair of curtain tracks 23 and 24 which are flush mounted in the ceiling and function not only as curtain tracks but also as an integral part of the suspended ceiling support grid. The two cur¬ tain tracks 23 and 24 are shown as co-linearly alined,and as they approach each other curve out of alinement and in- ward into engagement with a track switch 25.' A third cur¬ tain track 26 extends outward from the track switch 25 substantially orthogonally to the running length of the curtain tracks 23 and 24, and also forms part of the ceil¬ ing support grid. Suspended from the track system by car- riers 27 is a curtain 28 which, as seen in Figure 1, forms a cubicle when extended along the tracks .24 and 26 through the switch 25, and which forms a second cubicle, not shown,OM when the curtain is extended along tracks 23 and 26 through the switch 25.As best seen in Figures 2 and 3, the track switch 25 is seen to have a pair of symmetrical bottom or lower outer sections 29 and 30 of generally C-shape or U-shape, and a generally truncated triangularly shaped section 31 spaced between legs 29A and 30A of the outer sections 29 and 30. As best seen in Figure 3, the switch has a top section 32 having a top closure plate 33 from which de- pend a pair of outer sections 34 and 35 which are congru¬ ent with and matingly overlie the bottom outer sections 29 and 30 respectively, and also has a top triangular sec¬ tion 36 which congruently matingly overlies the bottom triangular section 31. A generally rectangular dual track switch slider 37 is held slidably captive between the top plate 33 and the bottom plates 29C and 30C of the lower outer sections 29 and 30. Secured to the slider 37 are a pair of ball chain pulls 38 and 39, the chain 38- being trained around pulley 40 and extending downward through an aperture in the bottom outer section 29, while the chain 39 is similarly trained around a pulley 41 and extends downward through an aperture in the bottom outer section 30.As best seen in Figure 2, the legs 29B and 30B of the bottom outer sections 29 and 30 form an opening into which the end of the common track 26 fits precisely and accurately, this opening also being shown in Figure 5 with a portion of the end of track 26 disposed therein with the actual tracks 56 on which the wheels of the curtain car¬ riers 27 ride being alined with track portions 29D and 30D formed respectively on the ends of legs -29B and 30B of the bottom outer sections 29 and 30 . In a similar man¬ ner, a pair of branch track openings to receive the ends of the tracks 23 and 24 are formed between the ends of legs 29A and 30A of the bottom outer sections 29 and 30 and the bottom triangular section 31. Track sections 29E and 31A form continuations of the carrier tracks of cur¬ tain track 23, while track portions 30E and 31B form the track continuations for the track portions of curtain track 24.The switch slider 37 is formed with a pair of curved track sections 42 and 43 which respectively con- nect the common track opening for track 26 with the branch track openings for tracks 23 and 24 as a function of the position of the switch slider 37. As shown in Figure 5 of the drawings, with one end of the switch slider against the end wall of bottom outer section 29, the curved switch slider track section 43 forms a continuous smooth track connecting section between branch track 24 and common track 26. When the switch slider 37 is shifted to the right so that the end disposed within the bottom outer section 30 is stopped by the end wall of section 30, then switch sli- der track section 42 forms a continuous track connection between track 23 and common track 26. Shifting of the switch slider 37 from one switch position to the other is accomplished by pulling downward on the ball chain pulls 38 and 39, downward pull on chain 38 causing the switch to assume the condition shown on Figure 5, whereas pulling downward on ball chain 39 causes the switch slider 37 to move laterally and connect tracks 23 and 26 by means of the curved track section 42.The switch slider 37 remains in stable switch posi- tion because of the over-center toggling .action of a spring toggle formed by an outer cylindrical telescopic section 44 and an inner section 45 with a compression spring 46 held captive within and between the inner and outer tele- scopically engaged toggle cylindrical sections 44 and 45. The free end of outer cylinder 44 is formed in the shape of a semi-circular cylindrical section 47 which seats in pivotal fashion in a semi-circular cylindrical socket 48 molded on the inner surface of leg 29B of bottom outer section 29. Similarly, the free end of toggle inner tele- scopic section 45 is similarly formed with a semi-circular cylindrical end section 49 which fits pivotally smoothly into a semi-circular cylindrical socket 50 formed on the inside of the switch slider 37, as best seen in the show¬ ing of Figure 5. The pivot end 47 is the fixed pivot while the pivot end 49 is the floating pivot, which latter turns within socket 50 and swings over toward the right as the slider 37 moves to the right under the urging of pull chain 39, the pivot end 47 pivoting within the socket 48 but un¬ dergoing no translational or shifting movement.The pull chains 38 and 39 are restrained from la¬ teral movement off of their associated pulleys 40 and 41 by being held captive laterally between the side guide posts 51 which depend from the top plate 33 and the adja¬ cent inner edges of the top outer sections 34 and 35. The switch 25 is also provided with a peripherally extending flange 52 which underlies the adjacent parts of the ceil- ing which have been cut out so that the switch may be up¬ wardly recessed for flush mounting with the ceiling un- dersurface. A switch support plate is positioned above the switch 25 arid overlying a pair of adjacent T-bar sup¬ ports 21, as best seen in Figures 2 and 4, to carry and support the mass of the switch 25 and provide sufficient mechanical support to oppose the downward pull exerted by chains 38 and 39 which actuate the switch mechanism, the support plate being designated as 53, and the switch be¬ ing shown secured thereto in Figure 4 by the screws 54. While the switch may be made in any desired fashion, it is illustrated as being formed of molded plastic to pro¬ vide a minimum weight.- UREAUOMPI | CLAIMS1. A curtain track system characterized by a) a curtain track system comprising first and second branch tracks and a common track, b) a track switch adapted for operative coupling to each of said first and second and common tracks, said track switch including shiftable track means for selectively interconnecting said common track to one of said first and second branch tracks, and act- uating means for selectively shifting said shiftable track means to connect said common track as desired to either of said first or second branch tracks.2. A track switch as described in claim 1 wherein said shiftable track means comprises first and second separate switch track sections, said first switch track section being movable into position to interconnect said first branch track to said common track when said actuating means is actuated in a first way, and said second switch track section being movable into position to interconnect said second branch track to said common track when said actuating means is actuated in a second way.3. A track switch as described in claims 1 or 2 including a hollow switch body having a separate track-end receiving opening for each of said first and second branch tracks and said common track, said shiftable track means compris¬ ing a slider unit held captive within said hollow switch body.4. A track switch as described in claim 2 wherein said first and second separate switch track sections are fix- edly intercoupled and movable as a unit.5. A track switch as described in claim 3 wherein said hollow switch body further includes a flange extending peripherally thereabout and outward from the lower edge gυ EOMPI of the switch body, said flange being adapted to closely underlie thelower surface of a ceiling into which the switch body may be upwardly recessed.6. A track switch as described in claim 3 wherein said hollow switch body further includes interior fixed track sections positioned to function as continuations of the external branch and common tracks and provide a smooth track continuation between said external tracks and said shiftabl-e track means first and second track sections.7. A track switch as described in claim 3 wherein said actuating means for selectively shifting said shiftable track means comprises a resilient toggle coupled at one point to said hollow switch body and coupled at another point to said slider unit.8. A track switch as described in claim 3 wherein said actuating means for selectively shifting said shiftable track means comprises a resilient toggle coupled at one point to said hollow switch body and coupled at another point to said slider unit, and wherein said hollow switch body further includes interior fixed track sections posi¬ tioned to function as continuations of the external branch and common tracks and provide a smooth track continuation between said external tracks and said shiftable track means first and second track sections.9. A track system as described in claim 6 wherein each said switch body track-end receiving opening has received therein a track section comprising in combination a) a pair of horizontal longitudinal extending parallel spaced apart tracks, and b) a pair of upstanding sidewalls interconnected with each other at an elevation above the level of said pair of tracks, said switch body track-end receiving opening being formed•BU E TΓOMPI l W1PO A*, in cross-section with lands and openings to interfit with and close fittingly receive thereinto at least portions of the ends of said track section tracks and sidewalls, with said tracks aligned with the said switch body inter- ior fixed track sections.10. A track switch and tracks sections as described in claim 9' wherein each said track section further includes a longitudinally extending horizontal flange extending la¬ terally outward from each of said pair of parallel spaced apart tracks, said flanges extending laterally in opposite directions outward away from one another and also engag- . ingly interfitting with lands and recesses formed in said switch body at said switch body track-end receiving open¬ ings.W1P0 | TODER E | TODER E |
WO-1979000688-A1 | 1,979,000,688 | WO | A1 | XX | 19,790,920 | 1,979 | 20,090,507 | new | C25B1 | C25B11, C25B9 | C25B1, C25B9, C25B11 | C25B 1/46, C25B 9/08 | ELECTROLYTIC CELL ESPECIALLY FOR CHLORALKALI ELECTROLYSIS WITH AIR ELECTRODE | Electrolytic cell, especially for chloralkali electrolysis, comprising an anode (1) disposed in an electrolyte room (2) and at least one air electrode (3) with an inner space (20), said air electrode being separated from the anode by means of a diaphragm or membrane (17). The air electrode comprises a layer (18) of an electrocatalytically active material, said layer being directly disposed onto the diaphragm or the membrane (17) or constituting an integrated part thereof. The layer (18) is hydrophobic but nevertheless permeable for the electrode so that it can penetrate into the inner space (20) of the air electrode (3) to be collected therein. The layer (18) of the electrocatalytically active material is in contact with process air in the inner space (20). | Electrolytic cell especially for chloralkali electrolysis with air electrode.The energy cost is a heavy item' in the calculus for electrolytically produced chlorine and alkali. An increasing cost for electrical energy will accentuate . these circumstances further. Technical developments in the chlor-alkali field therefore has- an objective to - reduce the energy consumption in the electrolytic pro¬ cess. One possibility to reduce the cell voltage is to introduce air cathodes so as to eliminate the energy consuming hydrogen. development in the cathode fingers. Hydrogen being developed in conventional electrolysers seldom finds a- meaningful use at the chlor-alkali plants. Introduction of air cathodes will reduce the cell voltage with something between 0.5 - 1 volt depend- ing on the current density, the temperature and the activity of. he.air electrode. This reduction of the cell voltage will evidently have ••'■ery great importance for the economics of the chlor-alkali process.The inventors have therefore shown a certain interest in this question and there are several designs of chlor¬ alkali cells with air cathodes described in the litera¬ ture, see e.g. the U.S. patent 3.262.868.Another more radical possibility is' to introduce a bi- . functional hydrogen electrode at the same time in order . to adjust the production of -chlorine and alkali.to the mar¬ ket demand with the minimum sacrifice of electrical energy for every specific market profile- for chlorine respectively alkali, see the U.S. patent 3.864.236. • •A particularly- advantageous design for air cathodes which are quite useful for bi-polar chlor-alkali cells is shown in the German Offenlegungsschrif 2627142. 1-41.•Chlorine and alkali are produced on a very large scale in all industrialized countries and the amount of ca¬ pital whiph has been invested in these chlor-alkali plants is very large. The useful life of these plants is also quite long. It is not unusual that plants last 20-30 years and even longer. However, it is ne- cessary to renovate the cells at frequent intervals, change anodes, put on new diaphragms etc. It has also been possible to develop existing cells towards better performance e.g. by the introduction of so-called di- mensionally stable anodes instead of graphite anodes in mercury cells as well as in diaphragm cells. These different cell types are described- e.g. in Kirk-Othmer Encyclopedia of Chemical Technology , Second Edition, Volume 1, pp. 668-707, J.S. Sconce Chlorine ACS monograph No. 154, 1962, and e.g. the U.S. patents 3.124.520, 3262.868 and other publications and patents. Pertinent information which is quite up to date from .many point of views is found in the Proceedings from the Chlorine Bicentennial Symposium, ECS, 1974, and Hardie: Electrolytic Manufacture of Chemicals from Salt The Chlorine Institute 1975.Work up to day to develop and introduce air cathodes in chlor-alkali electrolysis has been concerned with the task to develop a completely new electrolytic cell e.g. by means of bi-polar electrode designs. Much > would be gained however if a design could be envisaged which would make it possible to introduce air cathodes in existing cells of diaphragm or membrane type with monopolar electrodes. Such air electrodes could thenOMPI r WiPO be used with existing electrolytic plants and thus immediately give very important global conservation of electrical energy. The operating costs for the chlor-alkali process would also be reduced considerab- ly with such modification. It is fair to say that such an innovation would be even more important than the earlier introduction of dimensionally stable anodes.One objective for the present invention is therefore to make possible conversion of existing chlor-alkali .cells of diaphragm or membrane type with monopolar electrodes to air electrodes.A second objective is to reduce the consumption of electrical energy for the electrolysis considerably due to the fact that also existing plants may be con¬ verted to air electrodes.A third objective is to furnish a design which makes possible simple renovation of the air electrode on the same occasion as exchange of dimensionally stable anodes, membranes or diaphragms.A fourth objective is to reduce the chloride content in the alkali hydroxide solution.A fifth objective is to increase the concentration of the product solution particularly with diaphragm cells.Other objectives will be apparent from the description.The characteristic feature of the air electrodes for electrolysers according to the invention is that it forms a space which is separated from the surrounding outer anolyte, the surfaces of said space being covered with a separator consisting of an asbestos diaphragm or a cation permeable material; electrocatalytically active material, which is at least partly hydrophobic, 5 disposed therein whereby the separator and the electro¬ catalytically active material are mechanically supported by an electrically conducting supporting structure which is .furnished with means for supply and removal of air to a said space; means for removal of the alkali τ_Q hydroxide solution which is being formed at the reduc¬ tion of oxygen in the presence of electrolyte which is moving into said space from the surrounding outer space through the separator; and means to bring air and alkali hydroxide solution in contact with the side of15 the electrocatalytically active material which is facing the interior of said space.It shall be immediately remarked that the principle of the air electrode as described above differs in a very important respect from the state of art air electrodes2o or chlor-alkali cells since the electrolyte is brought into contact also with the back side of the air electrode (front side here means that side of the electrode which is facing the counter electrode, in this case the chlorine anode, back side is the other25 side of the electrode) . Conventional air electrodes have during normal operation no electrolyte in contact with the back side of the electrode, see e.g. U.S. patent 3.864.236 and 3.262.868.This new design principle gives a number of practical 30 and process technical advantages. One such practical advantage is of course that the air electrode according to the invention makes possible a functioning chlor¬ alkali cell with air electrodes. These practicalOMPI fa WiPO advantages should be apparent from the following de¬ scription. It has, however, also been found that the invention produces several very surprising process technical advantages compared to conventional air electrodes with catholyte disposed on the front side of the air electrode and not on its back side according to the present invention. It is thus possible to pro¬ duce a more concentrated alkalihydroxide solution with the embodiment for diaphragm cells which reduces steam requirements for the concentration operation. Another advantage of great importance is. that the chloride con¬ centration will be lower which is of particular im¬ portance for the diaphragm cells.The very low energy consumption, the high alkali con- centration and the low chloride concentration are factors of outmost importance for the economics of the chlor-alkali electrolysis. The present invention has in common with several other inventions in the chlor¬ alkali field, like dimensionally stable anodes, di en- sionally stable diaphragms and efficient membranes, constructive simplicity combined with very high tech¬ nical efficiency. The invention is meeting the ob¬ jectives which were formulated above in every respect. The invention shall now be described by means of a few examples. The air electrode can be introduced along three routes:(1) Addition to existing diaphragm and membrane cells with a minimum of constructive modification.(2). Radical modification of the cathode supporting parts of the cell including the cathode element at existing diaphragm and membrane cells.(3) Completely new design of the whole electrolyser so as to get an optimized embodiment of the invention.The invention shall now be described by means of the following drawings.Figure 1 shows in a schematic way the arrangement of the functional elements of a chlor-alkali cell with air electrode according to the invention.Figure 2 shows in the same way a corresponding cell wall part for a similar cell with a -conventional air elec¬ trode.Figure 3 shows the functional design of a bi-polar electrolytic cell with air electrodes according to the invention.Figure 4 shows how a conventional cathode with ■ hydrogen development may be modified so as to serve as an air electrode according to the invention for a chlor-alkali cell,e.g. of the type being developed by Hooker Chemicals,with a minimum of modification in other re¬ spects.Figure 5 shows a special embodiment with a porous elec- trolyte holding body disposed in the interior of the air electrode.Figure 6 shows another special embodiment with an air electrode to be used with membrane cells whereby the electrode is sectioned in elements intended for air, respectively electrolyte.In order to save space the description will be mainly concerned with the constructive design of the nev; air electrode. The state of art in chlor-alkali technology is well described in the standard references referred to above. Present designs of diaphragm and membrane cells are described in printed material published by the leading companies in the field, Hooker Chemicals and Diamond Shamrock. A detailed flow-sheet for a modern chlor-alkali plant with diaphragm cells has been produced by Diacell AB in Gavle, Sweden, 1977. The artisan will experience no difficulty to introduce and use the electrodes according to the invention for chlor¬ alkali electrolysis without any further advices in the present description.It should however be remarked that conversion from hydro¬ gen development to oxygen reduction will involve a few simple changes which can easily be carried out by the artisan. The sensible heat in the hydrogen gas stream is frequently recovered for the evaporation of the alkali hydroxide solution. The sensible heat in the warm air streamleaving the cathode spaces may be utilized in the same way. Sometimes hydrogen is used as a fuel in boilers for production of process steam. These steam generators must of course operate on a different fuel in the future. Piping which has been installed in an existing plant for the hydrogen system may be kept to be used for the air system after change from hydrogen development to oxygen reduction.The requirement for air, oxygen enriched air or oxygen for the oxygen reduction of course depends on the oxygen concentration in the supplied gas. If pure oxygen is used the supply will amount to about half of the earlier hydrogen flow on a volume basis in view of the stoi- chiometrics of the reaction. Inert components present in the oxygen may in this case be vented off periodically to prevent that the concentration of these inert compo¬ nents, like argon and nitrogen, will increase in the cathode spaces. When operating on air it may frequently be suitable with an excess corresponding to the double oxygen requirement, whereby the supply of air will amount to about five times the corresponding flow of hydrogen in the hydrogen mode of operation. In this case about half of the oxygen supplied will be consumed in the electrode reaction whereas remaining oxygen will leave with the outgoing air. It may sometimes be of advantage with preheat and moistening of the air supply. Sometimes one may also have use for the cooling and drying effect of supply of cool and dry air to the cathode space. It may also sometimes be of advantage to recirculate air back to the cathodes spaces after enrichment with fresh air, oxygen enriched air or oxygen. Such recirculation may also be of advantage to reduce the uptake of carbon dioxide by the alkali hydroxide solution. All these questions are to be viewed upon as practical questions of optimization which can be easily decided by the artisan from case to case depending on the operating conditions in question, desired product quality, etc.The carbon dioxide content of the air is a chapter on its own. This carbon dioxide is taken up by the alkali hydroxide solution and causes an increased content of carbonate in the electrolyte. In certain applications it is desirable to minimize the carbonate concentration and it is then necessary to first remove the carbon dioxide of the air in a special scrubber where the air is scrubbed preferably with an alkali hydroxide solu¬ tion which is then decarbonized in known manner e.g. by means of electrodialys or causticisin , etc. The design of the system for air supply does not present any problems for the artisan which is apparent from the description above.Change from hydrogen development to oxygen reduction at an existing plant requires a special procedure for the change-over which has to be decided from case to case depending on the extent of cell modification. It is frequently desired to carry out the change-over step by step without disturbing the production and further- more it is desired to use the facilities which are available for cell maintenance. It is then useful to utilize mobile aggregates for individual air supply to a cell unit. After a cell has been rebuilt it will be put back on its place in the cell hall and connected to the system excluding the pipe for outgoing hydrogen. The air supply is then connected whereafter the cell will run on oxygen reduction with no other interference with the system. In this way one may successfully mo¬ dify a certain number of cells and then join this group to the common air system. When a sufficient number of • cells have been converted the common hydrogen system is to be disconnected. Of course one may also follow other policies e.g. complete stop of production during the change-over period or connection of the converted cells to the new common air system already from the be¬ ginning. The much lower cell voltage with chlor cells with air cathodes also requires either modification of the electrical supply system or expansion of the cell hall so that the available system voltage will be used fully. In this way improved economy of operation may be combined with capacity increase.The active materials in a chlor-alkali cell has limited life and it is therefore necessary to remove a cell from time to time for renovation or a change of e.g. dia- phragm. The electrocatalytically active material in the air electrode has also limited life. It is therefore useful to choose materials and operating conditions so that exchange or reactivation of the electrocatalytic- ally active material may take place with the same time intervals as other operations of maintenance. Of course it is of a particular advantage to regenerate the electrocatalytically active material simultaneously with regeneration or exchange of diaphragm or membrane respectively. It is of course also extremely important . that the air electrode is designed in such a way that the electrocatalytically active material can be easily regenerated or exchanged. It is of. course particularly useful to apply this material on the supporting struc- ture by spraying, painting, dipping, electrophoretic precipitation or in other ways without use of mechanical operations.The materials which are used in air electrodes according to the invention are presently used in the chlor-alkali technology, the fuel cell technology, metal air battery technology, etc. As separator materials may be used diaphragms or membranes of the type that is now being used in chlor-alkali cells. Different kinds of dia¬ phragms are described in the U.S. patents 3.694.281, 3.723.264 and others. Also other types of diaphragms or membranes for chlor-alkali cells may be used.Publications pertaining to so-called Nafion membranes are found e.g. in the Proceedings from the Electrocrie- mical Society's meeting in Georgia, October 9-14, 1977, pp 1135-1150.The electrocatalytically active material contains cata¬ lysts for oxygen reduction of known type on the basisOMPI,fa 1P0 of active carbon, silver basis, metal oxides containing nickel and cobalt, so-called perovskite- and spinel structures and of course noble metal catalysts. These catalysts, containing conducting additives in the form of carbon, graphite, nickel powder and structure stabilizing additives like carbides, nitrides, etc. are bonded together to a porous structure of thin thickness frequently a few tenths of a millimeter preferably by means of sintered particles of Teflon. This will at the same time give the desired hydrophobic property to improve the air contact. This technology is now es¬ tablished above all by progress that has been made in the fuel cell fi ld. Here can be referred to the Swe¬ dish published applications 300.246, 329.385, 369.006, 349.130, 333.783, 371.913, 5742/72, Power Sources Sym¬ posium No. 6 and 7, Siemens Berichte 5, 1976, pp 266-271.The mechanically supporting structure may in all im¬ portant parts be designed according to designs which have been developed for cathode fingers, see e.g. U.S. patent 2.987.463. The supporting structure can be manufactured by nickel-coated carbon steel or other combinations of materials-which are resistant in the alkaline environment at the electrode potential for oxygen reduction in question. If the diaphragm is fabricated in known manner by dipping the structure in a slurry of asbestos fibre whereafter vacuum is put on the interior of the air electrode, the structure must of course be furniched with an interior support to take up the outside pressure. These interior supports are with advantage designed so that they simultaneously serve as baffles to bring supplied air in contact with the electrocatalytically active material disposed on the walls of the inner space. After this report on available known techniques which can be utilized in the application of the invention I shall now describe the constructive design of the air electrodes. I will now limit myself to the mechanical structure and may then rely on recommendations in the above description.Figure 1 shows completely schematically the functional design of a chlor-alkali cell with air electrode accord¬ ing to the invention. For the sake of simplicity only one single cell element is shown containing a so-called dimensionally stable chlorine anode (1) with a surround¬ ing anolyte room (2) and the air cathode with its inner room (3) . A cellbase plate (4) carries the anodes. The cathodes are disposed at the cell wall part (5) with means (6) for discharge of alkali hydroxide solu¬ tion and means (7) and (8) for supply and discharge of process air respectively. The cell cover (9) contains a pipe for discharged chlorine (10) and a connection for supply of alkali chloride solution (11) . Supply of electrical energy takes place by the connectors (12) and (13) respectively. The anode is insulated from the cellbase plate by the insulation (14) and the cellbase plate is of course electrically insulated from the cell wall part (5) with the insulating gasket (15) .As the artisan easily realizes, Figure 1 shows in prin¬ ciple a completely conventional chlor-alkali cell with exception for the new electrode. (The drawing is how¬ ever so to say constructively misleading since the air electrode is at the same time shown in a section by the surface which is facing the anode and in a section through the cell-wall part.) In reality the air electrode will look from the outside very much the same as a cathode finger in a conventional chlor-alkali cell. The air electrode contains the separator mate¬ rial (17) which may be an asbestos diaphragm or a Nafion membrane, the electrocatalytically active mate¬ rial (18) which may be a Teflon-bonded porous Raney silver catalyst or active carbon catalyst, the perfo¬ rated or foraminous supporting structure (19). which de¬ limits the inner room (3) of the air electrode. The supporting structure (19) is furnished with openings (21) and is preferably Teflon-coated so as to make the whole supporting structure electrolyte repellant and thereby facilitate capture of air bubbles for better contact between air and the electrocatalytically active material (18) . It may furthermore be of advantage to make use of a special supporting material (22). for the electrocatalytically active material. This supporting material could be a nickelwire mesh arranged on the supporting structure, porous graphite or carbon paper etc. The supporting material may also be applied on the interior side of the supporting structure,Figure 2 shows a conventional air electrode in a cell of the same type. Inspection of the figure reveals that there is here a special catholyte room (23) arranged between the separator (17) and the air cathode (16) which is not permeable for electrolyte, and a special gas room for air (241. This cathode is thus functionally built up in the same way as has been de¬ scribed for gas diffusion electrodes for electrolysers in the U.S. patent 3.864.236.In the operation of the cell according to Figure 1 the air is supplied via the conduit (7). and is then brought into contact with active electrode αaterial being ex¬ posed via openings (21).. in the supporting structure (19), The inner room is filled up by a more or less continuous air phase and a more or less continuous electrolyte phase, whereby the distribution between air and electro¬ lyte depends on the constructive design of the inner room, the hydrophobization, the baffles, the support- • ing structure, etc.Figure 3 shows how the invention may be used with bi¬ polar cells. This figure is also a pure principal sketch which shows the fundamental function. The figure shows a repetitive element in a pile of bi-polar electrodes (25) with intermediate insulating frame ele- ments (26) .. The notations are the same as in the pre¬ ceding figures. The separator (17) is here preferably a cation permeable membrane like Nafion.Figure 4 shows how the essential design according to Figure 1 can be achieved by rebuilding an existing chlor-alkali cell. For simplicity Figure 4 shows only a section through the supporting structure. The cell'- wall part with its cathode fingers has been dismounted in a known way and the asbestos diaphragm has been re¬ moved. To begin with the structure has been nickel- coated galvanically in the known way. A thin nickel wire mesh (22) has been disposed in such a way that it covers the perforated or foraminous part of the structure. This nickel wire mesh shall serve as support for the electrocatalytical active material. Furthermore- an air distributor (27) with holes (28) for supply of air evenly over the inner section of the cathode finger has been introduced in every cathode finger. This air distributor is connected to a main line not shown for incoming air which in its turn is connected to the com- mon air system. The electrocatalytically active mate¬ rial is then put on the nickelwire mesh by painting of a thin layer (0,1 mm), of a slurry of Raney silver of so-called SiemenJs type (see reference above) . A sus¬ pension of 100 grams of silver in 100 grams Teflon dis- '-persion (DuPont Teflon 30 N) is sufficient for 1 Sq.m.O . W1P The nickel wire mesh should have a mesh number above 60. Sintering is taking place at 350°C for 15 minutes in air.In order to facilitate transfer of electrolyte through the hydrophobic layer (which is frequently disposed on the air side of state of art air electrodes) , the layer is perforated with rollers with needles so as to pro¬ duce holes in the layer. These holes, frequently 0,2-1 mm in diameter may cover minor part of the elect- rode surface frequently in the range of 1-10%. After the electrode material structure has been sintered to¬ gether e.g. by heating up to 300 C for 20 minutes the asbestos diaphragm is supplied in known manner. It is also possible to sinter the electrocatalytically active material and the diaphragm in one and same operation..The modified cell wall part may now be mounted on its cell base plate in the cell hall with the difference that the connection to the hydrogen system is sub¬ stituted for connection to the system for discharged air and furthermore that the air space is connected to the system for air supply.An important thing is of course the adjustment of the hydraulic resistance for transfer of electrolyte from the anolyte room to the interior of the air electrode. One has here to find out by experimentation suitable hydrophobization, pore structure and eventual perfora¬ tion of the active air electrode material. One may also simultaneously reduce the thickness of the dia¬ phragm considering the transport resistance offered by the air electrode. (It is also possible to make diaphragm and electrode materials in to one unit which may be described as elimination of the separator.) There are in principal two possibilities. In one case the electrolyte is allowed to weep from the anolyte room into the interior room of the air electrode to be collected in the lower part of the air electrode where¬ by the air electrode is mainly filled up with air. The transfer of electrolyte into the catholyte room is depending on complicated electro-osmotic and other transport processes in the membrane and is only to a minor extent depending on the hydrostatic pressure differential between the two rooms. In the other case the catholyte space is mainly filled up with electro¬ lyte and the driving force for transport between the anolyte room and the interior of the air electrode is mainly the hydrostatic pressure difference. This re¬ quires thus that the air electrode is perforated as has been described above. A good contact is still ob¬ tained between the air and the electrocatalytically active material since the air bubbles are collected at the openings in the supporting structure. The air bubbles are hereby transported successively from level to level in the air electrode.Figure 5 shows another useful embodiment with a porous electrolyte-holding structure (29). disposed in the in¬ terior of the air electrode. This electrolyte-containing structure may be manufactured in position within the cathode finger by sintering of alkali-resistant polymers like polysulfon, penton, polyphenyleneoxide, etc., whereby the open porosity is produced by means of spacers like particles of sodium chloride which are then leached away. The electrolyte containing struc- ture also contains channels for addition of air (30) , respectively discharge of air (31) , and channels (32) to produce contact between the air and the electro¬ catalytically active material. The electrolyte-con¬ taining structure furthermore contains ribbons (33) or other contact points for conducting electrolyte from the electrocatalytically active material to the electrolyte containing structure. This design gives a completely controlled distribution of air and electrolyte in the air electrode with a controlled con- 5 tact between electrolyte, air and the electrocatalytic¬ ally active material.Figure 6 shows another special embodiment with separate air element and electrolyte elements disposed in the interior of the electrode. Figure 6 shows a view from10 above with standing perforated elements (34) and (35) , with electrode material (18) on the surface of the ele¬ ment (34) against the separator. These elements are thus inserted in the cathode fingers. The air is con¬ ducted towards the bottom of each element (34) . Alkali15 is flowing in the element (35) and is filling up this element almost completely. Other means according to Figure 1 are not shown in the drawing.Laboratory experiments with function models in prin¬ ciple designed as in Figure 3 and furnished with mate-20. rial as described above have shown that the electrode can be run at 150 mA/cm at 80 C, whereby cell voltage is reduced from 3,25 volt for corresponding convention¬ al cell to 2,40.volt. On the basis of these experi¬ ments a complete redesign of an existing chlor-alkali25 plant for diaphragm cells with a capacity' of 70,000 metric tons of chlorine per year has been carried out. Specific energy consumption is reduced with 24 %, the alkali concentration can be increased to 18 % and the capacity increased with 33 % without change of the30 electrical system.There is no difficulty for the artisan to get the same kind of improvement with other existing plants by meansUREAUO PI fa WiPO .Λ> of air electrodes according to the invention. There are furthermore no difficulties to new-design cells containing air electrodes according to the invention, whereby the operational and practical advantages be- come even more significant.What has been said above and described by examples and drawings shall not be considered a limitation of the scope of this invention. There are other possibilities within the scope of this invention for the artisan to make use of the spirit of this invention.<& O PI-PO | Claim 1Electrolytic cell for electrolysis of salt solutions with a positive electrode (1) in contact with an ano¬ lyte and a negative air electrode (3) comprising an at least partially hydrophobic electrocatalytically ac- 5 tive material (18) in contact with an alkaline catho¬ lyte whereby the anolyte and the catholyte are separat¬ ed by a separator (17) consisting of an asbestos dia¬ phragm or an cation permeable membrane disposed on a foraminous supporting structure (19) which forms a Q chamber (3) characterized in that the catalytically active material is disposed directly on to the separa¬ tor (17) or comprises an integrated part of the sepa¬ rator (17) and that the electrocatalytically active ma¬ terial (18) is permeable for the catholyte which is 5 produced in the electrochemical process in the electro¬ catalytically active material (18) so that the catho¬ lyte can penetrate into the chamber (3) which is fur¬ nished with means for discharge of the catholyte (6,33, 35) and means for supply (7,31) and discharge (8,32) of 0 air and means (21,27,28,34) for bringing the air in con¬ tact with the electrocatalytically active material.Claim 2Electrolytic cell according to Claim 1 characterized in that the chamber (3) consists of a cathode finger in a 5 known chlor/alkali cell of diaphragm type.Claim 3Electrolytic cell according to Claim 1 characterized in that the chamber (31 consists of a cathode finger in a known chlor/alkali cell of membrane type.0 Claim 4Electrolytic cell according to Claim 1 characterized in that a porous structure (29) carrying electrolyte is disposed in the chamber (3) .Claim 5Electrolytic cell according to Claim 1 characterized in that separate air elements (34) and electrolyte elements (35) are disposed in the chamber (3 ) . | LINDSTROEM AB OLLE; LINDSTROEM AB O | LINDSTROEM O |
WO-1979000692-A1 | 1,979,000,692 | WO | A1 | XX | 19,790,920 | 1,979 | 20,090,507 | new | D21C7 | B01J1 | B01J8, D21C7 | B01J 8/00F, D21C 7/08 | METHOD FOR TRANSFER OF MATERIALS TRANSPORTABLE BY LIQUIDS SUCH AS FIBRE MATERIALS | Method and device to transfer materials transportable with a liquid between various treatment stages, preferably from digesting (10-16) to a subsequent treatment (38) by means of circuits of circulating liquid. Material from one or several discontinuous treatment steps (10-16) are supplied to a subsequent continuous treatment step the material being fed into the continuous step (38) by displacement by means of a liquid portion (36) withdrawn from the said step. | Method for Transfer of Materials Transportable by Liquids Such as Fibre Materials.The present invention is concerned with a method of transfer of fibre material from one circuit of circulating liquid to another, where the fibre material is transported via circuit lines connected to a rotary feed valve. For coupling together various treatment vessels in processes for treatment of fibre materials it is known to use rotary feed valves for the transfer of the material . In this connection, the transfer is effected by the rotary feed valve having a rotor formed with one or several pockets which rotor is brought into various positions where connec¬ tion is established between circuit lines connected to the vessels.The object of the present invention is to make avail¬ able a method of the said kind which permits to couple several discontinuously operated treatment vessels with a continuous process so as to obtain the greatest possible yield from the process.This is achieved by endowing the method of the invention with the characteristic features stated in the appended claims.The invention whall hereinafter be described nearer in conjunction with the appended drawing, which illustrates an embodiment of a system in which the method of the invention is applied. The figure shows di agrammati cal ly an overall view of a digester house with a rotary feed valve attached therebehind for transfer of fibre material from the digesters to a detached washing vessel .In the figure, 10, 12, 14 and 16 denote treatment vessels for chips material , preferably digesters, into which the material is fed at the top in a hopper not labelled nearer and is discharged at the bottom upon finished treatment.OMPI^&?NAT1P5> The digesters 10-16 are of the so-called discontinuous type, i.e. the material is discharged in batches.According to the invention, the bases of the digesters are by lines 18, 20, respectively coupled together in pairs and by a common line 22 connected to an outlet of a rotary feed valve 24. This rotary feed valve has in the shown embo¬ diment six outlets as is described nearer in the Swedish- patent application 7609782-3. The line which is connected to the rotary feed valve 24 from the outlet line 22 is denoted 26. For -the sake of simplicity it is assumed in the subse¬ quent description that the -rotary feed valve 24 has one pock only which thus in the shown embodiment will take three positions of operation.In the first position, the pocket stands vertically and thus connects the line 26 from the digesters 10-16 with the line 28 which starts- from the diametrically opposed side of the rotary feed valve 24. As is disclosed in the aforecited patent application, the housing of the rotary feed valve is at the outlet side towards the line 28 provided with a screen, and when the pocket takes the aforestated first posi tion fibre material and cooking liquor will thus be fed from the line 26 into the pocket of the rotary feed valve 24, whereby the pocket is filled with fibre material and cooking liquor whereas the liquor content of the pocket from the third position - see more below - flows out -through the scre and into the line 28 which is equipped with a pump not de¬ noted more specifically. The liquor drawn off into the line 28 may partly be returned through lines 30, 32 to the digesters, and partly through a line 34 to further treatment as will be described more below.The rotary feed valve 24 which rotates in clockwise direction, will thereupon bring its pocket into a second position where a circuit line 36 from the detached washing vessel 38 located therebehind is connected with a circuit line 40 equipped with a pump not labelled nearer. In this position, possible remainder of cooking liquor is displaced-Bl3 EA (0- -PI WIPO4&ftNATlO § by washing liquor which is suppled -in the line 36, the cooking liquor flowing out into the line 40 which is connected to a line 42 leading to the line 34 which also contains cooking liquor. In the line 34, there is thus a flow of both cooking liquor from the discontinuous treat¬ ment and washing liquid from the continuous treatment.In the third position of the rotary feed valve, the line 40 is connected to a line 44 which is attached to the top of the washing vessel 38. Hereunder, the liquid ' supplied through the line 40 will displace fibre material and liquor in the rotary valve into the washing vessel 38 through the line 44, while simultaneously the pocket of the rotary valve 24 is filled with liquid from the continuous treatment stage. From the washing vessel 38 the fibre material is removed through a line 46 to further treatment, for example refining and/or treatment with oxygen gas, a treatment in 2 steps, which is described nearer in the Swedish patent application 7614754-5. Possible exhaust liquid from the further treatment can be recycled to the washing vessel 38 .via a line 48.That liquid which is not returned to the digesters 10-16 or the circulation of the rotary feed valve 24 is removed through the line 34 to evaporation, for example (not shown in more detail ). It may also, as in the shown embodiment, be fed into a receptacle 50 where possible residual gases are expelled and removed through a line 52, while tapped liquor from the receptacle 50 is withdrawn for evaporation, for example, through a line 54. It is evident from the above that it is possible by periodically in turn connecting the di sconti nuously operated digesters 10-16 to a detached washing vessel 38 via the rotary feed valve 24 to cause a discontinuous digester house to operate continuously behind the rotary feed valve, the fibre material thereunder pass ng a layer of liquid as is described in the Swedish patent 7408859-2. It is clear that the shown embodiment is an example only of realization of the invention and that the same can be varied within the scope of the appended claims without departing from the inventive idea.Especially shall be emphasized that the used rotary feed device can be formed out in various manners as also is shown and described in the patent application 7609782-3 cited above and that the rotary feed device is provided with required screen means for its function as also is evident from the named application and in the Swedish patents 7316616-7 and 7316617-5. | CLAIMS1. Method of transferring materials transportable with a liquid between various treatment stages, preferably from digesting to a subsequent treatment by means of circuits of circulating liquid, c h a r a c t e r i z e d in that material from one or several discontinuous treatment steps are supplied to subsequent continuous treatment steps by the material being fed into the continuous step by displace¬ ment by means of a liquid portion withdrawn from the- said step.2. Method • accordi ng to claim 1 , c h a r a c t e r i z e d in that the liquid accompanying the material from the dis¬ continuous treatment step is displaced by means of the liquid withdrawn from the continuous step before the material is supplied to the last-mentioned step.3. Method according to claim 1 or 2, c h a r a c t e r ¬ i z e d in that the material is a fibre material and that the continuous step is constituted by washing'of the fibre materi al . 4. Method according to any of the claims 1 - 3, c h a r a c t e r i z e d in that the treatment step con¬ sists of a subsequent digesting step, e.g. a sorption digesting step.5. Method according to any of the claims 1 - 4, c h a r a c t e r i z e d in that the extracted liquid is withdrawn from the discontinuous treatment and that the heat content of the extracted liquid is used for evaporation.6.' Method according to any of the claims 1 - 5, c h a r a c t e r i z e d in that the discontinuous treat- ment consists of digesting of fibre material and that the material is washed in the same treatment step prior to the transfer thereof to the continuous step. BURETTE __________■^?NATlO^>' 7. Device for carrying out the method according to any of the preceding claims for transfer of material transport¬ able with a liquid between various treatment steps comprisin circuits of circulating liquid disposed between the treatmen steps, c h a r a c t e r i z e d '.'n that the transfer is effected by means of a rotary feed valve (24) to which the circuits of circulating liquid are connected.8. Device according to claim 7, c h a r a c t e r i z e in that the rotary feed valve (24) is connected to two or more circuits of • ci rcul ating liquid, preferably three or four.9. Device accordi ng to claim 7 or 8, c h a r a c-t e r - i z e d in that one circuit of circulating liquid is connected to an accumulator, such as a flash tank (50) or the like for withdrawal of liquid from the discontinuous treatment step. | GLOEERSEN STIG; GLOEERSEN S | GLOEERSEN S |
WO-1979000697-A1 | 1,979,000,697 | WO | A1 | EN | 19,790,920 | 1,979 | 20,090,507 | new | F16K19 | null | B03D1, G05D23 | G05D 23/13B4D2B | A THERMOSTATIC MIXING VALVE | A thermostatic mixing valve is provided comprising a thermostat body (10) arranged in an elongated housing (1) and actuating an axially displaceable control member (8), which regulates the inlet areas for the warm and cold water The control member cooperates with a sleeve member (14) for regulating one of the inlet areas. The sleeve member is axially displaceable in the housing by the pressure from one of the liquids and this movement is limited by a stop ring (20). The end of the sleeve member (14) remote from the control member (8) cooperates with an axially displaceable closing sleeve (18) regulating the outlet area of the mixed water. Pressure means (21) actuated by an actuating lever (5) acts upon the closing sleeve by pivoting said lever about an axle (24) perpendicular to the housing. The mixed water temperature being regulated by rotating said lever, at which means being arranged to axially displaced the thermostat body (10). | A THERMOSTATIC MIXING VALVEBackground of the inventionThe present invention relates to a thermostatic mixing valve for two liquids, e.g. warm and cold water, and comprising an elongated housing provided with an outlet and an inlet for each of the liquids, an actuating member for adjusting the outflow and the temperature of the mixed liquid, a thermostat body sensing the temperature of the mixed liquid, said thermostat body being arranged to cooperate with a control member being axially displaceable in the housing for regulating the inlet areas of the liquids, a feed pipe extending axially in the housing being arranged for the first liquid, the end of the feed pipe remote from the inlet having a seat for the control member for regulating the inlet area of the first liguid, and a sleeve member, which with orϊe end forms a seat for the control member for regulating the inlet area of the second liquid flowing through a passage surrounding said feed pipe, and with its opposite end is arranged to cooperate with a closing sleeve, which is axially displaceable in the housing and which regulates the outlet area of the mixed liquid.A thermostatic mixing valve of a similar type is described in the US patent 3.685-728. This mixing valve is however provided with two separate actuating members, which have to be rotated separately for adjusting the outflow and the temperature resp. of the mixed liquid. Besides that a considerable liquid volume is housed between the regulation slots and the thermostat body, thus causing a long reaction time for the mixing valve at a change of pressure or temperature in the water pipe system. The outflow actuating member only closes the outlet,OMPI so that separate non-return valves have to be mounted in the inlet pipes in order to avoid a passage of liquid between the pipes when a negative pressure arises in any of them.In the German Offenlegungsschrift 2. 3.^59 is also described a thermostatic mixing valve with two separate actuating members,which have to be rotated separately for adjusting the outflow and the temperature resp. of the mixed liquid. Also in this nixing valve a consider¬ able liquid volume is housed between the regulation slots and the temperature responsive element and separate non-return valves have to be mounted in the feed pipes in order to avoid a passage of liquid between them.Summary of the inventionThe purpose of the invention is to provide a thermostatic mixing valve having a more compact and less space requiring design than the majority of the present available thermostatic mixing valves, which generally are big and bulky. The mixing valve shall be of one-grip type, i.e. the same actuating member shall be used both for temperature and outflow adjustment and the manipulation of the actuating member shall be simple. Besides the construction shall have a non-return valve function, so that there can be no passage between the inlet pipes when a negative pressure arises in one of the inlet pipes e.g. owing to a big discharge from the pipe or a break of the pipe. No separate non-return valves shall be needed in the inlet pipes.According to the invention a thermostatic mixing valve is provided, in which the above mentioned problems are solved and which is characterized thereby that said sleeve member is limitedly axially displaceable in the housing, by the pressure from the second liquid against a stop member, and with the actuating member in a closed position, the closing sleeve and the sleeve member on one hand and the sleeve member and the control member on the other hand being brought to sealingly contact each other and the control member against the action of a spring being brought to sea¬ lingly contact the seat of the feed pipe.Brief description of the drawingThe invention will now be further described with ■reference to the accompanying drawing showing an embodiment.The drawing is a vertical section through a mixing valve according to the invention.Description of a preferred embodimentThe thermostatic mixing valve comprises an elongated housing 1, at one end of which inlets 2 and 3 for warm and cold water resp. are arranged and at the central part of which an outlet 4 mixed tempered water is arranged. The outflow of the mixed water is controlled by an actuating lever 5 arranged at the end of the housing 1 remote from the inlets 2 and 3.One of the media, e.g. the warm water, flows from the inlet channel 2 through a centrally arranged feed pipe 6, which is springingly mounted in the axial direction. The end of the feed pipe 6 remote from the inlet 2 is arranged in a control member 8 and has .a seat 12, with which the control member 8 cooperates for regulating the delivery of warm water. The control member 8 is arranged just before a thermostat body 10 and is provided with a number of circularly placed openings 11 for the warm water and is arranged to control the delivery of cold water by increasing or decreasing a slot between the upper edge of the control member 8 and the lower end of a sleeve member 1*1 arranged above the control member 8 and surrounding the thermostat body 10. The control member 8 is by a spring 15 pressed upwards.The col water flows from the inlet channel 3 through a passage 16 surrounding the feed pipe 6 and through the slot between the upper edge of the control member 8 and the lower end of the sleeve member I . The warm water flows through the slot between the seat 12 and the control member 8 and through the openings 11 in the control member 8. The cold and warm water is mixed after the passage through the slot between the control member 8 and the sleeve member 1*1 and the openings 11 resp. The thermostat body 10 contacts the control member 8 and controls the position of the control member and thus the relation between the inflow areas for the warm and cold water.The mixed water flows around the thermostat body 10 and through a passage between the upper end of the sleeve member 14 and a closing sleeve 18 arranged above the sleeve member 11 and out through the outlet .The sleeve member can make a limited axial movement between the upper edge of the control member 8 and a stop collar 20 arranged outside the sleeve member l- 9 an outer shoulder 19 on the sleeve meber 14 being intended to abut said stop collar 20. The closing sleeve 18 is axially displaceable in the housing 1 and is. actuated by a pair of diametrically opposed arranged pistons 21, contacting the upper end of the closing sleeve 18.A yoke 23, which by means of screws 22 is connected to the actuating lever 5 _. is pivoted about an axle 2-\ arranged across the axial direction of the housing 1. The bottom part of the yoke 23 is curveshaped and by pivoting the yoke 23 about the axle 2-\ the curve3 actuates a pressure ring 25 arranged on the pistons 21' and 'presses this together with the pistons 21 , downwards. The pressure ring 25 is arranged about a circular inner portion of a top piece 30, which will be closer described below, said top piece 30 guiding the pressure ring 25, so that this only can make an axial movement.The piston 21 presses the closing sleeve 18 downwards against the sleeve member lM, which moves downwards and closes the cold water passage between the sleeve member l- and the control member 8. At the same time the control member 8 is pressed downwards against the action of the spring 15 and closes the warm water passage between the seat 12 and the control member 8. Since not only the outlet passage but also the inlet passages for the warm and cold water are closed when bringing the lever 5 to a closed position, there can be no passage between the inlet pipes, if a negative pressure would arise in any of them. Therefore separate non-return valves in the inlet pipes 2 and 3 are unnecessary.When opening the water supply in the mixing valve the lever 5 is pivoted upwards, at which the pressure from the curve shaped bottom part of the yoke upon theO Pl ^£ AT\0^ pressure ring 25 and the pistons 21 is discontinued. By the water pressure the sleeve member 14 is then lifted, so that the shoulder 19 contacts the lower edge 20a of the stop collar 20. The control member is by the spring 15 moved upwards a distance corres¬ ponding to the position of the thermostat body, which is determined by the setted temperature, at which warm and cold water can flow into the mixing chamber 17. The closing sleeve 18 is lifted by the water pressure, , since no pressure is longer exerted upon it from the pistons 21, and- the passage out through the outlet 4 is free. The maximum outflow is determined by the position of the stop collar 20, which is provided with external threads and screwed into an outer sleeve 26 extending all the way down to the inlets 2 and 3. The cold water passage lβ is defined by the outer sleeve26 and'the feed pipe 6.The thermostat body 10 contacts with one end surface the control member 8 and its opposite end is received in a bush 27, which by means of a partition wall 28 prevents the thermostat body to move upwards. The bush27 is arranged inside the closing sleeve 18 and is axially displaceable in relation to this..The bush 27 is at its upper part provided with internal threads for threaded engagement with the lower part of a spindle 29. The upper part of the bush 27 is received in a central through opening 30 in the top piece 30, which also is provided with two diametrically opposed holes for the pistons 4. The bush 27 and the top piece 0 are unrotatably connected with each other, the bush 27 having a non-circular cross-section corres¬ ponding to a non-circular cross-section of the top piece 30. Thus an axial displacement between the bush 27 and the top piece 30 can be performed. The top piece 30 is with its lower part screwed into the outer sleeve 26 and has an upper bowl-shaped- portion, in which the pressure ring 25 and the yoke ' 23 are received. The spindle 29 projects above the opening in the top piece 30 and is on this projecting portion provided with external axial flutes corres¬ ponding to internal flutes of an opening extending across the pivot axle 24. Thus the spindle 29 is unrotatably connected with the pivot axle 24 and with the yoke 23.When the actuating lever 5 is rotated about a vertical axle the rotational movement is transferred to the spindle 29, which is screwed into or out of the bush 27 thus displacing this downwards or upwards resp., since an axial displacement of the spindle 29 is prevented. The spindle 29 has above its' fluted portion a threaded portion, on which a nut 31 is screwed, which keeps the pivot axle 24 in place. A stop lug 3 unrotatably connected with the spindle 29 limits the rotational movement of the spindle.A check screw 33 is threaded into the spindle 29, said check screw 33 with its lower end projecting somewhat out of the spindle 29 and limiting the upward movement of the bush 27 by abutting the partition wall 28 of the bush 27. -.The position of the check screw 33 is adjustable by a screw driver slot at its upper end and in this way a desired maximum temperature can be set, which cannot be exceeded.When setting a desired temperature the lever 5 is rotated about a vertical axle and brings with the yoke 23 and the spindle 29, which is screwed into or out of the bush 27 thus forcing the bush 27 upwards or downwards resp. The bush 27 actuates the thermostat body 10, which cooperates with the control member 8 and thus provides a changed relation between the inlet areas for warm and cold water.If the temperature of the mixed water exceeds the set temperature the thermostat body 10 is expanded in the axial direction, thereby forcing the control member 8 downwards, at which the inlet area for the cold water is increased and the inlet area of the warm water is decreased, and the desired temperature is again obtained. It is appreciated that the reaction time is very short, since the regulation slots for both the warm and cold water are located very close to the thermostat body 10, at which the volume between the sensing surface of the thermostat body 10 and the regulation slots is small. This volume is adapted for the maximum flow.If the temperature of the mixed water decreases below the set temperature the thermostat body 10 is contracted in the axial direction, at which the control member 8 by the spring 15 is pressed upwards thus increasing the inlet area of the warm water and decreasing the inlet area of the cold water until the desired tempera- ture is obtained.It should be noted that when the temperature of the warm water is changed the supply of warm and cold water is simultaneously changed. The temperature compensation for the mixing valve, i.e. change of temperature when the warm water temperature is changed, is about 0,25°C/10°C change of the warm water temperature. The corresponding figure for other available mixing valves is about 1,8-4°C/10°C.The invention is of course not limited to the embodiment shown and described but can be varied within the scope of the claims . | C L A I S1. A thermostatic mixing valve for two liquids, e.g. warm and cold water, and comprising an elongated housing (1) provided with an outlet (4) and an inlet (2,3) for each of the liquids, an actuating member(5) for adjusting the outflow and the temperature of the mixed liquid, a thermostat body (10) sensing the temperature of the mixed liquid, said thermostat body being arranged to cooperate with a control member (8) being axially displaceable in the housing (1) for regulating the inlet areas of the liquids, a feed pipe(6) extending axially in the housing being arranged for the first liquid, the end of the feed pipe remote from the inlet having a seat (12) for the control member for regulating the inlet area of the first liquid, and a sleeve member (14), which with one end forms a seat for the control member for regulating the inlet area of the second liquid flowing through a passage (16) surrounding said feed pipe (6) and with its opposite end is arranged to cooperate with a closing sleeve (18), which is axially displaceable in the housing and which regulates the outlet area of the mixed liquid, c h a r a c t e r i z e d i n, that said- sleeve member (14) is limitedly axially displaceable in. the housing (1) by the pressure from the second liquid against a stop member (20), and with the actuating member (5) in a closed position the closing sleeve (18) and the sleeve member (14) on one hand and the sleeve member and the control member (8) on the other hand being brought to sealingly contact each other and the control member against the action of a spring (15) being brought to sealingly contact the seat (12) of the feed pipe (6).2. A mixing valve as claimed in claim 1, c h a r a c t e r i z e d i n , that the position ofOϋ said stop member (20) is adjustable for regulating the maximum outflow.3. A mixing valve as claimed in claim 1 or 2, c h a r a c t e r i z e d i n, that pressure means (21) axially displaceable in the housing are arranged to act upon the closing sleeve (18), said pressure means cooperating with the actuating member (5) and are actuated by this by pivoting said actuating member ♦ about an axle (24) extending across the axial direction ; of the housing.4. A mixing valve as claimed in claim 3, c h a r a c t e r i z e d i n, that said pressure means comprises a pair of pistons (21) arranged diametrically opposed in the housing (1), a pressure ring (25) being arranged on the pistons, a voke (23) which is fixed to the actuating member (5) is provided with a curve shaped portion (34) actuating said pressure ring (25) when pivoting the actuating member about the axle (24).5. A mixing valve as claimed in claim 4, c h a r a c t e r i z e d i , that the pressure ring (25) is arranged about a circular inner portion of a top piece (30) guiding the movement of the pressure ring.6. A mixing valve as claimed in any of the preceding claims, c h a r a c t e r i z e d i , that for setting the temperature a bush (27) is arranged, in which the upper end of the thermostat body (10) is received and which limits the upward movement of the thermostat body, said- bush (27) being axially and unrotatably displaceable in the closing valve (18) and at its upper part being provided with internal threads, for threaded engagement with a spindle (29), which is unrotatably connected with the actuating member (5).7. A mixing valve as claimed in claim 6,.c h a r a c t e r i z e d i n, that a check screw (33) is arranged in the spindle (29), the lower end of the check screw projecting below the spindle and limits the upward movement of the bush (27) and thus determines the maximum temperature of the mixed water which can be set, the position of the check screw (33) in. the spindle being adjustable.8. A mixing valve as claimed in any of the preceding claims, c h a r a c t e r i z e d i n, that the control member (8), the sleeve member (14), the closing sleeve (18), the bush (27), the spindle (29) and the feed passages (6,16) for the two liquids are arranged about a common central axis through the housing (1). | RIIS V; VAERGAARDA ARMATURFAB AB; VARGARDA ARMATURFAB AB | RIIS V |
WO-1979000701-A1 | 1,979,000,701 | WO | A1 | EN | 19,790,920 | 1,979 | 20,090,507 | new | C07C143 | C09K7, C07C143 | B01F17, C07C67, C07C301, C07C303, C07C309, C09K8, C11D1, E21B43 | C07C 143/90, C09K 8/584 | IMPROVED PETROLEUM SULFONATES | Petroleum sulfonates yielding improved results in enhanced oil recover processes are comprised of a reaction product obtained from a mixture of a major proportion of a petroleum oil feed stock, such as a crude or a portion thereof, and a minor proportion of an additive, such as an oxygenated hydrocarbon, i.e., an oxo-alcohol or the like, reacted with SO<u3>u under sulfonation conditions, mixed with about 0.50 to 20% (by reaction mixture weight) of water at the temperature in the range of about 50` to 150` C. for a relatively brief period of time and then neutralizing the resultant material with a base, such as NaOH. The neutralized petroleum sulfonated material thus obtained, which may or may not be extracted to remove unsulfonated organic material or salts, is then formulated into a slug for injection into an oil field for enhanced oil recovery. | Improved Petroleum Sulfonates Field of the InventionThe invention relates to enhanced oil recovery and' somewhat more particularly to improved petroleum sulfonate - products useful in enhanced oil recovery and a method of producing and utilizing such sulfonate products. Prior ArtThe petroleum industry has recognized for many years that only a small fraction of the original petroleum (i.e.,- crude oil) within a given reservoir is expelled by natural mechanisms. Further, it is recognized that con¬ ventional methods of supplementing natural recovery are relatively inefficient and economically unattractive. Typically, a reservoir may retain as much as half to two-thirds of the original petroleum therein, even after the application of currently available secondary recovery techniques, such as waterflooding. Conventionally, water- flooding invloves injecting a.t least water, through one or more input wells to drive petroleum from the reservoir for- mation to a geometrically offset production well. Further improvements in oil recovery can be attained with certain enhanced oil recovery techniques, wherein oil recovery sys¬ tems are formulated into micellar systems' with surface- active agent, injected into input wells and driven or pushed through the reservoir formation to provide additional amounts of petroleum.Surface-active agents or surfactants typically utilized for improving the efficiency of enhanced petroleum recovery methods must not only be economical but must also be compatible with the reservoir environment. Typically, such an environment includes localized higher temperatures, higher salt and/or polyvalent ion concentrations, adsorptive petroleum-bearing or petroleum-loving surfaces, minute pore spaces, etc., all of which potentially affect the surfactant and the petroleum recovery obtained by the use of such a surfactant. For example, petroleum retained within a reservoir after natural and/or secondary recovery processes are terminated, may be in the form of discontinuous globules or discrete droplets which are trapped within the pore spaces of the reservoir, along with connate, brackish or the like water at some particular temperature. Because of the normal interfacial tension between the reservoir* petroleum and water is high, such discrete petroleum droplet are unable to sufficiently deform to pass through the narrow constrictions of the individual pore channels. Similarly, reservoir petroleum appears to have a greater affinity to the petroleum-bearing surfaces, i.e., rocks, sand, etc. than does the water so that any applied force merely pushes the water to an area of less pressure, i.e., a production well, while leaving the petroleum in place on the reservoir sur¬ faces. When surface-active agents are formulated into an oil recovery system and injected into a reservoir, they function in numerous ways, one of which is to lower the interfacial tension between the flowable materials within a reservoir and permit the petroleum droplets to deform and flow with the surfactants in the flood water system toward a production well. It is generally -conceded that the interfacial tension between the flood water system and the reservoir petroleum must be reduced to an order of less than about 0.1 dynes/cm for effective recovery. Surface-active agents must also be stable in the presence of higher temperatures encountered in at least some reservoirs and be stable in the presence of highly brackish water or polyvalen ions present in certain reservoirs and yet be able to wash the reservoir surfaces so as to release all or almost all petroleum adsorbed therein so as to achieve an economical and effective recovery process.-βϋiiiiAUO Pl e - -,- WlP-° One of the more promising surface-active agents used in enhanced oil recovery are the petroleum sulfonates. Gen¬ erally, these agents comprise thet reaction products of a petroleum feed stock and a select material yielding a sulfo 5 radical to the petroleum feed stock, i.e., oleum or gaseous or liquid SO-. Depending on many variables, such as the nature of the initial petroleum feed stock, the nature of the sulfo radical yielding material, the sulfonation reaction conditions selected, etc. , the resulting petroleum sulfonates10 may be formulated with a wide variety of properties making them useful in enhanced oil recovery processes as well as in other fields of use, such as industrial surfactants, as blending agents for lubricating oils, as agricultural emulsifiers, dispersants, etc. ' However, economic and15- . efficient production of petroleum sulfonates is difficult and the art is replete with various suggestions, for achiev¬ ing a more or less universally acceptable reaction process, even though most, if not all of the prior art processes leave much to be desired in terms of product control,20. economic availability of feed stocks, field of optimum surface-active properties, etc. In our earlier referenced disclosures, we teach a' method of sulfonating petroleum oil feed stocks which provides a high yield of petroleum sulfonates and a method of formulating such sulfonates into25 enhanced oil recovery systems.As a continuous part of our work in this field, we have conducted numerous core flood experiments on various crudes with various slugs containing various petroleum sulfonates in an effort to obtain optimum petroleum recovery30 under various reservoir conditions. As a part of these studies, we noticed that certain petroleum sulfonates tend to yield good petroleum recovery at certain conditions but yield different results at other conditions. We undertook to investigate the reason for such divergent results.In enhanced oil recovery processes r the economics of a select recovery process and/or 'a surface-active agent, • » such as a petroleum sulfonate, are extremely stringent. Suggestions have been made in the art, that in order to minimize shipping and production costs, to either produce the petroleum sulfonate in-situ, as by injecting select* reactive material directly into a reservoir, allowing a reaction to take place therein and then flooding the resulting reservoir with a water system to intermix with whatever reaction products are formed therein or to produce the petroleum sulfonates at the reservoir site and then forumulate the resultant reaction product into a desired sl composition and inject such slug into the reservoir. How- ever, neither of these suggestions have proven satisfactory sincewith the first suggestion, no control of reaction conditions or reaction products is available and with the second, insufficient quality control results, particularly since initial feed stocks, reaction conditions, etc. may vary from site to site. Further, the reaction products obtained from a typical petroleum sulfonation reaction tend to be non-homogeneous and unstable over a period of time so that the properties of such products vary. Typically, a petroleum sulfonation acidic reaction product mixture tends to separate into at least two phases, comprised of sulfonated sulfonatable components, non-sulfonated but sulfonatable components and non-sulfonatable components. Upon standing, such acidic reaction product mixtures tend to change in composition and properties, apparently because some residual S03 or degenerate specie thereof is present within the reaction products and gradually reacts with sulfonatable components therein, although other theories or explanations for this apparent instability may be-BUREA0MP1 equally valid. Nevertheless, such non-homogeneity and instability limits the extent of usefulness for such reaction products and often necessitates fμrther processing before a final product is attained which is suitable for various 5 industrial and commercial purposes, such as enhanced oil recovery in diverse reservoir environments. U.S. Patent No. 2,928,867 suggest that stable alkaryl sulfonates (i.e., dodecylbenzene sulfonates) may be .pre¬ pared by sulfonating pure or relatively pure dodecylbenzene 10 or postdodecylbenzene, (a mixture of mono- and di-alkylbenzenes) with SO., under sulfonation conditions, cooling the resulting alkaryl sulfonic acid, adding a small amount of water to the cooled sulfonic acid over a relatively brief period of time and then neutralizing the resultant sulfonic acid with 15 caustic to obtain a pH-stable alkaryl sulfonate useful in detergent formulations. However, this prior art patent is silent as to enhanced oil recovery techniques or any surface-active agents useful in such oil recovery processes. The invention provides an economical and novel 20 composition of matter which exhibits improved and stable properties useful in enhanced oil or petroleum recovery, a method of producing such composition of matter and a method of enhanced petroleum recovery utilizing such composition of matter. 25 In accordance with the principles of the invention, a select petroleum oil feed stock, such as a topped crude, a heavy vacuum gas oil or some other partially refined or whole crude is admixed with a small amount (i.e., about 0.5% to about 15% by weight of petroleum oil feed stock) of 3Q an additive, such as comprised of an unsulfontable organic radical portion having an average molecular weight range extending from about 55 to 6000, having a boiling point in the range of about 100°C. to 260°C. and a preponderance of such radicals each having attached thereto at least one proton replaceable by a sulfo group and at least one moiety selected from the group consisting of an aromatic nucleus,' an olefinic carbon pair and an oxygen atom directly bonded to a carbon atom by at least one bond (i.e., a C, to C.g alcohol material, such as an oxo alcohol still bottom) and then the resultant additive-feed stock mixture is su *ifonate with S03 under sulfonation reaction conditions. A small amount (i.e.., about 0.5 to 20% by weight of the resultant crude acidic reaction mixture) of water is then added to the resultant sulfonation reaction mixture and the sulfonation reaction mixture-water mixture is held at an elevated temperature (i.e., in the range of about 50° to 150° C.) for a relatively brief period of time (i.e., ranging from about 2 to 60 minutes) and then neutralized with a base. The resultant petroleum sulfonate-product, which may first be subjected to an extraction process, if desired, is then formulated into a micellar system, such as a microemulsion or the like system and injected into select petroleum reservoirs for enhanced oil recovery.By practicing the principles of the invention, one is able to attain enhanced oil recovery yields on the order of 60% to 90% or more, as compared to typically lower yields obtained with similar petroleum sulfonates which have been non-water treated before neutralization by conventional prior art techniques.The novel stabilized petroleum sulfonate products obtained by the practice of the invention comprise, on a 100 organic weight percent total weight basis a) from about 2 to 90 weight percent of substan¬ tially non-sulfonated hydrocarbon material; b) from about 0 to 50 weight percent of non- sulfonated but sulfonatable hydrocarbon material;' URtATO PI 7λf_ 1P0 - RNA™θS c) from about 5 to 98 weight percent of monosul- fonated hydrocarbon material? d) from about 0 to 50 weight percent of poly- sulfonated hydrocarbon material; and e) from about 0.5 to 15 weight percent of an additive. Accordingly, a primary object of the present invention is the provision of a stabilized homogeneous petroleum sulfonate product which comprises sulfonated and non- sulfonated components, a method of attaining such sulfonate products and a method of enhanced subterranean oil recovery utilizing such sulfonated products.Other and further objects, aims, purposes, advantages, uses and the like of the present invention will be apparent to those skilled in the art from the following description of preferred embodiments thereof, although variations and modifications may be effected- ithout departing from the spirit and scope of the novel concepts of the invention. Sulfonation During the course of the instant disclosure, it is to be understood and intended that the terms sulfonation , sulfonated or equivalent, apply herein to any reaction which results in the substitution of a sulfo radical in a molecule of an initial starting material. Thus, it will be understood that these terms also encompass any sulfation reactions which may also be occurring, for example, with a petroleum oil feed stock containing a component having one or more hydroxy radicals per molecule. The hydroxy group of such component may or may not tend to react with sulfur trioxide. Thus, for example, such component-types as naphthols or substituted naphthols, are apparently characteristically sulfonated through the ring radical rather than through the hydroxy radical in the practice ofOMPI^SNATIO^' the method of this invention. Similarly, the petroleum oil feed stock components capable of reacting with a sulfonatin agent, such as sulfur trioxide, are sometimes referred to a sulfonatable or sulfatable components, and, more generally, as sulfonatable or reactable components, and it will be understood that these terms all refer to petroleum oil components capable of reaction with a sulfonating agent. Petroleum Oil Feed StockThe petroleum oil feed stock used as starting materia in the practice of this invention can be any petroleum oil feed stock known in the art. For example, gas oils, topped crude oils, heavy vacuum gas oils, lubricating oils, selected fractions recovered from lube oil treating process selected fractions from paraffinic, naphthenic, whole crude lightly distilled crudes, mixed base crudes or mixtures thereof. As workers in 'the art are .well aware, extensive characterizations of petroleum oil stocks and/or crudes are available, for example, see Evaluation of World's Importan Crudes (The Petroleum Publishing Co.), 1973, which contain a compilation of various characteristics of geographically diverse crude oils, while C. J. Thompson et al, Hydrocarbo Processing - Analyzing Heavy Ends of Crude , September 1973 pages 123-130, characterizes the higher boiling fractions of five different crude oils of different chemical composi- tion and geological origin. Similarly, the characteristics of various fractions or products obtained in refining petroleum or crude oil is known, for example, see W. L. Nelson, Petroleum Refining Engineering , 4th Ed. (McGraw- Hill Book Co.). However, for purposes of the invention, such extensive characterizations are generally not required. Any available petroleum oil feed stock which contains sulfonatable components therein may be used in the practice of this invention. Thus, the petroleum oil feed stocks may be any natural material, or blend of natural and syn¬ thetic petroleum oils, including whole or partially refined natural crude oils, or portions thereof, such as synthetic oil stocks and mixtures of any of the above.. The petroleum. 5 oil feed stocks may also contain waxes or may be partially « or completely dewaxed petroleum oils. Another petroleum feed stock which may be employed as a starting material is a raffinate obtained in solvent refining of petroleum frac¬ tions. One may carry out such refining or extraction with 0 various cyclic solvents, phenols, methyl ethyl ketones, liquid S02, etc. Both the resultant raffinate and the stripped extract may be subjected to sulfonation in accor¬ dance with the principles of the invention.In many instances, petroleum oil feed stocks use- 5 ful as starting materials in the invention exhibit -20° to 1400°F. (-29° to 760βC.) corrected atmospheric boiling range (although higher and lower boiling feed stocks may also be used) and have an API gravity ranging between about 5 to 60° at 60°F. (15.6°C). Preferred petroleum oil feed Q stocks also include crudes which have aromatic portions with molecular weights in the general range of about 200 through about 1000 and more preferably in the range of about 250 through about 800, while the most preferred range is about 250 through 500. The amount of aromatic compounds 5 or portions within a crude oil useful in the practice of this •invention is generally about 10% to 95% (although purified synthetic feed stocks having 98% or more aromatic compounds therein are also useful in the practice of the invention), and more preferably about 20 to 80%, and most Q preferably about 25 to 75%, by weight of aromatics, as de¬ fined in the American Petroleum Institute Project 60 Reports 4-7 under Characterization of Heavy Ends of Petroleum . Preferred petroleum oil feed stocks include - 10 -Texas crude oil, Libyan crude oil, Louisiana crude oil, California crude oil, Wyoming crude oil, Michigan crude oil Illinois crude oil, Ohio crude oil, Oklahoma crude oil, Mississippi crude oil, Canadian crude oil, as well as vario other geographically diverse crude oils. Preferred petro- leum oil feed stocks also include crude oils having aromati portions thereof which have a proton ratio of aliphatic radicals or compounds to aromatic radicals or compounds of approximately 3 through 20 and more preferably about 4 thro 18. Lightly distilled or topped crude oils, for example, where at least a portion of the hydrocarbons boiling below about 680°F. C320βC.) have been removed, may also be used as the feed stock. Of course, mixtures of various crude oils, or portions thereof, as well as blends may also be used as feed stocks in the practice of the invention.The petroleum oil feed stocks may also be a material which is derived by subjecting a petroleum crude to one or more of the following general types of refinery processes, including thermal or catalytic processes: topping, reforming, cracking, alkylation, isomerization, polymerization, desulfurization, hydrogenation, dehydro- genation, distillation (including atmospheric and vacuum) , sweetening, etc. Petroleum oils containing substantial amounts of aromatic compounds, naphthenic compounds and/or unsaturated compounds are also useful in the practice of the invention. Likewise, straight run or refinery naphtha streams may be sulfonated in accordance with the principles of the invention, although higher boiling fraction feed stocks are generally preferred. Also, petroleum oil stocks can be prepared by admixing together two or more different partially refined petroleum oils including crude oils so as to obtain, for example, some particular desired starting petroleum oil stock having a particular content of sul-O PITty- W1P0 fonatable components and/or having a particular boiling range.A wide variety of sulfonatable or reactable com- , pounds or materials are characteristically present in vari- ous petroleum oil feed stocks, including aromatics, olefins, as well as alicyclic and aliphatic hydrocarbon compounds (and it is recognised that some alicyclic and aliphatic paraffins may be less reactable than some other compounds) , etc. , all of which various classes of materials are sulfonat- able to variable degrees in accordance with the principles of the invention.In order to estimate the amount of reactable or sulfonatable components in a selected petroleum oil feed stock, one may resort to a number of known procedures. For example, one may utilize an ASTM process, such as ASTM Test No. D848-62, which generally comprises feeding a petroleum oil feed stock with an -excess of fuming (20%) oleum and then measuring the remaining layer' of oil. A number of other methods, for example, a silica gel chromatography method, may be used in place of the exemplary method set forth above to determine a more or less approximate content of sulfonatable components in any petroleum oil feed stock (ASTM Test No. D2007) .In summary, a petroleum oil stock useful as a starting material in the practice of the present invention is characterized by:(A) having an API gravity ranging from about 5° to 60° and somewhat more preferably from about 10° to 40° at 60°F. (15.6°C.) ;(B) having a boiling point in the range of about -20° to 1400°F.. (-29° to 760°C.) and somewhat more preferably from about 500° to 1100°F. (260° to 600°C), corrected atmospheric; and (C) containing from about 10 to 95 weight percent (100 weight percent total stock basis) of sulfonatable components. Preferred starting petroleum oil feed stocks may contain intially not more than about 3 to 10 weight percent (100 weight percent total stock basis) of com¬ bined elements selected from the group consisting of oxygen, sulfur and nitrogen and generally molecules con¬ taining such elements are not sulfonatable to any appre¬ ciable extent. Those skilled in the art will appreciate that petroleum oil feed stocks may also commonly contain quantities of water and of hydrocarbon molecules having incorporated thereinto atoms of oxygen, sulfur and ni¬ trogen. In general, for purposes of the present invention it is not necessary to eliminate such combined elements from a starting petroleum oil feed stock for use in the present invention, but it is preferred that a starting petroleum oil feed stock contain not more than the above indicated quantities of these elements. Additives In general, additives employed in this invention are organic species characterized as organic radicals, a preponderance of which have attached thereto at least one proton replaceable by a sulfo group and at least one moiety selected from the group consisting of an aromatic nucleus, an olefinic carbon pair, and an oxygen atom directly bonded to a carbon atom by at least one bond. Typically and preferably, a given additive specie and/or molecule may have attached thereto a plurality of such - 13protons and moieties and a mixture of different type additives may also be utilized. The presence of one or more of the additives in a liquid petroleum feed stock being subjected to a sulfonation reaction by this in- vention appears primarily to promote the compatibility of sulfonated oil components with unsulfonated or unsul- fonatable oil components under reaction conditions,, though there is no intent herein to be bound by theories or appearances. An apparent major function of an additive within' the reaction system is to promote compatibility of reactants and reaction products under reaction condi¬ tions (and it is to be noted that these additives, after sulfonation, have other functions in ultimate products of this invention) . The additives during the sulfonation reaction seem to maintain an adequate solution or disper¬ sion of petroleum oil components (reactants and reaction products) in such a way that adequate heat exchange and/ or temperature control is effected between the sulfur trioxide or gas phase, the petroleum oil feed stock additive mixture or liquid phase and the heat exchange surfaces and/or reactor walls under the reaction condi¬ tions. Thus, the additives may be designated compati¬ bility promoting additives and allow one to achieve an effective means of process and product control. The absence of one or more additive in an oil feed stock sulfonation process appears to result in gross component separation, lack of liquid compatibility, lack of uniform heat control, excassive polysulfonation, excessive sludge formation and an inability to maintain process control or reaction stability (although it is to be noted that certain low viscosity starting petroleum feed stocks and/or petroleum feed stocks mixed with solvents or diluents therefor, such as ethylene dichloride, trichloroethane, nitrobenzene, nitropentane, and the like may be at least partially sulfonated without the presence of a significant amount of additives). Nevertheless, improved reaction products and reaction control apparent- ly can be attained when at least some additives are present with the oil feed stock in the reaction zone. The additives also appear to reduce undesired oxidation of the oil feed stock., so that substantially less of, for example, reactant gaseous sulfur■trioxide is lost via reduction to sulfur dioxide. For example, in prior art processes of sulfonating petroleum oil feed stocks with gaseous or liquid SO,, as much as about 50% of the SO, is reduced to S02, depending on the degree of SO, input, oil type, etc. However, by following the princi- pies of the invention, the loss of SO, is kept relatively low.Also, the common prior art over-reaction of sulfonatable components in oil feed stock is apparently reduced by the presence of the additives so that less polysulfonates may be produced in the reaction products if so desired. In other words, the additives apparently provide an operator with a means for achieving- some de¬ sired and substantially controlled ratio of monosulfonates to polysulfonates and equivalent weight distribution. For example, when a petroleum oil feed stock is divided into two portions for sulfonation, one of which is ad¬ mixed with an additive and the other portion is sulfonated as such without an additive, and both such portions sul¬ fonated under otherwise identical conditions and SO- treat levels, the products recovered in each instance have different equivalent weights and monosulfonate con¬ tents. The equivalent weight, (£C ) , as determined by a silica gel analysis (ASTM Test No. D855-56) is almost invariably higher for the sulfonation product recovered from the portion containing the admixture of additive and oil feed stock. 'The monosulfonate con- : tent, as determined by a paratoluidine analysis is also generally higher for the product recovered from the portion containing the admixture of additive and oil feed stock. These results demonstrate that the addition of an* additive to a petroleum oil feed stock undergoing sul¬ fonation reduces the amounts of polysulfonates or low C(Jϋ monosulfonate by-products (which are generally un¬ desirable) , as compared to prior art sulfonation of petroleum oil feed stocks without additions of additives. When an additive is present, the mono to disulfonate content in the active portion of the resultant product is generally in the 3:1 to 50:1 ratio whereas without an additive, the ratio of mono to disulfonate ranges up to about 1:1. At optimum SO, treat levels, sulfonation of an additive containing petroleum oil feed stock yields a product which is superior to a reaction product from a non-additive containing oil feed stock (i.e., a mahogany sulfonate) . This superiority is shown by the higher €.00 and greater monosulfonate content in sulfonation products of an additive containing petroleum oil feed stock. At higher than optimum SO, treat levels, over- sulfonation occurs and a lower £CO and lower mono¬ sulfonate content results. -Accordingly, by a judicious selection of the amount of additive utilized and the SO, treat level utilized, an operator readily controls the amount of mono and polysulfonate in the ultimate sul- fonation product.The additives also tend to promote compatibility, solubilization, dispersion and/or coupling of the reaction products (sulfonated petroleum) with unreacted starting petroleum oil feed stock to yield a homogeneous' or substantially homogeneous solution, dispersion and/or micellar solution, under sulfonation reaction conditions..' While the exact chemical and/or physical functions of the additive described herein may not be fully understood, it is hypothesized that the additives somehow promote com¬ patibility between unsulfonatable and/or unsulfonated components in admixture with an oil feed stock and the sulfonated components thereof. Observations taken during a film.sulfonation reaction between unadulterated petro¬ leum oil feed stocks and diluted gaseous sulfur trioxide lead to tentative conclusions that, as the sulfonatable components in the petroleum oil feed stocks become sul¬ fonated, such sulfonated components tend to form an outer layer or boundary on the film or in a reaction mixture. At such outer location, the sulfonated components may be exposed to further sulfur trioxide and may tend to over¬ react, causing charring, polysulfonate formation, etc. Similar observations taken during a sulfonation reaction between a petroleum oil feed stock-additive mixture and diluted gaseous sulfur trioxide do not show any such outer layer, and it appears that the resulting sulfonated components remain within the film as a homogeneous mix¬ ture, a dispersion, or possibly an emulsion with the non- sulfonated components in the film, so that overreaction is substantially prevented or minimized, and the amount of polysulfonates in the ultimate product is characteristic¬ ally materially reduced.Of course, other explanations may be advanced as to the reason why the additives described herein promote increased yield of sulfonates during sulfona¬ tion of petroleum oil feed stocks and there is no intent to be bound herein by any theory or possible explanations.-BJj RtATOM I r- WIPO As explained hereinabove, the additives also appear to enhance the attainment of a desired equivalent weight (£,CU ). range within the reaction product, which may be a mixture of various sulfonated and non-sulfonated compounds. The equivalent weight or of a sulfonate may be defined in the case of a salt as the combining weight thereof, i.e., the weight of sulfonate contai »ning one gram atom of a cation (generally ammonium or sodium) . For monosulfonates, the CC or combining weight is iden- tical with the molecular weight. In the case of disul- fonates, the combining weight is just one-half of the molecular weight but is nevertheless referred to as the equivalent weight thereof. In other words, the ξ of petroleum sulfonate or of the reaction products may be defined as the sulfonate molecular weight divided by the average number of sulfonate groups per molecule. The U indicates the relative amount of monosulfonation and polysulfonation, i.e. , the & becomes lower as the polysulfonation increases. The additives of the invention may be used as mixtures with suitable solvents or as mixtures among themselves. The additives themselves may undergo sul¬ fonation or sulfation reactions and may result in a complex mixture with the other reaction products and may be usable as such or may be further processed before use thereof. Additives useful in the practice of this invention are chosen from a wide variety of chemicals, identified hereinafter, and which have the ability to effectuate at least one or more of the above dis- cussed functions, such as promoting compatibility between sulfonated and unsulfonated and/or non-sulfonated oil feed stock components, decreasing and controlling viscosity during the sulfonation reaction, providing an adequate solution or dispersion of oil components (reactants and reaction products) in such a way that adequate or stabilized heat control and/or heat exchange is effec¬ ted and thus providing a means of maintaining process control. Further functions of additives include: providing an improved sulfonation reaction; substantially increase the yield of petroleum sulfonates over the.here¬ tofore available processes; providing a control so that almost any desired ratio of monosulfonates to polysul- fonates can be achieved with low amounts of undesirable salts; promoting the formation of adequate solutions/ dispersions of reactants and reaction products under sulfonation and ultimate use (for example, in soluble, dispersion or micellar systems) conditions; providing a substantially theoretical yield of sulfonates from various oil feed stocks; providing improved operability in various continuous, batch, quasi-batch or quasi- continuous processes in various diverse apparatuses; re¬ ducing undesirable oxidation of the oil feed stock; provide a more efficient utilization of SO, so as to produce higher conversion to sulfonate activities as compared to reactions without additives; providing a means of reducing or controlling viscosity of the sul¬ fonation mixture; provide a means of effecting improved continuous sulfonation processes; reducing charring, oxidation and polysulfonation in the sulfonation reaction; reducing or preventing plugging or otherwise damaging reaction systems and components; being useful with an extremely wide variety of petroleum oil feed stocks; being adaptable to a wide variety of sulfonation processes and apparatuses; providing a means of achieving product composition control, i.e., by varying as desired the ratio of mono to polysulfonate and minimizing sludgeOMPI ft- W1PC) formation; enhancing post-reactor digestion by reacting with any residual SO, or H-SO. present in initial reaction t products; providing an option to eliminating the need for extraction; providing a means for reacting SO, with oil feed stock at lower temperatures in comparison to reactions without additives; contributing to phase separation of acid from unreacted oil in the reaction products; (capable of being hydrolyzed, if sulfated, so as to be removable from the reaction products id desired) ; capable of being functional within an enhanced oil recovery system, particularly when the sulfonation reaction products are first water-treated prior to neutralization or formulation into an oil recovery system providing a basis for solvent-free sulfonation; pro¬ viding petroleum sulfonates which xhibit an enhanced oil recovery property; etc. Additive systems also apparently provide an important means of maximizing both high monosul- fonation and commensurate sulfonate equivalent weight.Generally, these additives comprise relatively high boiling organic compounds including unsaturated aliphatic hydrocarbons, substituted and unsubstituted aromatics, olefins, oxygen-containing compounds, esters (especially high boiling esters), ethers, ether esters (especially high boiling ether esters) , certain catalytic phase oil's, polymer distillation residues, mixtures of alkylated benzenes and naphthalenes, mixtures thereof, alkoxylated derivatives of such compounds, and the like. These additives generally comprise organic compounds generally containing from 2 through 30 carbon atoms with¬ in their main hydrocarbon chain and may contain more car- bon atoms, for example, in side chains or in alkoxylated additives condensed onto the main compound or radical. Such organic compounds are of a type which promote compatibility of unsulfonated (sulfonatable and non- - 20 -sulfonatable) petroleum oil feed stocks with sulfonated components during SO, reaction conditions. Compounds of this type generally have boiling points in the range from about 212° to.932° F. (about 100° to 500° C.) or higher, depending upon the degree of substitution, if any. Additionally, such compounds generally are com¬ prised of unsulfonatable organic radicals having aη average atomic weight in the range of from about 55 through 6000, and somewhat more preferably in the range from about 75 through 1000,- and most preferably in the range of from about 100 to 350 (excluding any alkoxy or the like units, which may range up to about 1000 or more, attached thereto) and a preponderance of such organic radicals each have attached thereto at least one proton replaceable by a sulfo group and at least one moiety selected from the group consisting of an aromatic nu¬ cleus; an olefinic.carbon pair, and an oxygen atom di¬ rectly bonded to a carbon atom by at least one bond.Preferred groups of organic additives useful in the practice of the invention are selected from the classes consisting of alcohols, oxygen-containing com¬ pounds, hydroxy-containing compounds, substituted and unsubstituted hydrocarbons, high boiling esters, high boiling ethers, high boiling ester ethers, aromatic compounds, fatty acids and derivatives thereof, olefins, ketones, alkaryl compounds and mixtures thereof. A preferred class among this group is the oxygen or hy- droxy-containing compounds, both of which are sometimes referred to hereinafter as oxygenated or oxygen- containing compounds.A species of the oxygenated compounds (which include the hydroxy-containing compounds) useful in the practice of the invention comprise aliphatic alcohols.-&V REOMPI ,- -■ W1P0 Typical aliphatic alcohols useful in the practice of the invention are those which contain at least 4 carbon atoms per molecule (although C, to C, aliphatic alcohols may be used when such low molecular weight alcohols are alkoxylated with a plurality of alkoxy units) and preferably are C, to C ,8 aliphatic alcohols. Mixtures of aliphatic alcohols (some of which may be alkoxylated) may also be used in the practice of the invention. For example, one may employ octyl alcohol, nonyl alcohol, decyl alcohol, hexyl alcohol, .octadecyl alcohol, dodecyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, etc. or mixtures thereof. A particularly useful aliphatic alcohol is a tallow alcohol (which is a mixture of C, . to C, g fatty alcohols) . Another useful species of oxygen-containing or oxygenated compounds comprises phenolic compounds which include substituted phenolic compounds. Typical phenolic compounds comprise phenol, octyl pehnol, nonyl phenol, resorcinol, etc. as well as phenol compounds having one or more C, to C,g alkyl thereon, C- to C. alkoxylated phenols (including alkoxylated alkyl phenols) , polyalkoxylated (including polyalkoxylated polyalkyl phenols) phenol including mixed polyalkoxy¬ lated phenols, i.e., ethylene oxide-propylene oxide units, or mixtures thereof.A further useful species of oxygen or hydroxy- containing compounds comprises glycol and glycerol com¬ pounds, such as propylene glycol, butylene glycol, ethylene glycol, diethyl glycerol, etc. all of which may be alkoxylated, if desired.Yet a further useful species of oxygen or hydroxy-containing compounds comprises organic acids, such as C . to C_2 fatty acid, which may also be alkoxy- lated, if desired.A preferred species of oxygenated (hydroxy- containing) compounds useful in the practice of the in¬ vention are commercially available high-boiling alcohol- containing materials known as oxo alcohols or oxo bottoms and more particularly as oxo alcohol still bottoms, oxo alcohol distillation residue, oxopolymer products or oxo alcohol polymer bottoms. The preparation and de¬ scription of these alcohol materials is known, for example*, as set forth in a book entitled Higher OxoAlcohols , by L. F. Hatch, Enjay Company,. Inc., 1957, the disclosure of which is incorporated herein by refer¬ ence. The term oxo alcohol is used in the art as descriptive of the type of process employed in producing these alcohols synthetically. Alcohols having the desired functionality can also be obtained from natural sources as well as from available synthetic processing means, and functionality is not dependent on the source or synthesis process. Generally, oxo alcohols comprise a complex mix- ture of various alcohols, ether alcohols, esters, soaps, etc., for example, as described by E. H. Bartlett et al in an article entitled Oxo Ether Alcohols , published in Industrial and Engineering Chemistry, Vol. 51, No. 3, March 1952, the disclosure of which is incorporated herein by reference. Commercially available oxo alcohols include those in the C. to C, g range and two particularly attractice oxo alcohols are the Cg and C,Q materials, both of which are mixtures of isomers produced by the oxo process from branched C_ and Cg olefins. A typical oxo alcohol still bottom of this type which is useful in the practice of the invention has the following composition: Component % By WeightOctyl alcohol 2 - ■ 20Nonyl alcohol 5 - • 40Decyl and higher boiling c materials* 25 - ■ 90Esters 20 - • 80*Ether alcohols, saturated and unsaturated ethers, mixtures thereof, as well as other oxo reaction by-products.Another oxo alcohol still bottom which is an excellent 0 additive useful, in the practice of the invention has the following composition:Component % By WeightOctyl alcohol 5Nonyl alcohol 10 5 Decyl and higher boiling materials* 35Esters 45'Soaps 5*Ether alcohols, saturated and unsaturated ethers, mixtures thereof, as well as other 0 oxo reaction by-products.Any of the above oxygen or hydroxy-containing com¬ pounds may also be alkoxylated by a reaction with a select number of mols, say about 1 to 200 mols, of a C, - C. al- koxide, i.e., ethylene oxide, propylene oxide, butylene ox- 5 ide, an ethylene oxide-propylene oxide unit ormixtures thereof.Another class of additives useful in the practice of the invention comprise high boiling un¬ saturated (olefins) branched or straight-chain hydro¬ carbons (i.e., having a boiling point in the range of 0 about 100° to about 500° C). Generally, these compounds comprise C. to C2g hydrocarbons and preferably are Cg to C22 hydrocarbons, such as, for example C,4 or C,g ___ -olefins, mesityl oxides, tetradecene, octocosene. docosene, octodecene, etc., or mixture thereof.Yet another useful class of additives useful in the practice of the invention is high boiling ethers, i.e., having a boiling point in the range of about 100° to about 500° C. Typical members of this class are glycol ethers, such as available under the trademark CELLOSOLVE from Union Carbide Corporation, and which include such ethers as 4-methoxy butanol, 2-ethoxy ethanol, 2-propoxy ethanol, 2-butoxy ethanol, etc. Other typical ethers useful herein are those available under the trademark CARBITOL from Union Carbide Corpora¬ tion and which include such ethers as diethylene glycol ethyl ether, diethylene glycol butyl ether, etc. The preferred glycol ethers include• C . to C, glycol ethers, such as diethylene glycol, etc.Another class of additives useful in the prac¬ tice of the invention is high boiling ether esters (i.e., having a boiling point in the range of .about 100° to 500° C), such as available under the trademarks CARBITOL or CELLOSOLVE . Typical materials of this type are CARBITOL acetates such as methoxy diethylene glycol acetate or CELLOSOLVE acetates such as methoxy ethyl acetate, butoxy ethyl acetate, etc.Yet another class of additives useful in at- taining an improved degree of reaction between petroleum oil feed stocks and gaseous sulfur trioxide is the alkaryl compounds, typically comprising C_ to C,Q compounds having a boiling point in the range of about 100° to 500° C. Typical materials of this type include c, to C2Q alkyl substituted benzenes, such as dodecyl¬ benzene, cumene, thymol (p-propyl-m-cresol) , etc.An additional class of additives useful in the practice of the invention is esters. Typically, pre- ferred esters having boiling points in the range of from about 100° to 500°C. and comprise C. to C_. alkyl esters of C. to C22 aliphatic carboxylic acids, for example, methyl, ethyl, etc., esters of octyl, nonyl, decyl, lauryl, myristyl, palmityl, stearyl, etc. acids or mix¬ tures thereof. A preferred group of such alkyl ester acids are the methyl esters of Cg to C.g fatty acids, and, of these, the methyl esters of Cg to C,Q and C,Q to C,g are extremely useful. Useful esters may also be produced by reacting the above Cg to C20 aliphatic acids with the Cg to C2g aliphatic alcohols described earlier, all of which may be alkoxylated, if desired.Further additives useful in the practice of the invention include catalytic cycle oil, such as defined in U.S. Patent 3,317,422 (column 1, lines 55-72) , which is incorporated herein by reference, ultraformer polymer bottoms (a known commercially available material principally comprised of mixtures of alkylated benzenes and naphthalenes, and mixtures thereof) ,. as well as other like materials.In summary, an additive useful as a starting material in the practice of the present invention is characterized by:(A) being comprised of unsulfonatable organic radicals possessing an average molecular weight from about 55 to 6000;(B) having a boiling point in the range from about 100° to 500° C. (212° to 932° F.) corrected at¬ mospheric pressure, and (C) a preponderance of such radicals each having attached thereto at least one proton replaceable by a sulfo group and at least one moiety selected from the group consisting of an aromatic nucleus, an olefinic carbon pair, and an oxygen atom directly bonded to a carbon atom by at least one bond. (Of course, poly- functional molecules having a plurality of such protons ' ' and moieties attached thereto are also included as are various blends of additives.)Additives useful in the present invention can initially be admixed with other organic materials, such as alkane hydrocarbons, halogenated hydrocarbons, and the like, which do not appear to undergo sulfonation when exposed to sulfur trioxide. Preferably at the time of use in the practice of this invention, however, an additive composition contains a preponderance (i.e., not less than about 60 weight percent total additive composition basis) of at least one additive characterized as above. WaterIn general, the water employed in this inven¬ tion may comprise any available relatively pure water, including raw tap water, demineralized or softened water, deionized water, distilled water, etc., as well as other forms of water, such as steam. In selecting a water source, it is advisable to avoid water contain¬ ing a relatively high concentration of polyvalent ions therein, such as calcium or magnesium ions, although water with a relatively moderate or low concentration of polyvalent ions may be used, if desired.A relatively small amount of water, generally about 0.5 to 20% by weight of crude reaction mixture (as will be appreciated, higher amounts of water may be used without notable detriment, providing that the economics of handling additional material are taken into account; for example, additional amounts of water might be desired if a dilute oil recovery formulation is made directly) is added, as by injection, into the hot crude sulfonation reaction mixture obtained from con¬ taining SO, with a petroleum oil feed stock-additive mixture. After a brief digestion or contact period of about 2 to 60 minutes at an elevated temperature of about 50° to 150° C. , neutralization is effected by mixing the water-treated, sulfonation reaction mix-: ture with a sufficient amount of a base, such as a 50% NaOH solution to attain apH in the range of about 3 to 12 and preferably in the range of 6 to 11.As demonstrated hereinafter, the order of water and base addition is important and yields sul¬ fonate materials having improved oil recovery properties not available with somewhat similar sulfonate materials treated in some other manner. The exact nature of the water treatment step is not presently fully understood, however, it is noted that water-treated sulfonation reaction mixtures are capable of forming better micellar systems (i.e., requiring less of a co-surfactant, such as an alcohol, for example, hexanol) , exhibit a higher average equivalent weight, retain relatively lower over¬ all viscosity and provide improved phase stability and homogeneity, especially for the acidic reaction mix¬ tures, and, most important, provide improved oil re- covery when further processed, formulated into an oil recovery system and injected in a subterranean petro¬ leum bearing formation via a slug formulation. Sulfonation Process DetailsIn proceeding along the principles of the in- vention and in accordance with one of the more preferred embodiments of the invention, the petroleum oil feed stock is first mixed with an additive. In general, mixtures employed in the present invention comprise'BU EAUOMPl^ ATlO^ from about 0.5 to 15 weight percent of ah additive, and from about 85 to 99.5 weight percent of a petroleum oil stock, on a 100 weight percent total mixture basis. Preferably, a mixture employed in the present invention comprises from about 2 to 10 weight percent of an addi¬ tive and from about 98 to 90 weight percent of a petro¬ leum oil stock on a 100 weight percent total mixture basis.Preferably, in one mode, a film of such mix- ture is fed to a reaction zone of a reactor, such as a tubular reactor. A selected additive may be added if desired from a source thereof to an already formed film of oil feed stock prior to or simultaneously with SO, contacting or a select additive may be mixed with an oil feed stock prior to being fed, in film form, to a reaction zone. The mixture or just the petroleum oil feed stock may be heated prior to SO, contact, if desired.The reaction zone generally is one compatible with the reaction of gaseous SO, (sulfur trioxide) and a sulfonatable material. A wide variety of existing processes and apparatuses incorporate and utilize suitable reaction zones. Examples of such, prior art processes and apparatus include U.S. Patent Nos. 2,697,031; 2,768,199; 2,923,728; 3,056,831; 3,270,038; 3,328,460; 3,427,342; 3,438,742; 3,438,743 and 3,438,744.The contacting of sulfur trioxide with a mix¬ ture of petroleum oil stock and additive as above characterized is affected generally at a temperature ranging from about 25° to 200° C. (about 77° to 392° F.) although if solvents, such as liquid S02, are utilized, lower temperatures may be used. In the reaction from about 5 to 40 parts by weight of sulfur trioxide are contacted typically with each 100 parts by weight of-BU EO PI the (essentially moisture-free) mixture comprised of petroleum oil stock and additive being sulfonated. The total time of contacting of sulfur trioxide with such mixture is at least sufficient to sulfonate not less than about 10 weight percent of the total sulfonatable components present in the starting petroleum oil stock.Preferably, such contacting is continued for a time at least sufficient to produce a sulfonated compo¬ sition which is then water-treated so as to comprise a composition of this invention, as hereinafter defined.Since temperature, time and pressure conditions are not critical and may be readily adjusted by an opera¬ tor in accordance with a particular feed stock, reaction apparatus, process or desired end product, all such conditions will sometimes be referred to herein as time- temperature-pressure conditions sufficient to form sul¬ fonation.products.One excellent and commercially feasible method for continuous sulfonation is set forth by Knaggs et al in U.S. Patent 3,169,142 (owned by the instant assignee) , the disclosure of which is incorporated herein by reference. The method thereof, which will be described in further detail hereinafter is improved by the instant invention, particularly in relation to sulfonation of petroleum oil feed stocks. However, it will be appre¬ ciated that the invention may also be practiced by various other sulfonation methods, such as batch, cas¬ cading, quasi-continuous, etc.Generally, the contacting time varies from about 0.001 seconds or less to about 1800 seconds or more, depending on the type of apparatus used, the • desired degree of sulfonation, the extent of re¬ cycling (if any) of the reactants and/or reaction products, etc.As set forth earlier, a mixture of starting petroleum oil feed stocks and additive is fed, in a liquid form, which, in the preferred embodiment under discussion, comprises flowing a film of such mixture to a reaction zone of a reactor. In such a preferred embodiment, the liquid film of petroleum feed stock and additive is supported on a supporting and confining heat exchange surface defining the reaction zone. An apparatus which includes such a surface may comprise a tubular or multiple tube reactor, such as described in the above referenced Knaggs et al U.S. Patent 3,169,142 generally known as a falling film reactor and/or a more complex wiped film reactor, s ch as shown in U.S. Patent 3,427,343. Of course, in other processes, such as for example, in a batch SO, sulfonation process, the liquid mixture is simply fed to a reaction vessel which may include either a heat exchange surface along select portions thereof, or a cyclic looped external heat exchanger.The sulfonation reaction of this invention can be carried out using a gaseous SO,, optionally admixed with an inert gas, such as nitrogen or air. Generally, the ratio of inert gas to gaseous SO, falls within the range of from about 3:1 to 75:1 and preferably from about 5:1 to 50:1. In certain instances, it may¬ be desirable to utilize liquid SO,, admixed with or without a liquid or gas diluting agent, such as for example S02 refined light paraffinics, light crude oil distillates, air, nitrogen, pentane, and the like, and such a liquid mixture is within the scope of the inven¬ tion. An effluent diluent-gas can be recycled and SO, added thereto to thereby provide a closed system. Further - 31 -if desired, SO, may be utilized per se whether in liquid or gaseous form, although from a point of safety and reaction control, it is preferable to utilize a mix¬ ture of gaseous SO, and an inert gas. The gas mixture is preferably caused to impinge on the liquid petroleum- additive mixture and readily reacts with the sulfonatable components of such liquid as soon as sulfur trioxide comes in contact with at least some of the reactable components present in the liquid. This reaction is exothermic and good heat exchange capabilities may be required in the reaction system, such as by providing a reaction surface having a heat exchange means associated therewith or by providing an operable external heat ex¬ change system. The amount of additive present in the reaction zone generally is at least about 0.5% by weight based on the weight of starting petroleum feed stock. Generally, the amount of compatibility promoting additive utilized in accordance with the principles of the invention range from about 0.5% to about 15% by weight and a practical additive dosage is about 0.5% to 5% or 2% to 10% (same basis). As those skilled in the art will appreciate, the exact or optimum amount of additive utilized with a selected petroleum oil feed stock is dependent upon a wide variety of variables, such as characteristics of the oil feed stock, desired degree of sulfonation, availability of a select additive, etc. , and a specific amount for use in a given system may be readily deter¬ mined by those skilled in the art. The selection of particular reaction conditions, such as time, temperature, pressure, etc., depend upon a number of process variables, such as characteristics of petroleum oil feed stock, the amount and type of BUREAUOMPI^/?NATlO^ additive, the apparatus employed, the characteristics of the formed products, etc. Generally, the sulfonation is conducted using temperatures in the range of about 25° to 200° C. (77° to 392 °F.) and somewhat more preferably in the range of about 50° to 140° C. (122° to 284° F.). It is recognized that measurements of true reaction temperature under the dynamic conditions present within a reactor are very difficult to measure accurately. However, such temperatures can be estima- ted, for example, by means of thermocouple in the reaction zone and by observing the resultant temperature profile. The sulfonation process may also be run above or below atmospheric pressures.As noted above, the invention is adaptable to be used with a wide variety of prior art processes and apparatuses, upon which the invention is a substantial improvement. Thus, a particular reaction vessel may be in a horizontal, vertical or angularly inclined position, and be adapted for continuous, batch, quasi- continuous or cascading operation. Preferably, the reactable mixture is in the form of a falling liquid film, since such falling films appear to have advantages of improved reaction control, better versatility, simplicity of design and large-scale continuous opera- tion as well as other advantages.A preferred basic sulfonation process is described in the above Knaggs et al U.S. Patent No. 3,169,142. Briefly, sulfonation is carried out in accordance with that process by inducing -marked turbu- lence in a liquid film containing sulfonatable compo¬ nents with a pressurized stream of an inert diluent and vaporized sulfur trioxide which is impinged onto such a film. The inert diluent is gaseous and may be dry air, SO, converter gas from a sulfur burner catalytic converter which generally comprises a mixture of 5 to 10% SO, in dry air, nitrogen, carbon dioxide, carbon monoxide, sulfur dioxide, methane, ethane, pro- pane, butane, pentane mixtures thereof or other dry gases. The diluent gas may be passed only once or it may be recycled in the process, as desired.As the Knaggs et al process is practiced in accordance with the principles of the instant invention, 0 a selected petroleum oil feed stock mixed with an ad¬ ditive is caused to flow along the inner walls of a single tube or preferably a plurality of downwardly inclined reactor tubes in a film form. The film of the oil-additive mixture (which may be preheated) is. im- 5 pinged upon by a dilute vaporized sulfur trioxide re¬ agent at substantial velocities^ so as to create marked turbulence in the film. The sulfonation reaction itself is extremely fast, with the residence time of the sulfur trioxide inert gas mixture, which is usually directed 0 into contact with the film by means of a suitable gas inlet device, characteristically being less than about 0.5 seconds. The gas temperature in an exemplary embodi¬ ment ranges from about 25° to 80° C. (about 77° to 179° F.) at a line pressure ranging from about 2 to 20 psi. The 5 reactor itself may be of a single tube or a plurality of tubes of various diameters and lengths. To effect such a desired rapid reaction and rapid heat exchange, marked turbulence should be produced in the reaction zone, and the Knaggs et al process provides sufficiently rapid Q reaction times and heat exchange capabilities. The reactor effluent may vary over a broad temperature range, depending at least in part on the heat exchange capabilities of the reactor, the residence time of the materials within the reactor, the amount of sulfonatable components within the materials being sulfonated, etc.By proceeding in accordance with the principles of the invention, the extent or degree of reaction be- tween oil feed stocks and sulfur trioxide is generally increased on the order of 200% when additives are added to the petroleum oil feed stock prior to sulfonation reactions, as compared to similar reactions where no additive has been added. Under certain conditions, the increase in the extent of reaction is as high as 500% in comparison with prior art sulfonation processes in¬ volving no additives. Water Treatment DetailsIn proceeding along the principles of the in- vention, the relatively hot reactor effluent (generally comprised of petroleum-additive sulfonic acid crude reaction mixture) is admixed with a relatively small amount of water, heated or cooled to an optimum 'tempera¬ ture range and maintained under these conditions for a relatively brief period of time.Generally, the amount of water is relatively minor in comparison to the overall reactor effluent and typically ranges from about 0.5% to 20% or more (on a weight basis of the reaction mixture) and preferably comprises about 3 or 5% to about 10%. As will be appre¬ ciated, substantially more water may be added, if desired, but such is not required or advisable unless one seeks to directly produce a dilute slug or oil recovery system. In a preferred continuous embodiment of the invention, the water treatment step is accomplished by withdrawing the reactor effluent from the reactor via a suitable conduit and injecting water into the conduit to admix within the crude reaction product therein as the mixture flows along the conduit. However, this step may, if desired, be performed batchwise or quasi- continuously by collecting the crude reaction products in a suitable container and adding water to the con¬ tainer from the bottom thereof while either allowing excess material to cascade over the upper container walls into, for example, a neutralization container or the like or simply collecting a predetermined amount of crude -reaction product within a given container and adding, with admixture, the requisite amount of water (typically based on amounts of reaction mixture pro¬ duced from the known amount of reaction materials intro¬ duced into the reactor) . The water added to the relatively hot petroleum- acid sulfonic acid crude reaction mixture may be at room temperature or may be heated somewhat above room temperature, such as in the range of about 50° to 150° C. and somewhat more preferably to a temperature in the range of about 80° to 100° C. Higher water temperatures may be used if desired, however, pressure may then be required to prevent excessive losses of water vapor and the like and such higher temperatures do not appear to materially aid the resultant water-treated products. Similarly/ lower water temperatures may be used if desired, however, heat may then be required to raise the temperature of the crude sulfonic acid-water mixture sufficiently high for the reaction to occur relatively quickly. Addition of water to the crude sulfonation reaction mixture is generally accomplished by an exo- therm and a rise in temperature.The water treatment time period may be rela¬ tively brief on the order of about 1 or 2 minutes. BUREAUOMPI^SNATIO≤^ although longer periods on the order of about 60 or more minutes may be utilized if desired. Preferably, con¬ tact between the crude petroleum-additive sulfonic acid • > reaction mixture and the added water extends over a period of about 3 or 5 minutes to about 30 minutes. Substantially longer contact periods may be employed if desired, but such are not generally required.«The resultant acidic water-treated sulfona¬ tion reaction mixture is relatively stable and homo- geneous, even at room temperatures. These acidic water- treated reaction mixtures are less viscous than com¬ parable non-water-treated reaction mixtures and are thus much more handleable for further processing. Typically, the crude sulfonic.mixtures, with or without water treatment, may be subjected to neutralization, extraction, deoiling and/or desalting processes in any order desired or convenient. - Generally, proper selection of the type and amount of additive and proper control of the reaction conditions in the initial sulfonation process minimizes an excessive presence of unsulfonated feed stocks and/or salts in the crude reactor mixtures and in many instances these further processing steps may be avoided.Typically, the crude acidic water-treated 'reaction mixture is first neutralized, and optionally desalted and/or extracted to attain active sulfonate materials useful in various fields, such as in formula¬ ting desired micellar systems for use in enhanced oil recovery. Neutralization is conventionally accomplished by the addition of an alkali (such as NaOH, NH.OH,KOH, NH,, etc.) generally as a somewhat diluted aqueous solution, i.e., a 50% NaOH solution. The amount of alkali added is calculated to be sufficient to achieve a pH of about 3 to 12 in the resultant mixture and some¬ what preferably to achieve a pH of about 6 to 11. ProductsIn general, a product of this invention is a mixture of petroleum oil feed stock and additive, as explained above, which has been sulfonated with sulfur trioxide treated with a small amount of water, neutralized and preferably although not necessarily extracted as explained above. Such a product comprises a substantially homogeneous and stable material, at least under reaction, conditions (and even at room temperatures) and typically is sulfonated to an extent such that at least about 10 weight percent of the sulfonatable components thereof are sulfonated (total product composition weight basis) . In summary, a product of this invention is characterized by:(A) from about 5 to 98 weight percent of monosulfonated hydrocarbon material;(B) from about 0 to 50 weight percent of polysulfonated hydrocarbon material; and(C) from about 2 to 90 weight percent of non-sulfonated hydrocarbon material.Such product composition is prepared by con¬ tacting a liquid hydrocarbon mixture .with a gaseous sulful trioxide composition at a suitable temperature, subjecting the resultant crude reaction products so attained to a water-treatment process and neutralizing the so-treated crude products which may then be utilized as such in a desired microemulsion system or may be subjected to extraction to remove salt and/or free oil that may be present within the crude products so- attained, all as described above.Many of the described additives are also sul- - 38 -fonated or sulfated wholly or partially during the sul¬ fonation reaction between petroleum oil feed stocks and sulfur trioxide. For example, the alcohol additives and the ether alcohol additives are generally sulfated during such reaction, while the alkaryl additives may be sulfonated during the reaction. Such fully or par¬ tially sulfonated additive derivatives also function as additives as such, and may be initially added to a petroleum oil feed stock to promote compatibility be- tween petroleum sulfonates and oil under the reaction conditions or may be blended with the ultimately at¬ tained reaction products as an aid in forming stable micellar dispersions used in oil recovery processes. Further, these additive derivatives do not detract from the useful characteristics of the ultimate reaction product and may remain therein. In some instances, high additive levels may be preferred to further enhance oil recovery properties, particularly in higher salinity systems, etc. In certain instances, it may be desirable to separately sulfonate select additives and admix such separately sulfonated additives with sulfonated petro¬ leum products (which may or may not include additives therein) , or to sulfonate on select portions of an additive molecule, such as on an aromatic portion there- of, to increase the salinity and/or hard water tolerance of the resultant sulfonated petroleum product (which, of course, may comprise a mixture of various specific sulfonated petroleum products) .The water-treated reaction products of the invention are preferably neutralized and may be used as such without further purification (such as desalting, deoiling or phase separation, etc.) and generally comprise a mixture of petroleum sulfonates, unsulfonated petroleum feed stock components, sulfonated and un¬ sulfonated additives, along with various other minor constituents, such as salts. If desired, the sul¬ fonates may be separated and/or the additives recovered for recycling, however, from an economical viewpoint, such further purification or separation of materials may not be justified and from an oil recovery view-, point such separation of materials is not recommended. Further, when neutralized, the amount of alkali (such as NaOH, NH4OH, KOH, H-j, etc.) may be so controlled that the resultant products have a pH in the range of about 3 to 12 and preferably in the range of 6 to 11.The reaction products and/or components there¬ of, such as the petroleum sulfonates have numerous. fields of use, for example, as industrial surfactants, as blending agents for lubricating oils, as surface- active agents, as emulsifiers, dispersants, etc. A particularly attractive use for the reaction products of the instant sulfonation process (which include the additives, which themselves may be sulfonated) is in petroleum recovery operations, particularly as sur¬ factants for aiding the recovery of crude pils from so-called depleted fields or wells, for example, as described by G. P. Ahearn in an article in the Journal of American Oil Chemists' Society, October 1969 (Vol. 46), pages 540A et seq. , entitled Surfactants for Oil Recovery or in the U.S. Patent No. 3,302,713, both of which are incorporated herein by reference. -The petroleum sulfonate products obtained in the practice of the invention are extremely useful in forming so- called dispersion or micellar systems and/or micro- emulsions or emulsions as well as other systems which are used in enhanced or secondary recovery of petroleum. The petroleum sulfonates obtained in the practice of the invention may be added to or used to replace all or part of various other surface-active agents in various prior art oil recovery systems, such as described, for example, in U.S. Patent Nos. 3,254,714; 3,297,084; 3,307,628; 3,330,343; 3,348,611; 3,356,138; 3,368,621; 3,408,611; 3,476,184; 3,493,047; 3,493,048; 3,497,006; 3,500,912, 3,504,744; 3,506,070; 3,506,071; 3,653,440; 3,769,209; •3,830,301; 3,873,453; 3,885,626; and 3,885,628 (all of which are incorporated herein by reference) , as well as in other somewhat similar systems. In many instances, no further changes in the compositions of such oil recovery systems, whether micellar, dispersion, emulsion or otherwise, will be required. In other instances where larger or smaller amounts of petroleum sulfonates (reaction products) obtained in the practice of the invention are required, workers skilled in the art can readily determine the optimum amount by routine produc¬ tion of a desired system and routine evaluation of such system, for example, with the aid of core-flooding tests or the like. Further Processing of ProductsIn further embodiments of the invention, the above described basic petroleum oil sulfonation process may be supplemented by a number of further optional processes. For example, the reaction products (a mix¬ ture of petroleum sulfonates, unsulfonated oils, sul¬ fonated and unsulfonated additives, etc.) neutralized to a pH in the range of about 3 to 12 may be subjected to extraction, deoiling and/or desalting processes.Generally, proper selection of the type and amount of additive and control of the reaction conditions in the basic sulfonation process minimizes an excessive OMPIS 7ΛAr,- W1PO - _; -- 41presence of unsulfonated oils and/or salts in the reaction products (typically the amount of salts in neutralized products may range from about 0.1 to 10% by weight) ; and in many instances these further process- ing steps may be avoided. This constitutes a further advantage of the invention. However, in those instances where such optional steps are desired, they may be * performed, for example, by adding water or a mixture of water and an alcohol, such as C, - C5 alcohols or semipolar organic compounds, for example, isopropyl alcohol or benzene to the reaction products to achieve a phase separation and then simply removing the unsul¬ fonated (unsulfonatable and non-sulfonated) oils or raffinate phase, which is substantially insoluble in the hydrophilic solvent. If desired, the unsulfonated oils may be recycled through the sulfonation reaction or may be otherwise disposed of and any alcohol or other valuable component therein recovered for further use. This deoiling process may be followed by or preceded by a desalting process wherein the water-treated acidic reaction products are neutralized to form a desired salt, such as with sodium or ammonium hydroxide and the re¬ sultant salt precipitates from the solution and which can then be separated by centrifugation, filtration, etc. (although small amounts of salt may remain in the product without detrimental effect) . The deoiling process may also be performed on the neutralized reaction products, if so desired, and since some solvent may carry over with the extracted phase, such phase may be distilled or otherwise purified to recover any sol¬ vent therein for further use, or left in, if desired. Separation, such as may occur on cooling of essentially unreacted oils from crude sulfonic acid mixtures may be effected by decantation or other phase separating processes, although the water-treatment step of the invention tends to minimize any such separation.Additionally, the reaction products may be subjected to a digestion process whereby the reaction products are held or stored in a container for some period of time, such as 20 minutes, while they are main¬ tained at some desired temperature or cooled down from the heat of reaction. In a modified form of the digestion process , the reaction products are maintained at a select temperature and some heat may be applied. Such a digestion process is recommended to react traces of dis¬ solved sulfur trioxide with sulfonatable oil components and/or sulfonatable additive components and to reduce the sulfuric acid content in the reaction products. The digestion process may be coupled with a number of further steps. For example, additional amounts of additives may be intermixed with the reaction products during digestion or thereafter. Many of the additives described herein tend to further reduce the sulfuric acid content and react with any sulfur trioxide present in the reaction products. The additives added at this stage may be the same or different from those present in the sulfonation reaction zone. A further optional treatment of the sulfonation reaction products comprises a sequential combination of digestion and heat treatment. Typically, after digestion, the reaction products are heated or held at a temperature ranging from about 35° to 150° C. (95° to 302° F.) for a brief period of time. This combination of steps is designed to further complete the sulfonation reaction and reduce the sulfuric acid content in the ultimate reaction products'. -BUREAT OMPIΛ,. r iPO _ Yet a further optional treatment of the reaction products involves digestion, followed by heat- treatment and further addition of additives to effect a complete reaction as set forth above. In addition, other conventional steps may be utilized following the initial- sulfonation reaction, such as degassing, filtration and/or neutralization. For example, the water-treated sulfonation reaction products, which are acidic in nature, may be first neu- tralized, such as with an economical material, for ex¬ ample, sodium hydroxide, followed by removal of resul¬ tant salt, as by the addition of a suitable solvent and then followed by filtration, centrifugation, etc.Thus, one has the option of utilizing any combination of the post-sulfonation steps described here¬ inabove to achieve desired characteristics in the reaction product. Under certain reaction conditions, generally at somewhat higher reaction temperatures, immediate neutralization of the water-treated reaction products is preferable so as to avoid decomposition of reaction pro¬ ducts, possible desulfonation or other undesirable reactions.With the foregoing general disclosure in mind, a number of detailed examples are presented which will illustrate to those skilled in the art the manner in which this invention is carried out. However, the examples are not to be construed as limiting the scope of the invention in any way and the examples merely point out the efficacy of the invention in attaining the high degree or extent of reaction between sulfonatable components of various oil petroleum feed stocks with gaseous sulfur trioxide in the presence of the additives described hereinabove and demonstrate a preferred utility BV-iRtATT*OMPI1^SNATIO ' of the so-attained sulfonated compositions.DEMONSTRATION I A series of runs, shown below, were conducted ■ to demonstrate the improved performance of petroleum sulfonates obtained in accordance with the invention against otherwise substantially identical sulfonates which, however, had not been subjected to water tre *at- ment as required by the principles of the invention. A select petroleum feed stock, generally characterized as a paraffinic petroleum oil having the following properties:Average molecular weight 390 API Gravity (at 60° F.) 14.3Pour Point (in ° F.) +70 Boiling Range (in ° F.) 661° to 904° was admixed with 4% (by weight of feed stock) of an oxo alcohol polymer bottoms (identified as Houdry Cg alcohol bottoms) , was then sulfonated via the techniques of Knaggs et al U.S. Patent No. 3,169,142 in a laboratory model six-foot reactor tube whereby a liquid film of the above petroleum feed stock-additive mixture flowing within the reactor tube was impinged by a gaseous mix¬ ture of nitrogen (or some other inert gas) and sulfur trioxide, containing a ratio of about 95:5 of nitrogen to sulfur trioxide. The gas mixture temperature at the initiation of the sulfonation reaction was maintained at about 35° C. (95° F.) and the pressure of the gas mixture within the reaction zone (i.e., the interior of the reactor tube) was about 3 to 5 psig. The petroleum feed stock-additive mixture was heated to a feed temperature of about 50° to 55° C. (122° to 131° F) The reactor tube was steam-jacketed and the crude sul¬ fonation product outlet temperature was about 110° C. BUREAO-V-PI P (230° F.). The liquid film feed rate was set at about . 100 gr./min. and the gas velocity into the reactor tube was set at about 95 ft./seel so that an SO, feed rate of about 15 to 20 gr./min. was attained. The crude sulfonic acid so-obtained was then separated into four portions and two portions, designated I-A and I-B, respectively, were treated as follows:»Portion I-A was neutralized with a 50% NaOH solution until a pH of about 10 was attained. The re- suiting crude sodium petroleum sulfonate was then ad¬ mixed with isopropanol and water in the ratio of 2:1:1 (all by weight of sulfonate to alcohol to water) and maintained at about 140° F. for one hour. Three layers formed and were separated in a conventional manner. The middle layer, which comprised mainly of sodium petroleum sulfonate, unreacted feed stock, salt, water and isopro¬ panol was heated under vacuum to remove the alcohol and some water. The resulting material was analyzed as comprising about 60% active sodium petroleum sulfonate. Portion I-B was first mixed with 7.5% water(based on weight of reaction mixture) and maintained at about 85° to 95° C. for about 6 minutes. Thereafter, the so water-treated crude sulfonic acid material was neutralized with 50% NaOH to a pH of about 10, and separated as described above for portion I-A, correcting for the 7.5% water addition. After stripping alcohol and some water, as above, the remaining material was analyzed as comprising about 60% active sodium petroleum sulfonate. The sodium petroleum sulfonates, designated sanple I-A and I-B, respectively, were then identically formulated into microemulsion slugs and tested for oil recovery performance using an-Illinois crude oil with a standard Berea sandstone core prepared as follows:2 x 12 cylindrical Berea sandstone cores were fired at 825° F. for 24 hours, side surfaces there¬ of encapsuled with an epoxy resin flushed with a stan- dard brine solution (water containing 1.5% NaCl and100 ppm of Mg and Ca ) ; saturated with the Illinois crude oil; flushed with the above standard brine solu- tion (secondary recovery) and the residual oil, after brine flushing, was calculated and used to determine the percentage of tertiary or enhanced oil recovery attained by forcing the respective slugs through such cores. Pertinent data is set forth below:TABLE ASlug CompositionSam¬ Water Act. Co-Sur-, Residual Oil Slug2 , ple Treat Sulf..NaCl factant RecoveryI-A No . 3.0% 1.5% 0.7% 29.1% 0.05 I-C Yes 3.0% 1.5% 0.65% 52.7% 0.051. n-Hexanol2. Pore Volume3. The slug was followed by an aqueous solution of 1500 ppm of Dow-Pusher 700 in 0.5% NaCl. As can be seen from the above data, petroleum sulfonate treated in accordance with the principles of the inven¬ tion provide substantially better oil recovery and it will be appreciated that deliberately low slug pore volumes were utilized to accentuate differences, whereas higher pore volumes are more generally utilized under actual field conditions and substantially greater oil recovery is expected (typically 60% to 95% oil recovery) . The above described microemulsion slug composi-OMPI tions were tested for oil recovery performance using an Oklahoma crude oil with the earlier described standard Berea sandstone cores. Pertinent data is set forth below:TABLE BSlug CompositionSam- Water Act. Co-Sur--, Residual Oil Sl*ug2 , pie Treat Sulf. NaCl factant Recovery P.V. 'I-A No 3.0% 1.5% 0.71% 48.9% 0.05I-B Yes 3.0% 1.5% 0.65% 64.2% 0.051. h-Hexanol2. Pore Volume 3. The slug was followed by an aqueous solution of 1500 ppm of Dow-Pusher 700 in 0.5% NaCl. As can be seen from the above data, petroleum sulfonates treated in accordance with the principles of the invention provide substantially better oil recovery with diverse crudes.A third portion, designated I-C, of the crude sulfonic acid obtained under the sulfonation conditions earlier described was neutralized by admixing therewith a 50% NaOH solution until a pH about 10 was attained, substantially as described earlier.A fourth portion, designated I-D, of the crude sulfonic acid obtained by the earlier described sulfona¬ tion conditions, was admixed with about 7.5% water (by weight, based on weight of reaction mixture) and ain- tained at about 80° to 90° C. for about 6 minutes. The so-treated materials were then neutralized with a 50% NaOH solution until a pH of about 10 was attained, sub¬ stantially as described earlier. The resulting samples, without phase separa tion (i.e., crude) were then formulated into micro- emulsion slug compositions and tested for oil recover performance using an Illinois crude oil with the earli described Berea sandstone cores. Pertinent data is s forth below:TABLE CSlug CompositionSam- Water Act. Co-Sur-, Residual Oil Slug- pie Treat Sulf. NaCl factant Recovery P.V.I-C Yes 3.0% 1.5% 0.51% 47% 0.05I-D No 3.0% 1.5% .0.54% 40% 0.051. n-Hexanol2. Pore Volume3. The slug was followed by an aqueous solution 1500 ppm of Dow-Pusher 700 in 0.5% NaCl.As can be seen from the above data, even crude petrole sulfonates treated in accordance with the principles o the invention provide better oil recovery relative to comparable sulfonates not treated in accordance with the principles of the invention.DEMONSTRATION II In another run, a different petroleum oil fe stock, comprising a combination of about 67% by weigh of paraffinic feed stock described in Demonstration I earlier and about 33% by weight of another paraffinic petroleum oil feed stock having the following properti Average Molecular Weight 480API Gravity 14.8Pour Point (in ° F.) +60°Boiling Range (in ° F.) 596 to 1009° was admixed with 4%. (by weight of feed stock) of the oxo alcohol polymer bottoms described in Demonstration I above, and sulfonated in the mariner described in α Demonstration I. The crude sulfonic acid reaction product so- obtained was separated into two portions, respectively designated II-A and II-B and each portion was then separately treated as follows:Portion II-A was neutralized with a sufficient amount of a 50% NaOH solution thereto until a pH of about 10 was achieved. The crude sodium petroleum sul¬ fonate was then subjected to phase separation (partial unsulfonated oil extraction and desalting) and stripping of alcohol and some water used for extraction as described earlier. The remaining material was analyzed as con¬ taining about 60% active sodium petroleum sulfonate.Portion II-A was first mixed with about 7.5% by weight water (based on weight of sulfonic acid) and maintained at about 85° to 90° C. for about 6 minutes. Thereafter, the so-water treated crude sulfonic acid material was neutralized with 50% NaOH solution thereto until a pH of about 10 was achieved. Phase separation and stripping were then carried out as described above, leaving about 60% active sodium petroleum sulfonate. Suitable size samples of the above sulfonates were formulated into substantially identical micro- emulsion slugs and'tested under substantially identical conditions for oil recovery using standard Berea sand¬ stone cores, prepared as described earlier and an Illi- nois crude oil. Pertinent data is set forth below: TABLE ESlug CompositionSam- Water Act. Co-Sur--, Residual Oil Slug2 , pie Treat Sulf. NaCl factant Recovery P.V. 'II-A Yes 3.0% 1.5% 0.42% 38% 0.05II-B No 3.0% 1.5% 0.52% 16% 0. *051. n-Hexanol Q 2. Pore Volume3. The slug was followed by an aqueous solution of 1500 ppm of Dow-Pusher 700 in 0.5% NaCl. As can be seen from the above data, petroleum sulfonates derived from mixed feed stock and treated in accordance 5 with the principles of the invention provide substantiall better oil recovery than non-treated, but otherwise identical material.DEMONSTRATION Til In another series of runs, the paraffinic 0 petroleum oil feed stock described in Demonstration I above, was sulfonated in the reactor tube as described earlier, using different additives identified below in the amounts specified below (all % are by' weight) . The so-obtained crude sulfonic acids were each maintained 5 separate from the others and each was subjected to the 7.5% water treatment, neutralization, phase separation and stripping described above. The sodium petroleum sulfonates derived from these runs were then tested for oil recovery performance using standard Berea sandstone 0 cores, prepared as described earlier and an Illinois crude oil. Pertinent data is set forth below: TABLE F... .... -_-_,Slug CompositionWater Act. Co-Sur-, Residual Oil Slug2 , Sample Additive ... Treat . Sulf. NaCl.. factant . . Recovery. . P..v.. 'III-A 4% OxoAlcohol Yes 3.0% 1.5% 0.78% 86% 0.204% Octadecene .III-B 8% NA3 Yes 3.0% 1.5% 0.82% 89% 0.201. n-Hexanol e2. Pore Volume3. Nonylphenol-alkoxylated material having an equivalent weight of about 2950As can be seen from the above data, petroleum sul¬ fonates derived from a feed stock- dditive mixture containing different amounts of different additives from those utilized in Demonstration I, above, provide improved oil recovery.DEMONSTRATION IV In another series of runs, portions of a naphthenic petroleum oil feed stock characterized as follows: _ Average. Molecular Weight 398 -Pour Point (in ° F.) +30°Aniline Point (in ° F.) 119° Boiling Range (in ° F.) 723° to 903° were admixed with the various additives identified below in the amount specified and each portion was then sul- fonated substantially as described in Demonstration I. The respective crude sulfonic acids were subjected to the 7.5% water treatment, phase-separation and strip¬ ing as described earlier. The respective sodium petroleum sulfonates derived from these runs were then tested for oil recovery performance using standard Berea sandstone cores, prepared as described earlier and an Illinois crude oil. Pertinent dat'a is set forth below: TABLE GSlug Composition Water Act. Co-Sur-, Residual Oil Slug- ,Sample . Additive. Treat Sul . NaCl. factant Recovery P.V. 'IV-A 4% Octadecyl benzene Yes 3.0% 1.5% 0.82% 46% 0.20IV-B 4% C8~C10. fatty acid mixture Yes 3.0% 1.5% 0.90% 73% 0.20IV-C 4% Octadecene Yes 3.0% 1.5% 1.10% 75% 0.201. n-Hexanol2. Pore Volume3. The slug was followed by an aqueous solution of 1500 ppm of Dow-Pusher 700 in 0.5% NaClAs can be seen from the above data, petroleum sul¬ fonates derived from feed stock-additive mixtures con¬ taining different feed stock, different amounts of different additives from those utilized in Demonstration I provide improved oil recovery results, although the specific alkaryl additive here utilized was not as effective as the fatty acids or the olefin here utilized for this specific crude oil and oil recovery system.DEMONSTRATION V • In yet another test, a petroleum oil feed stock having the following characteristics: Average Molecular Weight 390 API Gravity 14Viscosity (55 at 210° F.) 80 Pour Point (in °F.) 65 was admixed with 2% (by weight of feed stock) of n- hexanol and 2% (by weight of feed stock) of n-octanol and the resultant liquid mixture was sulfonated in the laboratory reactor tube earlier described under the following operating conditions:Liquid feed temp. 190° F. Liquid feed rate 99.9 gr/min. Gas velocity 95 ft.'/sec.Inert gas/S03 temp. 179° F. Reactor jacket temp. 182° F.Crude product temp. 213 °F. Pressure 3.5 psiThe crude reaction product was collected and 7.5% water was injected into such reaction product. The resultant • mixture was then maintained at 80° to 85° C. for about 5 minutes, followed by neutralization with 50% NaOH as described earlier. Analysis of the so-derived crude sodium petroleum sulfonate, designated sample V-A was as follows:Actives 28.9%Free Oil 46.0%Water 17.9%Salt 7.3%Equivalent Weight ■461The above sample V-A was then formulated into a micro- emulsion slug containing 3% actives therein and wa*s tested for oil recovery performance using ah Illinois crude oil with standard Berea sandstone cores, pre¬ pared as described earlier. The formulated slug was pressure-injected into a test core, following by 0.52 P.V. of a polymer pusher, such as a commercially available polymer pusher, under the trade designation Dow Pusher 700 and 1.0 P.V.2 of the standard brine solution (water containing 1.5% NaCl and 100 ppm ofMg and Ca ) . The pumping rate was controlled so that a frontal velocity of liquid within the core was about 12 inches per 24 hours and pressure traces were obtained using transducers and strip chart recorders operationally coupled to the test core. The pressure applied to the core varied from about 0.76 to 1.7 psig.Pertinent data is set forth below:TABLE H -Slug CompositionSam- Water Act. Co-Sur-, Residual Oil Slug- , pie Treat. S.ulf. NaCl factant . Recovery P.V. 'V-A Yes 3% 1.5% 0.08% 60.9% 0.151. n-Hexanol2. Pore Volume 3. The slug was followed by an aqueous solution of 1500 ppm of Dow-Pusher 700 in 0.5% NaCl.DEMONSTRATION VI In the micellar slug formulation typically formulated with petroleum sulfonates of the invention, 3.0% of an active petroleum sulfonate is admixed with 1.5% NaCl in water to yield a cloudy solution. Hexanol (or some equivalent co-surfactant) is then in¬ crementally added, as with a microliter syrine, to attain a visually clear solution. One more drop of hexanol produces a solution separation into two phases. The volume of hexanol added to produce a clear solu¬ tion relative to the total slug volume is referred to as the percent of hexanol uptake. Many workers in the field of enhanced oil recovery via micellar systems use a slug composition formulation near the above-defined clear point as the optimum formulation for maximum oil recovery. Thus, according to presently available information, hexanol (or some equivalent co-surfactant) uptake is generally related to maximum oil recovery and provides a con¬ venient method of determining the relative efficiency of various petroleum sulfonates.As will be appreciated, the less hexanol re- required to reach this optimum point, the more econo- nomical is the particular formulation. It was earlier shown that water treatment of petroleum sulfonic acid produced in accordance with the principles of the in¬ vention reduces the hexanol uptake of micellar system slug formulations formed from such products and yields improved oil recovery. The instant demonstration shows additional parameters involving the principles of the invention.O P7λ „r_ WWIIPP In this test, petroleum oil feed stock de¬ fined in Demonstration V was admixed with 4% (by weight of feed stock) of an oxo-alcohol polymer bottoms (iden¬ tified as U.S. Steel C,Q alcohol bottoms) and the resultant mixture was sulfonated in the laboratory reactor tube earlier described under reaction conditions approximately identical to those utilized earlier.The crude sulfonic acid so-obtained was col¬ lected and a portion thereof was separated into 17 samples, respectively designated VI-A through VI-Z and Vl-Control, which were then further treated (i.e., heated with or without the addition of water) , neutral¬ ized, extracted, formulated into slug compositions and treated with hexanol as described earlier. Pertinent data is set forth below: TABLE I. .t Water % Hexanol (1)Samples Added Temp. (° C.) Time (Min.) UptakeVI-A 0.5 150 60 (2)VI-B 1.5 100 30 0.32VI-C 1.5 150 30 — (2)VI-D 3.0 100 2 0.34VI-E 3.0 100 6 0.30VI-F 15.0 50 2 0.42VI-G 15.0 50 30 0.37VI-G* 15.0 50 30 0.35VI-H 20.0 50 2 0.42VI-1 20.0 50 60 0.40VI-V 7.5 92 5 0.28 >VI-W 7.5 95 3 0.24VI-X 7.5 94 2 0.25VI-Y 5.0 92 3 0.28VI-Z 10.0 93 3 0.25Vl-Control None None None 0.421. Volume % of primary hexanol added to 3.0% Active/1.5% NaCl aqueous micellar solutions to achieve a visually clear point at 25° C.2. Evidence of sulfonic acid decomposition reported duriiιq the* hicfh teimpeπiture As can be seen from the above data, the VI- Control sample (no water treatment) slug required 0.42% hexanol to reach the clear point whereas with an iden¬ tical sulfonic acid provided with an addition of 7.5% water and held at a temperature of 95° C. for 3 minutes (Sample VI- ) only required 0.24% hexanol. The above data exhibits a trend showing that reduced water addi¬ tion (to 0.5%) and increased reaction temperatures (to 150° C.) results in acid deterioration but does show improvements in hexanol uptake. Similarly, the above data indicated a trend showing that increased water addition and increased reaction time at decreased reaction temperatures (Sample VI-F through VI-I) and/or decreased additions of water 'and increased reaction times and temperatures (Samples VI-B and VI-C) result in im¬ provements in hexanol uptake (i.e., less hexanol is re¬ quired) but more optimal results, can be obtained when the previously defined preferred water treatment para¬ meters are selected. DEMONSTRATIO VIIIn another test for hexanol uptake efficiency, the slug formulation was changed to the following:10% active sulfonate 30% total hydrocarbon 1% NaCl59% water and minor amounts of inorganic material. The above slug formulations were then admixed with incremental amounts of hexanol to the clear point as explained earlier.In this test, an amount of petroleum sulfonic acid from Demonstration VI was isolated and divided into ten samples, designated Vll-Control and VII-1 - VII-9,OIKPI' ^ NATIO^ and each sample was then treated and studied for hexanol uptake as described earlier. Pertinent data is set forth below:TABLE JWater Temp. Time % HexanolSample Addition (° C) (Min.) UptakeVll-Control No 0.36%VII-1 No 90 5 0.23VII-2. 5% 90 5 0.15VII-3 7.5% 90 ' • 5 0.11VII-4 10.0% 90 5 0.15VII-5 No 100 5 0.34VII-6 5% 100 5 0.04VII-7 7.5% 100 5 0.03VII-8 10% 100 5 0.15VII-9 No 120 5 0.26As can be seen from the above uptake data, a definite reduction in the amount of hexanol uptake occurs with water-treated samples whereas non-water treated but digested samples (samples heated to reaction temperatures) for an identical period of time as the water-treated samples) show an erratic hexanol uptake.DEMONSTRATION VIIIn order to study the relationship of water treatment relative to the mode of neutralization, an amount of the crude petroleum sulfonic acid from Demon¬ stration VI was isolated and divided into three samples, designated Samples VIII-A, VIII-B and VIII-C, which were then treated as follows:Sample VIII-A - 7.5% of H20 added, heated at 95° C. for 5 minutes and then neutralized with 50% NaOH to a pH of about 10. Sample VIII-B - Non-water treated sulfonic acid added to 50% NaOH until a pH of about 10 was achieved.Sample VIII-C - 50% NaOH added to non-water treated sulfonic acid until a pH of about 10 was achieved. The resulting products were then analyzed and pertinent data is set forth below:TABLE KSample Equivalent Weight % Hexanol Uptake4 41199 0.16VIII-B 401 0.53VII-C 410 0.24As can be seen from the above data, the lowest hexanol uptake is achieved with the water-treated sample, Another indication of an improved sulfonate product is the higher EW for the water-treated sample. The above data also indicates that under these conditions it is preferably to add a base to an acid rather than vice versa. | CLAIMS:1. A method for preparing petroleum sul¬ fonates comprising the sequential steps of intimately contacting from about 5 to 40 parts by weight of sulfur trioxide with 100 parts by weight of a flowable liquid mixture, which comprises on a 100 weight percent total mixture basis: from about 85 to 99.5 weight percent of a petroleum oil feed stock, and from about 0.5 to 15 weight percent of an additive, said petroleum oil stock being characterized by having an API gravity ranging from about 5 to 60° at 60° F., having a boiling point (corrected atmospheric) ranging from about -20° to 1400° F. , and containing from about 10 to 95 weight percent (100 weight percent total stock basis) of sul- fonatable components, said additive being characterized by being comprised of uηsulfonatable organic radical portions possessing an average molecular weight range from about 55 to 6000, having a boiling point in the range from about 212° to 932° F. corrected atmospheric, and a preponderance of such radicals each having attached at least one proton replaceable by a sulfo group and at least one moiety selected from the group consisting of an aromatic nucleus, an olefinic carbon pair, and an oxygen atom directly bonded to a carbon atom by at least one bond, said contacting being con¬ ducted at a temperature of from about 77° to 392° F., said contacting being continued for a time at least sufficient to sulfonate at least about 10 weight per¬ cent of the total sulfonatable components present in said petroleum oil stock so as to attain a crude acidic sulfonation reaction mixture; and intimately contacting said crude acidic reaction mixture with about 0.5% to about 20% by weight, on a 100 weight percent total reaction mixture basis, of water and maintaining the so-attained mixture at a temperature of about 50° to about 150° C. for a period of time ranging from about one minute to about 60 minutes. 2. A method as defined in claim 1 wherein the amount of water brought into intimate contact with the crude acidic reaction mixture is about 2% to about 10% by weight, on a 100 weight percent total reaction mixture basis.. 3. A method as defined in claim 1 wherein the crude acidic reaction mixture-water mixture is main¬ tained at a temperature of about 80° to about 100 °C.4. A method as defined in claim 1 wherein the crude acidic reaction- mixture-water mixture is maintained at said temperature for a period of time ranging from about 2 to about.30 minutes.5. A method as defined in claim 1 including intimately contacting the crude acidic reaction mixture- water mixture attained after step II with a sufficient amount of a base to attain a pH within the resultant mixture in the range of about 3 to 12.6. A method as defined in claim 5 wherein the amount of base brought into intimate contact with said crude acidic reaction mixture-water mixture is sufficient to attain a pH within the resultant mixture in the range of about 6 to 11.7. A method as defined in claim 5 including extracting the base-treated crude acidic reaction mixture- water mixture so as to remove precipitated salts and free oil.8. A method as defined in claim 1 wherein said flowable liquid comprises a film and a continuous reaction takes place. 9. A method as defined in claim 1 wherein said flowable liquid is confined within a reaction vessel and a batch reaction takes place'.10. A method as defined in claim 1 wherein said flowable liquid is confined within a reaction vessel and a continuous adding of reactants, and con¬ tinuous removal of reaction products takes place to effect a quasi-continuous sulfonation.11. A method as defined in claim 1 wherein said petroleum feed stock includes aromatic portions which have a molecular weight in the range of about 200 through about 1000.12. The method of claim 1 wherein said con¬ tacting is continuously accomplished by the steps of forming a flowing liquid film of said mixture on a temperature-controlled reaction surface; impinging. said liquid film with a mixture of gaseous sulfur trioxide and an inert gas so as to attain a sulfonation reaction between sulfonatable components in said film and sulfur trioxide; controlling the reaction temperature so as to maintain said reaction temperature in the range of about 77° to about 392° F. , and injecting about 2% to about 10% water into the so-attained reaction mixture while maintaining the temperature of the resultant mixture in the range of about 50° to 150° C. for a period of time ranging from about 2 to about 30 minutes.13. A method as defined in claim 12 wherein said additive includes at least one C~ to C-0 main hydro¬ carbon chain and is characterized as having a boiling point in the range of about 212° to 932° F.14. A method as defined in claim 13 wherein said additive is selected from the group consisting of unsaturated aliphatic hydrocarbon compounds, substituted and unsubstituted aromatic compounds, olefinic compounds, oxygen-containing compounds, hydroxy-containing compounds, ester compounds, ether compounds, ester-ether compounds, •' ketone compounds, fatty acid compounds and mixtures thereof.15. A method as defined in claim 12 wherein said additive is a C, to C~ R oxygen-containing compound characterized as having a boiling point in the range of about 212° to 932° F. 16. A method as defined in claim 15 wherein said oxygen-containing compound is a hydroxy-containing compound.17. A method as defined in claim 16 wherein said hydroxy-containing compound is a Cβ to C2g alcohol. 18. A method as defined in claim 17 wherein said alcohol'is selected, from the group consisting of hexanol, octanol, nonanol, decanol, octadecanol, do- decanol, lauryl, myristyl, palmityl, stearyl and mix¬ tures thereof. 19. A method as defined in claim 15 wherein said oxygen-containing compound is an oxo alcohol still bottom.20. A method as defined in claim 19 wherein said oxo alcohol still bottom is comprised of about 2 to 20% by weight of octyl alcohol, about 4 to 40% by weight of nonyl alcohol, about 25 to 90% by weight of decyl and higher boiling materials and about 20 to 80% by weight of esters.21. A method as defined in claim 19 wherein said oxo alcohol still bottom is comprised of about 5% by weight of oxtyl alcohol, about 10% by weight of nonyl alcohol, about 35% by weight of decyl and higher boiling materials, about 45% by weight of esters and about 5% by weight of soaps.22. A method as defined in claim 15 wherein said oxygen-containing compound is a phenolic compound.23. A method as defined in claim 22 wherein said phenolic compound is selected from the group con¬ sisting of phenol, C, to C,g alkyl phenols, C, to C,g alkyl C, to C200 alkoxy phenols and mixtures thereof.24. A method as defined in claim 15 wherein said oxygen-containing compound is a glycol compound. 25. A method as defined in claim 15 wherein said oxygen-containing compound is alkoxylated with about 1 to 200 mols of a 0,- to C4 alkylene oxide per ol of oxygen-containing compound.26. A method as defined in claim 15 wherein said oxygen-containing compound is a tallow alcohol.27. A method as defined in claim 12 wherein said additive is a C. to C . Q olefinic hydrocarbon characterized as having a boiling point in the range of about 212° to 932° F. 28. A method as defined in claim 12 wherein said additive is a Cβ to C4Q aromatic.29. A method as defined in claim 12 wherein said additive is a C 4. to C6, ether characterized as having a boiling point in the range of about 212° to 932 ° F.30. A method as defined in claim 29 wherein said ether is selected from the group consisting of 4-methoxy butanol, 2-ethoxy ethanol, 2-propoxy ethanol, 2-butoxy ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol butyl ether and mixtures thereof.31. A method as defined in claim 12 wherein said additive is a C. to C,g hydrocarbon ether ester characterized as having a boiling point in the range of about 212° to 932° F.32. A method as defined in claim 31 wherein . » said ether ester is selected from the group consisting of acetate ester of diethylene glycol monoethyl ether, acetate ester of ethylene glycol monoethyl ether, acetate ester of butylene glycol monoethyl ether and mixtures thereof.33. A method as defined in claim 12 wherein said additive is a C7 to C,Q alkaryl compound character¬ ized as having a boiling point in the range of about 212° to 932° F.34. A method as defined in claim 12 wherein said additive is a C, to C. alkyl ester of a Cg to C2Q aliphatic acid characterized as having a boiling point in the range of about 212° to 932° F.35. A method as' defined in claim 34 wherein said alkyl ester acid is a methyl ester of a C,2 to C, 8 fatty acid. 36. A method as defined in claim 34 wherein said alkyl ester acid is a methyl ester of a Cg to C, Q fatty acid.37. A method as defined in claim 34 wherein said alkyl ester acid is a methyl ester of a C.. to C28 fatty acid.38. A method as defined in claim 12 wherein said additive is a Cg to C2g alkyl ester of a Cg toC28 aliphatic alcohol characterized as having a boiling point in the range of about 212° to 932° F. 39. A method as defined in claim 12 wherein said petroleum oil feed stock is selected from the group consisting of crude oil, topped crude oil and mixtures thereof. BUREAUOΛiPI ^?NAT\0^ 40. A method as defined in claim 1 wherein said amount of the additive in said mixture ranges from about 0.5% to about 5% by weight 'of said petroleum oil feed stocks. 41. A method as defined in claim 1 wherein said amount of additive in said mixture ranges from about 2% to about 10% by weight of said petroleum oil feed stocks.42. A method of claim 1 wherein said-con- tacting is continuously accomplished by the steps of forming a flowing liquid film of said mixture on a temperature controlled reaction surface, said additive being selected from the group consisting of oxo alcohol still bottoms, C. to C2g aliphatic alcohols, alkoxy- lated phenols, diethylene glycol monoethyl ether, alkoxylated nonyl phenols, alkoxylated tallow alcohol, 2-butoxy ethanol, acetate ester of diethylene glycol monoethyl ether, Cg to C,Q alcohols, Cg to C..- fatty acid methyl esters, isopropyl palmitate, hydrogenated12 to C,g fatty acid methyl esters, acetate ester of ethylene glycol monobutyl ether, Cg to C,Q fatty acids, branched chain C,g alkyl benzene, branch chain do- decylbenzenes, palmitic acid, C,. to C.g -olefins, mesityl oxide, acetate ester of ethylene glycol mono- ethyl ether, and mixtures thereof; impinging said liquid film with a mixture of gaseous sulfur trioxide and an inert gas so as to attain a sulfonation reacton between sulfonatable components in said film and sul¬ fur trioxide; controlling the reaction temperature so as to maintain said reaction temperature in the range of about 77° to about 392° F. ; and injecting about 2% to about 10% water into the so-attained reaction mix¬ ture while maintaining the temperature of the resultantJOΛIPI yy. VvViipPoO mixture in the range of about 50° to 150° C. for a period of time ranging from about 2 to about 30 minutes.43. A process of producing, as defined in •' claim 1, petroleum sulfonates having an average equiva- lent weight of from about 35o to 550 and being suitable for use in subterranean oil recovery processes, said contacting being accomplished by the steps comprising: forming a flowable liquid of said mixture on a temperature controlled reaction surface; contacting said liquid with a gaseous sulfur trioxide so as to attain a sulfonation reaction between sulfonatable components in said liquid and sulfur trioxide; controlling the reaction temperature so as to maintain said reaction temperature in the range of about 77° F. to about 392°.F.; and intimately con- tacting said crude acidic reaction mixture with about 0.5% to about 20% by weight, on a 100 weight percent total reaction mixture basis, and maintaining the so- attained mixture at a temperature of about 50° to about 150° C. for a period of time ranging from about one minute to about 60 minutes.44. The process of claim 1 wherein said con¬ tacting is continued for a time at least sufficient 'to produce a sulfonated composition which comprises on a 100 organic weight percent total weight basis from about 5 to 98 weight percent of monosulfonated hydro¬ carbon, from about 0 to 50 weight percent of polysul¬ fonated hydrocarbon, and from about 2 to 90 weight percent of non-sulfonated petroleum.45. A sulfonation product produced by the method of claim 1.46. A sulfonation product produced by the method of claim 12.47. A sulfonation product produced by the method of claim 42. '48. A method for subterranean oil recovery, comprising injecting an oil field with an amount equal to about 1-50% pore volume of said field of a surfactant system comprised of a material selected from the group consisting of water and oil, and containing about 0.001 to 30% by weight of a sulfonation reaction product as* defined in claim 45 and lesser amounts of compatible electrolytes, and other synergistic surfactants. . 49. A method for subterranean oil recovery as defined in claim 48 including injecting said oil field with a mobility control agent after injection of said surfactant system in said field. | STEPAN CHEMICAL CO; STEPAN CHEM CO | KNAGGS E; NUSSBAUM M |
WO-1979000702-A1 | 1,979,000,702 | WO | A1 | XX | 19,790,920 | 1,979 | 20,090,507 | new | F17C7 | F22B1, C10G9, B05B1 | F17C7, F17C9 | F17C 7/04 | ELECTRIC LIQUEFIED PETROLEUM GAS VAPORIZER | A compact economical electrically heated vaporizer (10) having a fast response time and capable of vaporizing liquified petroleum gas at a rate of 37.85 to 151.41 liters or more per hour with safety and without excessive superheating and/or cracking of the liquified petroleum gas utilizes a metal casting (12) having a closed internal cavity separated into two chambers (18 and 20) by an integral barrier (21). The casting (12) serves as a pressure vessel and heat sink as well as providing a heated interface between electric resistance heaters (40) received in passageways (36) in the barrier (21) and the liquified petroleum gas. The heat generated by the heaters (40) is disseminated uniformly throughout the casting (12) surrounding the chambers (18 and 20). A liquified petroleum gas inlet (26) at one end of the casing connects with the end of one chamber (18). Multiple small passageways (30 and 32) in the barrier (21) at the other end of the casting connect the other end of the one chamber (18) to the adjacent end of the other chamber (20). The passageways (30 and 32) are configured to create a turbulent flow which improves heat transfer. An outlet (28) connects with the other end of the other chamber (20) for discharge of the vaporized gas. The electrical and temperature controls for controlling the operation of the heaters (40) and the flow of liquified petroleum gas through the chambers (18 and 20) are housed within an enclosed chamber formed by an end cover (16) on the other end of the casting. The temperature sensors for the temperature controls are received in passageways (38) in the barrier (21). | TITLEELECTRIC LIQUEFIED PETROLEUM GAS VAPORIZERTechnical Field This invention relates to an apparatus for uni¬ formly and economically vaporizing liquefied petroleum gas. Background ArtElectric vaporizers for vaporizing liquefied petroleum gas are known. Such units employ electric re¬ sistance heaters which are directly immersed in storage tanks for the liquefied petroleum gas or which are im¬ mersed in a liquid bath to heat the liquid bath which in turn, heats the liquefied petroleum gas to vaporize the same. U.S. Patent Nos. 2,166,922; 2,193,006; and 2,775,- 683; all disclose the use of electric resistance heaters for vaporizing liquefied petroleum gas, the resistance heaters enclosed directly in the storage tank holding the liquefied petroleum gas. U.S. Patent No. 2,348,546 dis- closes an electric vaporizer in an installation adjacent the liquefied petroleum gas tank through which the lique¬ fied petroleum gas is fed. Direct heating of liquefied petroleum gas described by the above references creates a safety hazard. Additionally, the high temperature of a heating element directly in contact with the liquefied gas causes excessive cracking of the liquefied petroleum gas.Indirect heating of liquefied petroleum gas by water baths, oil baths or other such means performs well when high vaporization capacity is needed; however, for low or medium vaporization capacities such units are both uneconomical and inefficient. DISCLOSURE OF INVENTIONThe primary object of this invention is to pro- vide an electric liquefied petroleum gas vaporizer unit which is compact, economical and safe.-BUKEAi OMPI , W1PO Another object of this invention is to provide an electric liquefied petroleum gas vaporizer utilizing a highly heat-conductive metal casting heated by electric resistance heaters, the casting functioning as a pressure vessel and heat interface between the heat source and the liquefied petroleum gas, as well as a heat sink to uni¬ formly vaporize liquefied petroleum gas.A further object of this invention is to pro¬ vide an electric liquefied petroleum gas .vaporizer cap- able of uniformly vaporizing the liquefied petroleum gas without excessive superheating and/or cracking of the liquefied petroleum gas and which gives superior response time.A further object of this invention is to pro- vide an electric liquefied petroleum gas vaporizer which is capable of vaporizing liquefied petroleum gas to the full capacity of the unit within minutes after it is started.These and other objects are accomplished by a compact, economical vaporizer employing a heat-conduc¬ tive casting having a closed internal cavity bridged by an integral divider dividing the cavity into two separate chambers. The chambers are interconnected at the end op¬ posite the point of entry of the liquefied petroleum gas by multiple passageways of considerably reduced dimension relative to the dimensions of each of the chambers. The passageways increase the efficiency of the unit by creat¬ ing turbulence which promotes heat exchange for more ef¬ ficient vaporization. An inlet opening in the casting for liquefied petroleum gas communicates with one of the chambers and an outlet opening in the casting adjacent the inlet opening communicates with the other chamber. Passageways in the integral divider are provided for installing electric resistance heater units which allow close control of the system. The heat generated by these units is uniformly disseminated by conduction over the 3 surface area of the casting surrounding each of the cham--- bers. Temperature sensing means are included in the casting for maximum control of the power delivered to the electric resistance heaters to' maintain the temperature of the casting uniform.BRIEF DESCRIPTION OF THE DRAWINGSFig. 1 is a perspective view of the vaporizer unit in relation to a storage tank for liquefied petro¬ leum gas; Fig. 2 is a vertical cross section through the vaporizer of Fig. 1 along section line 2-2 of Fig. 1;Fig. 3 is a cross section of the vaporizer unit along section line 3-3 of Fig. 2.; andFig. 4 is a wiring diagram of the vaporizer unit employing three resistance heaters. BEST MODE FOR CARRYING OUT THE INVENTIONReferring to Fig. 1, the vap'orizer unit 10 is shown in relation to a storage tank for liquefied petro¬ leum gas 1. An inlet liquid gas line 2 of sufficient size to supply the vaporizer unit at full flow capacity and accommodate rapid flow changes in or out of the unit with minimum pressure drop extends from the storage tank to the vaporizer unit. Generally the liquefied petroleum gas may be pumped from the storage tank to the. unit by a pump (not shown).The vaporizer unit 10 may be an integral metal casting 12 which is of a highly heat conductive material such as aluminum. The casting may be jacketed with one or more layers of a heat insulating material if desired. The casting is supported on legs 14 which are secured to a concrete pad or other suitable support. Liquefied gas enters the vaporizer unit through line 2 and is heated during its passage through the casting and exits the unit as a gas vapor through outlet line 3 which is directly above the inlet line 2. If desired, the inlet and outlet to the casting can be reversed. The casting may beiϊuκε-urOMPI A 'A,r__ WW11PPOO .*£ 4 mounted horizontally or vertically. A pressure relief valve 4 is threaded through the casting 12 to communicate with the interior of the vaporizer unit for safety pur¬ poses. An outlet solenoid valve 5 connects to gas vapor outlet line 6 as illustrated. This outlet valve acts as a safety device and prevents vapor flow from the outlet line beyond the valve until the unit is properly operating. The valve closes if the unit functions im- properly. The electrical wiring for the solenoid is op¬ eratively connected to the controls for the unit through a conduit (not shown). Other types of control valves may be used if desired.All of the electrical components for control of the unit as well as the wiring therefor are housed within end cover 16 located at the opposite end of the casting from the liquid gas inlet and gas vapor outlets 2 and 3. In this way all of the wiring is enclosed and is totally out of contact with any liquid gas or gas vapor. The start and stop push buttons 7 and , 8 for the unit are lo¬ cated within the support leg 14 adjacent the end of the casting where the electrical controls are located. By locating all of the wiring and electrical controls inter¬ nally in the unit the end cover 16 can be readily removed for servicing of the unit without having to cut or remove any wiring.Fig. 2 illustrates a vertical cross section of casting 12. The casting is cylindrical and may be symme¬ trical about its vertical and horizontal axes. The shape of the casting is not critical, however, and may be of any desired configuration. The casting has an internal cavity separated into two chambers 18 and 20 by an inte¬ gral divider 21. As illustrated the chambers 18 and 20 are of equal size although this is not critical. The openings 22 and 24 at the end of the casting adjacent the end cover 16 are plugged with a suitable material so that no gas flow can escape the casting. Liquid gas inlet pipe 2 is threaded into the lower opening 26 and gas va¬ por outlet pipe 3 is threaded into the upper vapor outlet 28 of the casting as illustrated in Fig. 2. The two com- partments 18 and 20 within the casting are interconnected by passages 30 and 32 which are of considerably reduced size relative to the size of the compartments 18 and 20. The passages 30 and 32 are configured to create a turbu¬ lent flow of the gas or gas-liquid mixture in the casting to aid in heat transfer from the walls of the casting to the liquefied gas. As illustrated in Fig. 2 each of the passageways is wedge-shaped. •The integral divider 21 separating the internal cavity of the casting into the two compartments 18 and 20 includes integral multiple fins 34 extending from the divider respectively.into the chambers 18 and 20. The fins 34 expose a greater amount of the surface area of the casting to the liquefied gas being introduced into the internal cavity of the casting to aid in heat trans- fer. The integral divider 21 also includes multiple bore openings 36 extending the length of the casting between the passageways 30 and 32 interconnecting the chambers 18 and 20. These passageways are designed to receive elec¬ tric resistance heaters as will be described. One or more additional bore openings 38 are provided in the in¬ tegral divider of the casting between the passageways 36. These passageways 38 are designed to receive temperature sensing means, the temperature sensing means connected to control means for controlling power to the electric re- sistance heaters. A liquid gas carryover sensor 39 ex¬ tends into the upper chamber 20 through the plug in open¬ ing 22 to sense, by measurement of temperature, liquefied gas carryover from the unit.One or more electric resistance heater units 40 enclosed in a sheath of the same diameter as the diameter of passageways 36 is inserted in the passageways as il- lustrated in Fig. 2. A close fit of the electric resis¬ tance heater in the casting is desired to insure maximum heat transfer between the resistance heater and the cast¬ ing. The close fit also plugs each of the passageways 36 to maintain the explosion-proof condition of the electri¬ cal system of the unit. A ledge 33 at the end of each passageway 36 keeps the resistance heater from being pro¬ jected from the casting, should an explosion occur.The vaporizing unit is capable of readily meet- ing the demand for vaporization capacities ranging from- 37.85 to 151.41 or more liters per hour. The same cast¬ ing can be used for vaporization of 37.85 liters per hour as for' 151.41 liters per hour. The only difference in the units is in the number and size of electrical resis- tance heaters utilized. For example, a unit capable of vaporizing 37.85 liters per hour utilizes one 2.5 kw ele¬ ment. A unit vaporizing 75.71 liters per hour utilizes two 2.5 kw elements and a unit vaporizing 113.56 liters per hour utilizes three 2.5 kw elements. A 151.41 liters per hour unit would employ three 3.25 kw elements, etc.Each of the electrical resistance heaters 40 is connected to a source of electrical power through control and safety relays which are interconnected with the tem¬ perature sensing means to insure proper operation of the unit. Fig. 4 illustrates a wiring diagram for the vapor¬ izer unit.. Resistance heaters 40 are connected through contacts 41, 42 and 43 of control relay 44 and contacts 45, 46, 47 and 48 of safety relay 49 to a source of suit¬ able voltage such as a source of single phase 240V, 50/60 Hz power or three phase power. The unit is started by allowing liquefied gas to flow into the lower chamber 18 of the unit and depressing switch 7 until the unit has warmed to operating temperature (about 43.33°C). When the switch 7 is released solenoid outlet valve 5 is ac- tuated to allow vapor flow through line 6. Temperature sensing means connected to operating temperature switch-BUKhOMPI 51 retains the switch in closed position until the maxi¬ mum operating temperature (about 98.89°C.) is reached. When the switch 51 closes it deactivates control relay 44 to open contacts 41, 42 and 43 to disrupt current flow to 5 the resistance heaters 40. A high temperature sensing means is positioned in the casting and set at a predeter¬ mined temperature (such as about 148.89°C). If the tem¬ perature of the casting exceeds the predetermined temper¬ ature safety switch 52 opens, interrupting current to10. safety relay 49, resulting in opening of contacts 45, 46, 47 and 48 to interrupt power to the heaters 40. When any of the safety limits are reached, solenoid valve 5 closes. Manual restart of the unit is required. A liquefied gas carryover switch 53 connected to sensor 3915 in the casting remains open until it senses the absence of liquid. The safety switch 53 is manually bypassed during startup.The vaporizer is started by allowing liquefied petroleum gas to flow into the lower chamber 18 of the20 vaporizer unit through the inlet line 2. The vaporizer unit is warmed up to minimum operating temperature by pressing the start switch 7 as previously mentioned and holding it for two to three minutes. When the start but¬ ton is released the outlet solenoid valve 5 opens to al-25 low gas vapor to exit the vaporizer unit through gas va¬ por line 6. The flow of gas vapor at full capacity of the unit is generally available five minutes after the start switch is initially depressed. Should, for some reason, the temperature of the unit exceed the preset temperature30 of the high temperature switch which is generally about 148.89°C. the power will be disconnected to the electric resistance heaters. The liquid carryover switch 53, pre¬ viously described, provides an extra safety measure. Should liquefied gas be sensed, solenoid valve 5 closes,35 power to the electric resistance heaters is disrupted and manual restart is required. The liquefied petroleum gas enters the lower chamber as a liquid and is heated to its vaporization point. The passageways 30 and 32 between the upper and lower chambers are small enough to create turbulence and disperse the liquefied gas into small droplets which rapidly flash to gas vapor as the liquefied gas flows through the passageways. The upper chamber further heats the vaporized gas to a .proper superheated condition. The unit is stopped by pressing switch 8 to deactivate relays 49 and 44, outlet valve 5 and heaters 40.The unit as described is a compact versatile unit for vaporizing liquefied petroleum gas employing a heat sink in the form of a highly heat conductive metal casting also serving as a pressure vessel and heat inter- face between a source of heat and the liquefied petroleum gas.. Flow surges can be readily accommodated.. Excessive superheating of the liquefied petroleum gas is prevented by the relatively low temperature of the heat sink in contrast to direct contact of the liquefied petroleum gas with a heat source which causes cracking of the gas, re¬ sulting in polymerization, tarry residues and undesired components to form. The unit can go from no load to full load almost instantaneously — a matter of seconds and can thus quickly respond to load changes.OMPI | CLAIMS:1. A compact economical electric vaporizer unit for vaporizing liquefied petroleum. gas comprising: a heat-conductive casting having an internal cavity bridged by an integral divider dividing the ca¬ vity into separate chambers, multiple passageways through one end of the divider interconnecting the separate chambers, the pass¬ ageways of considerably reduced dimension relative to the dimension of each of the chambers, a liquefied petroleum gas inlet opening in the casting spaced from the multiple passageways and communi¬ cating with one of the chambers, a gas outlet opening in the casting adjacent the inlet opening and spaced from the multiple passage¬ ways communicating with the other chamber, one or more passageways in the integral divider holding electric resistance heater units, c-ne or more temperature sensing ports in the casting including temperature sensing means, electric power means connected to the electric resistance heaters, and control means operatively connected to the sensing means and electric power means for maintaining the temperature of the casting uniform.2. The vaporizer of claim 1 wherein the inter¬ ior surface of each of the chambers includes fins to in¬ crease the overall surface area to which the liquefied petroleum gas entering the chambers is exposed. 3. The vaporizer of claim 1 wherein the cast¬ ing is symmetrical about its vertical and horizontal axes.4. The vaporizer of claim 1 including an end cover sealing the exposed ends of the electric resistance heater units and control means therefor.5. The vaporizer of claim 1 wherein the cast-OMPI ing is an aluminum casting.6. The vaporizer of claim 1 wherein contact of the electric resistance heaters with the casting is such as to insure maximum heat transfer between the electric resistance heater units and the casting.7. The vaporizer of claim 1 wherein .the tem¬ perature sensing port and sensing means are located be¬ tween the electric resistance heater units.8. The vaporizer of claim 1 wherein the cham- bers are of equal volume and wherein the multiple pass¬ ageways are configured to minimize liquid petroleum gas carry-over and create turbulent flow of the liquefied petroleum gas as it passes from one chamber to the oth¬ er. 9. The vaporizer of claim 1 wherein the cen¬ tral cavity provides a labrinyth passageway leading to the outlet opening for vaporizing liquefied petroleum gas introduced into the inlet opening.10. A compact economical vaporizer having a vaporization capacity of ten to forty gallons of lique¬ fied petroleum gas per hour or more, comprising: a heat-conductive aluminum casting having an enclosed central cavity bridged by an integral divider dividing the central cavity into at least two separate vaporization chambers, multiple passageways interconnecting the two chambers, the passageways of considerably reduced dimen¬ sion relative to the dimension of each of the vaporiza¬ tion chambers, a liquefied petroleum gas inlet opening in the casting at the opposite end of the casting from the mul¬ tiple passageways communicating with one of the cham¬ bers, a gas outlet opening in the casting adjacent the inlet opening communicating with another of the cham¬ bers,BUO W1 11 passageways in the integral divider, each hold¬ ing an electric resistance heater unit, . temperature sensing passageways in *he casting adjacent the electric resistance heaters including tem¬ perature sensing means, electric power means connected to the electric resistance heater units at the end of the casting oppo¬ site the inlet and outlet openings, control means at the end of the casting oppo¬ site the inlet and outlet openings operatively connected to the sensing means and electric power means for main¬ taining the temperature of the casting uniform, and an end cover sealing the exposed ends of the electric resistance heaters and control means. | DICK IND INC SAM; SAM DICK IND INC | DENSMORE B; DRAGOY J |
WO-1979000706-A1 | 1,979,000,706 | WO | A1 | XX | 19,790,920 | 1,979 | 20,090,507 | new | B23Q3 | null | B23B31, B23Q3, B60B30 | B23B 31/40C1, B23B 31/40C2B | WORKPIECE HOLDER | A workpiece holder for supporting an annular workpiece (34) such as a tire for a vehicle. The holder (10) includes a plurality of elements (27) movable radially outwardly into engagement with an inner surface of an annular workpiece (34) in response to movement of a cam (32). The gripping force applied to the inner surface of the tire by this arrangement is only slightly greater than that required to support the tire carcass thus overcoming the problem of core breakage. | DescriptionWORKPIECE HOLDERBackground of the InventionThis invention relates to a workpiece holder for supporting an annular workpiece by engagement between radially extending elements of the workpiece -holder and the inner surface of the workpiece.In one process of making large tires fo'r earth oving vehicles, layers of rubber and wire are .applied to the surface of a toroidal shaped hollow and core which remains within the tire carcass during the construc¬ tion of the tire. The sand core is eventually dissolved as one of the final steps in making the tire. The sand core is somewhat fragile and care must be taken so as not to apply excessive force thereto during the manufac¬ turing operations. Excessive force could crush or otherwise cause the sand core to fail.In the latter steps of the manufacturing process, tire materials, such as uncured rubber, breaker plys and belts are applied to the tire carcass as it is being rotated about its axis. Heretofore, the carcass has been supported during such rotation by an apparatus having shoes which . grip the„outer of the carcass, during application of materials to the sidewalls. Application of tire materials to the crown area of the tire involves other fixturing and a separate carcass handling step. This is both time consuming and adds to the manufacturing cost.Thus it is desirable to support the tire ~_ ) _ carcass by gripping the inner surface so that tire mate¬ rials can be applied to both the sidewalls and the crown area. One of the problems with gripping the tire carcass from the inside is that the sand core is more prone to_OMPI -2-breakage if excessive force is applied to the inner surface or if the force is applied unequally. Preferab the gripping force applied to the inner surface should only slightly greater than that required to support the 5 tire carcass. However, this creates another problem in that normally-one support apparatus is used for several sizes of sand cores wherein the weight of the carcass _.-_. -varies thereby requiring different gripping forces for each of the several sizes.10 Summary of the InventionThe present invention is directed to overcomi one or more of the problems as set forth above.According to the present invention, this is accomplished by providing a workpiece holder having a15 plurality of elements slidably maintained by a support structure and which extend radially relative to a longi tudinal axis of the support structure. A cam engages the inner ends of the elements and movable along the longitudinal axis between a first position at which the20 ■ elements.are retracted and a second position at which t elements are extended into engagement with an inner surface of an annular workpiece..Brief Description of the DrawingsFig. 1 is a diagrammatic elevational view of 25 workpiece holder embodying the present invention.Fig. 2 is a sectional view taken along the li II-II of .Fig. 1.Detailed DescriptionReferring now to the drawings, a workpiece ho 30 10 includes a support structure 11 having a spindle 12 extending into preferably a hollow member 13 of a mount frame 14. The spindle 12 is rotatably connected to the BUREOMPI member 13 by a pair of bearings 16, 17. The spindle 12 extends from a hub 18 and has a bore 19 therein extending along a longitudinal axis X . The bore 19 is concentric with an opens into a bore 21 in hub 18. A plurality of spokes 22 are connected to the hub 18 and extend radially outwardly therefrom. Each of the spokes has a bore 23 therein opening into bore 21 of the hub 18. A bearing 24 is positioned with in each of the bores in the spokes. A plurality of elements, preferably rods 26,- are individually slidably -positioned within the bearings 24 in bores 23 of spokes 22. Each of the rods 26 has an arcuate shoe 27 connected to i'ts outer end portion with each shoe 27 having a resilient pad 28 on the outer surface. Each of the rods 26 has a roller 29 rotatably connected to the inner end portion thereof. A plurality • of springs 31 are individually connected to the shoes 27 and to the hub18 for resiliently retracting the rods 26 from an extended position shown in the drawings toward the longitudinal axis X .A circular cam 32 is slidabl positioned within the bore 21 and has a convex cam surface 33 in engagement with the rollers 29. The cam 32 is movable along the longitudinal axis X between a first position at which the rods 26 are at a retracted position and a second position at which the rods 26 are extended into engagement with an inner surface of a workpiece indicated at 34.The convex cam surface 33 is defined as a surface of revolution in which a curved line is revolved about the axis X . In the present instance, the curved line is an arc having a radius R .A means 38 is operatively connected to the cam 32 for moving the cam between the first and second posi¬ tions. The means 38 can be, for example, a fluid cylinder 39 and a spring 41. The cylinder 39 is connected BUREAOMPI fa WIPO to the hollow member 13 and has a.piston rod 42 extendin into the bore 19. The piston rod 42 is screwthreadably connected to one end of a rod 43 which has its other en connected to the cam 32 by a pair or .bearings 44. The bearings 44 provide for relative rotation between, the c 32 and rod 43. The spring 41 is preferably a constant rate spring and exerts a force on the piston rod 42 and rod 43 for urging the cam 32 toward its second position Selective introduction of fluid into a chamber 46 of th cylinder moves the piston rod 42 and hence the cam 32 t its first position.A means 47 for rotating the support structure 11 relative to the mounting frame 14 includes a motor means 48, a drive sprocket 49 connected to the motor means, a sprocket 51 on the spindle 12 and a chain 52 entrained around the sprockets.A plurality of arms 53 are pivotally connecte to* brackets 54 of the mounting fr'ame 14. Each of the arms 53 is movable from a first position at which a dis end portion 56 is at a position for' locating the workpi 34 relative to the shoes' 27 as shown by the solid lines the drawings and a second position at which the distal end portion 56 is free of contact with the workpiece, as shown by the phantom line in Fig. 1. In use, fluid is introduced into the chamber- to retract the piston rod 42 of the cylinder 39 against the bias of spring 41. This in turn moves the cam to i first position at which the rods 26 are retracted by th springs 31. With the arms 53 at their first position, the workpiece 34 is positioned so that the inner surfce encircles the shoes 27. The fluid is then vented from the chamber 46 so that the spring 41 exerts a force against the piston rod 42 which in turn moves the cam 3 toward its second position. This movement of the cam causes the rollers 29 to follow the convex cam surface of the cam thereby extending all the rods 26 simultaneous¬ ly so that the shoes 27 engage the inner surface of the workpiece and center the workpiece 34 relative to the axis X . The relative position of rods 26 on the convex cam surface 33 and the available force of the spring 41 at the instantaneous position of cam 32 determines the amount of radial force being exerted against the work- piece. Specifically, the convex cam surface functions as a variable angle ramp such that the ramp angle decreases as the cam moves toward the second position. The increase in radial force caused by the decrease in ramp angle more' than offsets the decrease in radial force caused by the decrease in the available force of the spring 41 as it expands with the net result being that the force exerted by the rods increases as the rods are extended in response to the cam moving to its second position. Thus, the force exerted against the workpiece increases as the diameter of the inner surface of the workpiece increases. Since the diameter of the inner surface is generally indicative of the size and weight of the workpiece, a greater force is automatically exerted against a larger and heavier workpiece while a lesser force is exerted against a smaller and lighter workpiece. Prior to rotating the support structure 11 and hence the workpiece 34, the arms 53 are moved to their second position.To remove the workpiece 34 from workpiece holder 10, .fluid is again introduced into chamber 46 for moving cam 32 to its first position.In view of the foregoing, it~ Ts readily apparent that the structure of the present invention provides an improved workpiece holder for supporting an annular workpiece. The rods are moved radially outwardly in unison by the cam so that the force exerted by the rods is uniformly distributed against the inner surface of the workpiece. Further, since the amount of radial force exerted against the inner surface by the rods increases as the rods are extended, a greater force is automatically exerted against a larger heavier workpiece than is exerted against a smaller lighter workpiece. Thus, the workpiece holder can suitably support any of several sizes of workpieces without any modification or adjust¬ ment thereto during changing of workpiece sizes. Other aspects, objects and advantages of this invention can be obtained from a study of the drawings, the disclosure and the appended claims.l-ΛJREΛ | Claims1. A workpiece holder for supporting an annular workpiece (34) having an inner surface characterized by a support structure (11) having a longitudinal axis X ; a plurality of elements (26) having inner and outer end portions and being slidably maintained by said support structure; a cam (32) engaging said inner end portions of said elements and being movable along the longitudinal axis between a first position at which the elements are at a retracted position and a second position at which the elements are extended into engagement with said inner surface of the workpiece; means (38) for moving the cam'between said first and second positions; and a bearing (44) rotatably connecting said cam moving means (38)to said cam (32).2. The workpiece holder of claim 1 wherein said cam (32) has a convex camming surface (33) , said inne end portions of the elements being in contact with the • convex cam surface, and wherein, preferably, said cam moving means (38) includes means for exerting a force against the cam for moving the cam from the first position to the second position.3. The workpiece holder of claim 2 wherein said force exerting means includes a constant rate spring (41) , said cam moving mean's includes a fluid cylinder (39) connected to said cam for moving the cam from the second position to the first position.4. The workpiece holder of claim 1 wherein said support structure (11) includes a bore (21) concentric with said axis, said cam (32) being slidably positioned within said bore, and wherein, preferably, said support structure includes a plurality of spokes (22) each having a bore (23) extending radially relative to said axis, said elements being rods (26) slidably positioned within the bores in the spokes .5. The workpiece holder of claim 1 wherein the outer end portions of the elements each include an arcuate shoe (27) , . wherein, preferably, the inner end portions of the elements each include a roller (29) rotatably connected to the element and rollably engaging said cam, and wherein, preferably, resilient means (31) are connected to the elements for moving the elements to the retracted position in response to the cam being moved to said first position.6. The workpiece holder of claim 1 includin mounting frame (14) , means for rotatably σonnecting th support structuie to the mounting frame, and means (48) for rotating the support structure relative to the mounting frame.7. The workpiece holder of any of claims 1-6 including a plurality of arms (53) pivotally connected to said frame and having distal end portions, said arms being movable between a first position at which said ddstal end portions are positioned for engagement with said workpiece and a second position a which the distal ends are at a position free of contac with the workpiece.8. The workpiece holder as claimed in claim2 wherein said convex cam surface (33) functions as a variable angle ramp such that the ramp angle decreases the cam moves from a first positon towards a second pos 9. The workpiece holder as claimed in claim 1, wherein said support structure (11) comprises a spindle (12) extending into a hollow member (13) of a mounting frame (14) , said spindle is rotatably connected to said member by bearing means (16, 17) , extends from a hub (18) , and has a first bore (19) therein β.tending along said longitudinal axis, said bore (19) being concentric with and opens into a second bore (21) in said hub, said plu¬ rality of elements, preferably rods (26) , are individually slidably positioned within bearings (24) and are indi¬ vidually associated with a plurality of springs (31) for resiliently retracting the rods (26) from an extended position toward said longitudinal axis, and a fluid cylinder (39) .is connected to the hollow member and has a piston rod (42) extending into said first bore (19) ,* said piston rod being connected to one end of a rod (43) which has its other end connected to said cam by said bearing (44) .10. A tire carcass holder, characterized by - the features of one or more of the preceding claims. | CATERPILLAR TRACTOR CO | DENNIS R |
WO-1979000722-A1 | 1,979,000,722 | WO | A1 | EN | 19,791,004 | 1,979 | 20,090,507 | new | B65D41 | B65D21 | B65D17, B65D43 | B65D 17/20, B65D 43/02S3D, L65D 101/00A7, L65D 543/00Y10B2, L65D 543/00Y1F2C, L65D 543/00Y1M6, L65D 543/00Y8D1E, L65D 543/00Y8D3N, L65D 543/00Y8S1B2, L65D 543/00Y8S1D2, L65D 543/00Y8S3B4, L65D 543/00Y8S3B8, L65D 543/00Y8S3D2 | CONTAINER WITH SIDE WALL,COVER AND TEARING DEVICE PRODUCED AS A UNIT | Container unit produced in one piece e.g. by injection moulding of plastics and comprising a side wall (2), a circumferential tearing strip (4) and a closure (1). The container unit is closed after filling from the bottom by means of an attached bottom (3). The tearing strip (4) is positioned between the upper edge of the side wall and the closure so that after the tearing off of the strip a frame (7) is left on the underside of the lid which frame fits inside the upper edge of side wall, whereby an individual fit is obtained by every single container. Consumption of material for a separate lid to be used by reclosure is avoided. The tearing strip (4) bordered by weakening lines (6) is removed by a radial pull in a protruding pulling flag (5). The pulling flap (5) has a sealing string (14) connected to the closure (1) so that even if the lid is put on it can be observed that initial opening has taken place. The upper surface of the lid has a protrusion (11) to serve as a grip for the fingers when the lid (1) shall be lifted. Protrusion (11) on the upper surface of the closure of a container unit rests against an internal shoulder of another container when they are stacked. The frame of the lid and the edge zone of the side wall may have complementary holding members for example with spring locking effect. | Container with side wall, cover and tearing device produced as a unit.Technical field of the inventionThe invention relates to a container with side wall, cover and tearing device for the cover produced as a unit to be closed after filling by means of a separately produced bottom.Technical backgroundFrom the Danish patent specification No. 127,376 an injection moulded container of plastics comprising on one hand a container part with a container body, an aperture and a tearable closure and on the other hand a bDttαm part is known. The cross-section of the container diminishes from the bottom to the closure which can be torn open without the use of tools. The container units are shaped in a way allowing stacking.The tearing device of the known container unit is a circular tearing strip situated in the upper top face of the container. The tearing strip is bordered by- weakening lines in the material and has. a grip ring by means of which the ringshaped strip and that part of the closure surrounded by the strip can be torn from. he container. After the opening of the container a lid can be put on the upper protruding ridge around the aperture. The known container offers important advantages as it consists of only two separate units viz. a container unit and a bottom unit, which units after filling from the bottom are united suitably by friction welding. The container is opened by pulling the ring in the axial direction and after the tearing of the closure the separate lid can be put on.Disclosure of the inventionThe present invention is based on the recognition that in spite of the advantages of the known container in relation to those known previously it suffers from a number of disadvantages in the production as well as in use.The invention aims- at the solving of the problem to devise. a 'container construction, which is less resource demanding, simpler to produce and more consumer-friendly. According to the invention, the problem is solved thereby that the tearing device is a circumventing tearing strip around the container wall between its upper edge and the lower edge of a frame around the closure, which after the removal of the tearing strip is adapted to fit into the upper edge zone of the con¬ tainer wall as a reusable lid.In the construction according to the present in¬ vention, the closure and the lid are combined to a single part, whereby the resource consumption becomes less. Further, a circumferential protruding edge around the container opening, which in the known con¬ struction is necessary for several reasons, is avoided. This also reduces the consumption of material, especi¬ ally in the case of containers having large openings, for example buckets or tins for paint.Further, circumferential irregular protrusions occurring when the closure is broken by tearing, and which is troublesome especially when pouring viscose liquids is avoided. Seen from the point of view of moulding technic, the container according to the invention offers the___ . v.i- advantage that the material, which normally is introduc¬ ed into the mould at a place situated centrally in the top surface of the closure, shall not move upwards as well as downwards when it is leaving the surface of the clo- sure.By the construction according to the invention, another problem by containers which have to be closed by a lid after the opening is solved at the same time. When container and lid are produced .completely separate- ly or just connected by a single string of material, it often happens that lid and container do not fit together even if there has been shown great diligence 'by the production of the forms. This is due to the small va¬ riation in material and in the production procedure. When the lid and that part of the container, on which the lid shall be fitted, are produced in one piece, these irregularities will have no effect, and the lid will always fit the container.In a suitable embodiment of the container unit according to the invention, the frame of the lid and the upper edge area of the container wall have mutually complementary holding means resulting in the necessity of exerting greater force by the removal of the lid, so that the risk that the lid falls off, if the con- tainer is tipped over, is less. The holding means can be corresponding circumferential protrusions contacting each other with spring-lock effect.It is an advantage that the tearing strip has an integral pulling member offering a safe grip for exert- .ing a radial pull in the tearing strip. Such a radial pull will in general give a better control over the opening procedure than the axial pull, which is to be exerted in connection with the known container.In order .to ease the removal of the reusable lid, the container unit is suitably designed, so that the upper, surface of the lid at least in some places protrude beyond the frame to form a grip for the fingers.The construction according to the invention opens up the possibility in a simple way to produce a sealing, so that the consumer can check whether the container has been opened before. This is expediently obtained by means of a sealing string produced integrally with the lid and the pulling device, which string automatically tears when the pulling device is actuated for opening of the container. In connection with container units of plastics having continuously dimishing cross-section from the bottom to the lid allowing several identical container units to be stacked, it is normal to provide the wall of the container with stacking protrusions on the in- side, so that it is avoided that the stacked container units to be conveyed separately to a filling machine are sticking together owing to the close contact. Such stacking protrusions occurring as local thickening of the wall often results in suckings showing as depres- sions in the outer side of the container wall. Such de¬ pressions destroy the appearance of the container and make it difficult to put printed matter or decoration on the wall. This disadvantage can be avoided in a con¬ tainer unit according to the invention by designing the upper surface of the lid protruding above the frame, preferably a radial flange, so that by stacking it will contact a corresponding shoulder at the inside of the adjacent container situated in such a place that the two adjacent container units cannot be pushed so close together that jamming or sucking occurs by the separa¬ tion. Because the shoulder is only produced by inturn- ing of the material in the wall without changing the thickness of the wall, no suction problems will arise. The' flange on the upper surface of the lid further protects the pulling device and prevents that it is in the way by the stacking.^ _~\} List of Figures, short description of an embodiment.The invention is explained in detail in the following by reference to an example of an embodiment of a container unit according to the invention and with referende to the drawing, in whichFig. 1 shows a container unit according to the invention seen in perspective,Fig. 2 a longitudinal cross-section of a container unit according to the invention with closure and container wall and tearing strip between closure and wall,Fig. 3 an axial cross-section through a separate bottom to be put on the container unit,Fig. 4 an axial cross-section through two container units stacked one into the other,Fig. 5 an axial cross-section through a container unit with mounted bottom and with the container lid put on the container after removal of the tearing strip, arid Fig. 6 two with bottom assembled containers stacked one upon the other.The drawing shows a container with a lid 1 and a tapering side wall 4 and a bottom 3. The container is produced by injection moulding of plastics in two units, one of which is shown in Figs. 1 and 2 and comprises the closure 1, the wall 2 and the intermediate tearing strip 4 with a pulling flap 5, by means of which the closure 1 can be removed from the container wall 2. • The tearing strip' 4 is produced with weakening lines 6, which can be more or less discontinuous in order to create suitable flowing paths for the plastics between closure and wall during the moulding. On the under side of the lid 1 is a circumferential -frame 7 having an outwardly projecting wedge shaped rib or bead 8 the whole way around and designed for meshing the lower edge 9 of a narrowed edge zone 10 in the upper part of the container wall 2 when the lid after removal of the 5 tearing strip is put on the container.Flush with the upper side of the lid is an outward protruding flange 11 and the container wall2 is designed with an inward going part 12 forming a shoulder 13 against which the flange 11 of the10 lid can rest when several container units are stacked within each other as shown in Fig..4 in the' usual way to save room by the storing and transport of this kind of container units.Between the pulling flap 5 and the flange 715. is moulded a sealing string 14 which is broken when the tearing strip 4 is removed by pull in the pulling flap. The sealing string 14 is weakened at the pulling flap so that after having been broken it remains on the flange 7 as shown in Fig. 5,20 thereby indicating that the container has been opened even if the lid 1 rests on and closes the container. As can be seen in Fig. 4 the flange 7 and the narrowed upper part of the container form a space for the pulling flap 5 so that this does not get in25 the way by the stacking of the container units.As can be seen in Fig. 2 the container wall 2 has below a circumferential groove 15 corresponding to an upwards protruding rib ' 16 along the circumference of the bottom 3 as can be seen in30 Fig. 3. When the container has been filled in a position with the closure facing downwards, the bottom3 is put on the container unit with the rib 16 within the groove 15, and these units are welded together preferably by friction welding.35 The bottom 3 has a depression 17, Fig. 3, which corresponds to the top surface of the lid inclusive the flange 7, so that filled containers can be put one upon the other in a stable stack as shown in Fig. 6.The container units can be filled up to a volume corresponding to the lower edge of the tearing strip 4 on the complete container even with a foaming fluid owing to the auxiliary container volume derived from the height of the tearing strip and the frame 7.-BUREAU-?____ | PATENT CLAIMS 1. Container with side wall, cover and tearing device produced as a unit to be closed after filling by means of a separately produced bottom, characterized in that the tearing device is a circumventing tearing strip (4) around the container wall (2) between its upper edge and the lower edge of a frame (7) around the closure (1) , which after the removal of the tearing strip (4) is adapted to fit into the upper edge zone(10) of the container wall (2) as a reusable lid. 2, Container unit according to claim 1, characterized in that the frame (7) of the lid and the upper edge zone (10) of the container wall have mutually complementary holding means (8, 9).3. Container unit according to claim 1 or 2, characterized in that the tearing strip (4) has a pulling flap (5) for manually opening of the container by a radial pull.4. Container unit according to claim 1, 2 or 3, characterized in that the upper surface of the.lid at least in some places (11) protrudes beyond the frame (7) to form a grip for easing the removal of the lid.5. Container unit according to claim 1, 2, 3 or 4, characterized by a sealing string (14) produced integrally with the lid (1) and the pulling flap (5) .6. Container unit according to claim 3 or 5 produced in plastics and with a continuously decreasing cross-section from the bottom to the lid, so that several identical container units can be stacked, - characterized in that the upper surface of the lid protruding beyond the frame, referably a radial flange(11) is designed so that by stacking it rests against a correspondingly designed circumferential shoulder(13) inside the adjacent container and situated so that two adjacent container units cannot be pushed one into the other so that a jaming or sucking occurs by the separation.lϊURE-t ________ 'WilO | HARILD N; LEGARTH HARILD PACKING & MACHI; LEGARTH HARILD PACKING & MACHINERY SA | HARILD N |
WO-1979000726-A1 | 1,979,000,726 | WO | A1 | XX | 19,791,004 | 1,979 | 20,090,507 | new | F24H1 | F24H1 | F24H1, F28D7 | F24H 1/22, F24H 1/40 | BOILERS FOR HOT WATER | A hot water boiler, particularly for central heating and hot water supply in small dwellings where an economic unit with an output less than about 0.3 megajoule/hr (30,000 but/hr) is required, has a compact cylindrical heat exchanger (110) with central combustion chamber (20) and forced draught. Water circulates through double-pass longitudinal waterways (12) in the monobloc heat exchanger body (111), in crossflow relationship to hot gases forced through short, narrow, annular radial passages (23). One or more walls (22) separating these passages may be replaced by a hollow wall within which water can circulate, increasing the heat exchange surface available. | - -BOILΞRS FOR HOT WATER'Technical Field The technical field of this invention comprises • boilers for producing hot water, and heat exchangers suitable for use in such boilers, whether incorporated in a boiler or not.More specifically, the invention relates to heat exchangers for indirect heat exchange between a first fluid medium and a second fluid medium, the heat exchanger comprising a generally cylindrical hollow body having longitudinal passage means for said second fluid medium, said'heat exchanger being adapted for flow of said first medium within the hollow body away from the axis of said body and towards its circumference and having a heat exchange matrix through which the first medium must pass during such flow and through* hich said longitudinal passage means extend. Such a heat exchanger will be referred to herein as a heat exchanger of the kind, hereinbefore specified . The invention further relates to boilers for producing hot water, such a boiler including a heat exchanger of the kind hereinbefore specified and being adapted for use in a central heating system, or for. producing hot water for other purposes, or both;, and to central heating systems including such a boiler. Background ArtHot water boilers for production of domestic -hot water or hot water for a central heating system, conventionally comprise a segmental, cast-iron hear exchanger which is typically of a somewhat rectangular configuration and which has a combustion zone belov: it. Fuel, such as gas or oil, and air are fed to a burner in the combustion zone and there burnt so that the hot combustion gases rise generally upwardly through the heat exchanger, to be discharged, typically, at the top or at the back of the latter. In such a heat exchanger, the water passages may follow any desired or convenient path usually partly horizontal and partly vertical. Boilers of this conventional kind have been mad in large quantities, down to very small sizes. In particular, small boilers for mounting on a wall are use in small houses and flats quite extensively, to provide the modest amount of hot water needed for supplying the radiators in two or three rooms and for supply to the -ho water taps of the dwelling. Whilst such boilers are found t-o perform, in general, quite satisfactorily, thei manufacturing cost is higher per kilowatt of power outpu than that of larger units having a higher power output. This is because many factors in the manufacturing cost, as is well known, either do not vary with the power output of the unit being manufactured, or else are not proportional to its power output.Boilers of conventional construction, having generally-rectangular heat exchangers of cast-iron, are in use having power outputs of the order of 0.4-2 megajoule/hr (40,000 btu per hour), but it is not economic to manufacture such boilers for outputs very much smaller than this. However, provision of a boiler having a substantially greater heating capacity than the system calls for is generally wasteful, particularly in that such a boiler will tend to use more fuel that it need do At the same time, there are many situations where boiler having a heating or power output capacity of about, or ' substantially smaller than, about 0.3 megajoule/hr could be used with advantage. Examples of such situations include one-room or two-room flats, very small terrace o semi-detached houses. This is particularly so since recent escalations in building costs have driven cεvelop -5- of property to build smaller and smaller dwellings, in which space for any kind of appliance is scarcer than in the past, but where nevertheless there is a requirement for central heating as well as hot water for other purposes.Reduced heating capacity is not, however, confined to small buildings, but is becoming possible more and more in buildings of all sizes, old and new, as the application of modern thermal insulation techniques reduces very substantially the heat, losses and therefore the heating requirement. Another consideration is that of size. A central heating system having a small heat input requirement will in general be installed in a place where space is limited, such as a small flat or apartment. Although the recent advent of wall mounted boilers has to a certain extent alleviated the problem of finding space for the boiler^ in that it no longer needs to be placed on the floor, wall space may also be difficult to find in a small room. This is particularly so since any boiler requires a certain amount of free space around it to allow proper circulation of air for safety reasons. Again, since the boiler requires to be installed where a proper flue can be fitted, this in practice usually means that the choice of wall is limited to an outside wall where a suitable flue, either of the balanced type or otherwise, can be arranged. It is thus desirable - and particularly for boilers of the smaller power output ranges - that the boiler, including its casing and accessories such as control unit, pump (if any), and pipe co'nnections, shall be as small as possible, so that the likelihood is increased that it can be found a suitable position in a small room where a flue can be conveniently placed and where cold water, and gas or oil, can easily be brought to the boiler. Proposals for compact boilers of comparatively small power output have been made in the past. In one such boiler, the shell-type heat exchange is of fabricated construction and cylindrical in shape. A gas burner is mounted coaxially in the heat exchanger shell, and combustion air is supplied to the burner by fan. Longitudinally extending pipes, arranged on a common pitch circle, are arranged through the heat exchanger shell to serve as water passages, and the hot combustion gases flow outwardly and freely from the burner towards the circumference of the shell, there to be collected and directed to the flue. Arranged betwee each water pipe and the next within the shell, there is a matrix of balls, so that the hot gases, to reach the outer circumference of the shell, have to pass through these matrices. Heat exchange from the hot gases to the water in the pipes thus takes place mainly through the balls and thence to the pipe walls. This ball matrix type of boiler has many promising features, but it has not yet been found possible to develop it to a stage at which it can be competitive with a conventiona boiler. Disclosure of Invention t is a principal object of the invention to provide a boiler for heating water for central heating and/or other purposes, which can be made in sizes such that the power output may be substantially smaller than in conventional boilers for hot water, but which can be made relatively inexpensively whilst being at the same time robust and of satisfactory reliability and efficiency.Another object of the invention is to provide for such a boiler, a heat exchanger which can be nade i conventional materials and which is essentially sinple in design.A further object of the invention is to provide such a boiler of compact form such that, having regard to its heating capacity, it can be made small enough to be conveniently installed in a very restricted space.Principal advantages of the invention with reference to the background art reside in the achievement of the above-mentioned objects. To this end, the invention provides, in a first aspect thereof, a heat exchanger of the kind hereinbefore specified whose body has a number of radial passages, narrow relative to •their radial length, these passages leading from a central bore of the body to an annular, circumferential space v/hich serves as a manifold chamber for the first medium. The arrangement is such that the first medium passes between the bore and the annular space along a comparatively short path but in contact with a relatively large surface area constituted by the sides of the radial passages, being constrained in axial directions but free to flow in radial directions. The radial passages, each of which has the form of a segment of an a'nnulus, are intersected by transverse walls which enclose longitudinal passage through which the second medium flows.In preferred embodiments, at least one cf the radial walls of the matrix, separating one radial passage from another, is hollow, having an annular passage which is connected with the longitudinal passages. This permits the second medium to circulate not only in the latter, but also in the annular interior of the (cr each) hollow wall, thus substantially increasing ~he surface area available for heat transfer between * he two fluids. In a second aspect, the invention provides ay. WwiiPrOυ boiler for hot water, in which the heat exchanger is o kind according to the said first aspect of the inventi the hollow cylindrical space within the heat exchanger bore being a combustion chamber from which hot gaseous products of combustion of a fuel/air mixture pass thro the radial passages of the heat exchanger to. the annul circumferential space already mentioned, giving up the heat in the process to water flowing in the longitudin passages and in the hollow walls, if provided, which separate one radial hot gas passage from another. It envisaged that in a boiler according to the invention, forced draught is required. To this end, the boiler incorporates a fan or blower, which may be mounted in combustion chamber itself or in the air inlet upstream of the latter.Boilers according to the invention may be of any size and power output, but are particularly advantageous in that they can be made in small sizes such as to give power outputs smaller than those obtainable from currently-known boilers of conventiona construction. Domestic boilers of conventional kinds generally give outputs in the approximate range 0.3 to 1.3 megajoule/hr (30,000 to 125,000 bth/hr) (boiler to water). We have obtained results with a boiler of the novel kind described herein, in which the heat exchang diameter was about O.38 metre (15 inches) and the length of its body about 9 cm (3*1 inches). A figure o 0.121 megajoule/hr (11,500 btu/hr) was obtained for th boiler output into water flowing at the rate of about 41 Kg/min (9 lb/min). Both the combustion efficiency and gas-to-water efficiency were comparable with those obtainable with conventional boilers. Another similar boiler of comparable size gave a boiler output of 0.22 megajoule/hr (20,900 btu/hr) into water flowing at the rate of 3--+ Kg/min (7-5 lb/min), again with satisfactor -7- efficiencies.As to boiler size, it will be evident from the heat exchanger dimensions quoted above that a boiler of the kind described herein can be made to overall dimensions such that its overall volume is similar to that of a conventional boiler having the same power output; and that the overall size of the boiler, when made so as to give smaller power outputs than the conventional types, will be correspondingly smaller. Accordingly, from the point of view both of power output and of overall size, the boilers as described herein can be seen to be useful, not only as an alternative to conventional boilers, but more especially as an economically- iable means for obtaining hot water and central heating in very small dwellings where the total hot water requirement is not sufficient to justify a conventional boiler.The boiler may be made free-standing, or arranged for mounting on a wall, or even for example inside a suitable cupboard. They may be readily adapted for use with either gas or fuel oil, or with any other suitable fuel.Embodiments of the invention are described in the Specific Description, by way of example only, with reference to the drawings.Brief Description of DrawingsFigure 1 is a partly diagrammatic, cut-away view in perspective showing principal components of a central heating boiler in a first embodiment of the invention;Figure 2 is a diagrammatic representation illustrating the water circuit of the heat exchanger of the boiler shown in Figure 1;Figure 3 is a sectional elevation, -taken on the two radial planes represented by the line III-III inOMPI_ [, VVIPO /?NATlO -8-Figure 4, and showing the heat exchanger of a boiler in a second embodiment;Figure 4 is an end view of a heat exchanger body member, as seen in the direction, and viewed on the 5 plane, denoted by the arrows IV-IV in Figure 3;Figure 5 is a view similar to Figure 4 but sho the other end as seen in the direction, and viewed on the plane, denoted by the arrows V-V in Figure 3;Figure 6 is a sectional view taken on the plan 0 VI-VI in Figure 5;Figure 7 is an inside view of a rear cover pla of the heat exchanger, as seen in the direction, and viewed on the plane, denoted by the arrows VII-VII in Figure 3; and 5 Figure 8 is a scrap section showing how, in a second embodiment, the fan in the .combustion chamber of the first embodiment may be replaced by a blower externa to the heat exchanger. Specific Description 0 In the following description three embodiments of the invention are described, the first with reference to Figures 1 and 2 having a heat exchanger 110, the second with reference to Figures 3 to 7 having a heat exchanger 210, and the third with reference to Figure 8, 5 the third embodiment being the same as the second embodiment except as will be described. For ease of identifying the parts of the boiler which differ from on embodiment to another, the following notation is used fo the reference numerals so far as practicable. Two-figur 0 numerals relate to parts common to all the embodiments, while three-figure numerals between 100 and 199 are used for parts described only for the first embodiment. Three figure numerals between 200 and 299 are used for parts first described with respect to the second embodiment 5 (some of these appear also in Figure 8); whilst parts described only for the third embodiment are identified by numerals between 300 and 399- Where two parts in two embodiments, whilst different in some way from each other, nevertheless have the same or a similar function, the last two figures of their reference numerals are, in general, the same for both parts.Referring to Figure 1, a small domestic gas- fired boiler for producing hot water, for central heating and for supply to hot water taps, includes a heat exchanger generally indicated at 110. The heat exchanger 110 is arranged for indirect heat exchange between a first fluid medium, in the form of hot products of the combustion of gas, and a second fluid medium which is the water to be heated. The heat exchanger 110 comprises a generally cylindrical, hollow heat exchanger body member 111 in which are formed longitudinal water passage means. These latter take the form of eight waterways 12, of pear-shaped cross-section. As will be seen hereinafter, the heat exchanger 110 is adapted for flow of the hot combustion products (hereinafter referred to as hot gas ) away from the axis of the heat exchanger body 111 and towards its circumference.Describing the heat exchanger in greater detail with reference to Figures 1 and 2, it consists of four principal parts, viz. the heat exchanger body member 111, a front cover member 113, rear cover member indicated at 154 in phantom lines in Figure 1, and a circumferential shroud 15- The body member 111 consists, in this example, of a single, -generally cylindrical body member which is a one-piece iron casting. The body member 111 has disc-like front and rear walls 117 and 116 respectively, between which there is situated a toroidal heat exchange matrix 118 through which the waterways 12 extend. At its radially inner edge the heat exchange matrix 118 defines a central, coaxial bore 19 of the heat exchanger body member; the central space within this bore constitutes a combustion chamber 20. The front and rear walls 117,116 extend radially outwards beyond the circumference of the heat exchange matrix 118, so that there is between them an annular,- circumferentia space 21. This space 21 is closed by the encircling shroud 15, which is shown in Figure 1 spaced away from the heat exchanger body 111 but which in the assembled heat exchanger is sealingly secured around the latter by any suitable means (not shown). The annular space 21 serves as a hot gas collecting or outlet manifold chamber.The matrix 118 comprises a plurality of annula walls 22 which are disposed in radial planes and which separate a number of annular passages 23. The passages lead directly and radially from the combustioon chamber to the hot gas collecting chamber 21, and are interrupte only by the longitudinally extending walls 24 which enclose the waterways 12. The bore 19 is thus surrounde by radially extending direct and indirect heat exchange surfaces definin .annular paths for the hot gas along the passages 23, these heat exchange surfaces being the radial sides 25 of the walls 22 and of the end walls 117,116 in the matrix, together with those surfaces (not shown) of the longitudinal walls 24 which are exposed to the hot gas.It will be noted that hot gas is able to flow through the matrix freely in radial directions (and to this end the annular passages 23 are free of any obstruction such as to reduce the flow rate), but are constrained by the annular heat exchange surfaces of the matrix against movement in axial directions. Thus the hot gas is positively guided in true radial flow through the matrix 118. The rear wall 116 of the heat exchanger -body 1 has on its outer surface two integral, arcuate flanges 126 projecting longitudinally, the ends of each of the flanges 126 being joined by an integral flange 127. The flanges 126,127 are matched by, and abut, corresponding flanges of the rear cover member 15-, so that the end wall 116 and cover member 5^- together enclose a cold water inlet chamber 128 and a hot water outlet chamber 129.The boiler has air inlet means in the form of an inlet pipe 30 leading into a mixing chamber 31 which is bounded by a wall 32* of the rear cover member 5**^, by the heat exchanger rear wall 116, by part of each of the flanges 127, and by corresponding parts of the cover member flanges (not shown in Figure 1) abutting with the latter. A fuel gas inlet 35 is provided to introduce gas into the inlet end of the mixing chamber 3 , and the outlet end of the latter, on the axis of the heat exchanger, opens into the combustion chamber 20.A hot gas exhaust pipe 3*^* is arranged coaxially within the air inlet pipe 30 but does not communicate therewith. The exhaust pipe H - is fixed through the heat exchanger rear wall 116 and leads from the hot gas collecting manifold 21; it is arranged to be connected, by any suitable means not shown, to a conventional flue. It will however be realised that, with this coaxial arrangement of the two pipes 30 and 3*^, a balanced flue can very conveniently be provided.A cylindrical burner 35 of known pattern is mounted coaxially in the combustion chamber 20, the latter being provided with an annular locating flange 36 for this purpose.The front end of the combustion chamber is in this example closed by the front cover member 113, through which there extends a drive shaft 137. carrying a fan 138. The latter is mounted coaxially within theOMPI WIPO4- -12- burner 35, and its shaft 137 is driven by an externally mounted electric motor 139-The water circuit of the heat exchanger is illustrated diagrammatically in Figure 2. The boiler has water inlet means in the form of a cold water pipe 140 leading into the inlet chamber 128 (Figures 1 and 2), and water outlet means in the form of a hot wat pipe 141 leading from the outlet chamber 129 (Figures 1 and 2). The inlet chamber 128 leads into a first group of four of the longitudinal waterways of the heat exchanger, indicated at 121, 1211, 12111 and 12IV in Figure 2. The front cover member 113 is arranged with longitudinally projecting flanges such as 142, Figure 1 abutting corresponding flanges, such as 43, of the fron wall 117 of the heat exchanger, so that a pair of separate water manifold chambers 144,145 are formed between the front cover member 113 and the front wall 1 The waterways 12 I and 12II lead into the manifold chamber 144, whilst the waterways 12 and 12 lead into the manifold chamber 145- Leading from the chamber 144 to the hot water outlet chamber 129 are two further ones of the waterways 12, viz. those indicated 12 and 12 . The two remaining waterways, 12 and 12 , lead from the other manifold chamber 45 to the hot water outlet chamber 129- The four waterways 12 , 12VI, 12VI1, 12VI11 thus constitute a further group to return the water through the heat exchanger to the rear end of the latter.The boiler itself comprises the heat exchanger 110, the air inlet pipe 30, ho.t gas exhaust 3-* burner 35, fan 138 with its shaft 137 and motor 139, an other necessary but conventional parts (not shown), suc as an igniter in the combustion chamber, electrical control equipment, fuel gas valve, thermostat etc. The heat exchanger 110 is- fixed on a suitable mounting -13- within a cabinet, not shown, in which the other components can conveniently be also arranged.In operation, water passing first through the waterways 12 to 12 and then through the waterways 12 to 12 is heated by cross-flow heat transfer from the hot gases forced radially through the annular passages 23 of the heat exchanger matrix 118 by the fan 138, as indicated by arrows in Figure 1. The hot gases are of course the product of combustion, at the burner 35, of the gas-air mixture created in the mixing chamber 3 •Referring now to Figures 3 to 7, these Figures illustrate parts of a modified heat exchanger 210 for a boiler which, in all respects. other than those which will be evident from the description now to follow, and from the drawings, is constructed, and operates, in the same way as that described with reference to Figures 1 and 2.In the heat exchanger matrix 218 in this second embodiment, two of the annular walls, shown at 2 0 and 251, are thicker than the walls 22 in the embodiment of Figure 1, and are made hollow to define in each wall 250,251 an internal,. annular water, passage 252. The passages communicate with the waterways 12 by means of ports 253 through the longitudinal walls 24 of the latter. This causes some water to be diverted from the waterways 12 into the passages 252.In this embodiment there are fifteen waterways 12, divided into two groups, viz. a first group of seven leading water from the rear of the heat exchanger to the front, and a second group of eight through which the water is returned to the rear. The respective water inlet and outlet chambers 223 and 229 are again bounded by the rear cover member, 254, and the rear wall, 216, of the heat exchanger 210, and by mating flanges 258,259; 260,261; and 262,263 respectively of the cover member 25^* and end wall 216 (Figures 3, 5 and -14-7). However, in this embodiment the front cover member 213, Figure 3, has a pair of coaxial flanges 264 defining a single annular manifold chamber 265, in plac of the two chambers 144,145 of Figures 1 and 2. It will -be understood that the annular water passages 252 need not each be provided with fifteen ports 255, i.e. one for every one of the waterways 12. The ports 253 can if desired be provided, in respect of each of the passages 252, at only some of the waterways 12; selection of waterways for provision of these port can be made having regard to the most desirable water flow pattern, to ensure that all the water is heated adequately whilst avoiding stagnation within the passages 252. The hot water outlet pipe is shown at 241 inFigures 3 and 7, and the cold water inlet pipe at 240. The mixing chamber 31 is arranged between the mating flanges 262 of the rear cover member and 263 of the heat exchanger rear wall, the fuel gas inlet being indicated at 268 in Figure 6. An opening 269 is provided in the rear cover member 25 for the air inlet pipe 30τ Figure to be sealably fixed therein, whilst an opening 270 is formed in the heat exchanger rear wall 216, Figures 5 a 6, for the hot gas exhaust pipe 3*. The front end of t combustion chamber 20 is closed by an end plate indicat by phantom lines at 271 in Figure 3«It will also be noted from Figure 6 that the annular walls 22,250,251 of the heat exchanger matrix 11 may advantageously be cut away to form recesses 272 in their outer circumference, opposite the hot gas exhaust to permit smooth flow of the hot gas at this point. •Referring to Figure 8, this shows a modification in which, in place of the fan 138 in the combustion chamber of the boiler shown in Figure 1, a blower 373 is provided in the air inlet means to induce - 5- forced draught through the boiler. In this example, the rear cover member, 35 -, is extended radially beyond the heat exchanger 210, as indicated at 37^, to provide a blower chamber 375 which is an extension of the mixing 5 chamber 31- The blower 373 is arranged in the chamber 375, its motor 339 being mounted on the outside of the latter. Air from the inlet pipe 30 is diverted to the blower 373 through a small auxiliary chamber 376 fixed to the cover member 35-. Although Figure 8 is drawn as a10 modification to the boiler described with reference to Figures 3 to 7, a similar arrangement, in which a blower is provided at the air inlet instead of in the combustion chamber, may of course be made as a modification to that shown in Figures 1 and 2.15 Many variations, besides those already described, may be made to the boilers and heat exchangers described 'herein. For example, the water inlet and water outlet may be at the front end of the heat exchanger; alternatively the inlet may be at one end and the outlet20 at the other. The waterways through the heat exchanger matrix, and the chambers connecting these waterways at their ends, may be so arranged with respect to each other that water passes through the heat exchanger in a 'single pass or in more than two passes. There may be25 any desired number of waterways, and these may be of any suitable cross-section. There may be any desired number of annular walls in the heat exchanger matrix, and consequently any number of annular or radial hot gas passages through the matrix. The heat exchanger body30 need not consist of a single body member, but may comprise more than one such member, bolted in end to end relationship. | AMENDED CLAIMS(received by the International Bureau on 23 July 1979 (23.07.79))1. (Amended)- A heat exchanger for indirect heat excha between a first fluid medium and a second fluid medium, the heat exchanger having a generally-cylindrical hollo body including a heat exchange matrix (118) and comprising at least one generally-cylindrical body member having a central bore (19), and a plurality of radial surfaces (25) defining first annular passages (2 for permitting flow of said first medium therethrough, said first annular passages being narrow in relation to their radial extent and leading radially from the bore towards an annular circumferential space (21) encircling the matrix, some of the said radial surfaces being the sides of at least one radial wall (22,250,251 separating one said first annular passage from the next the said radial surfaces and first annular passages being intersected by transverse walls enclosing longi¬ tudinal passages (12) for the second medium, characterised in that at least one said radial wall (250,251) is hollow by virtue of an internal second annular passage (252) therein for the second medium, the or each second annular passage being in communicati with .the longitudinal passages (12) but not with che first annular passages (23), so that said second mediu can circulate in the hollow wall or walls. 2. (Cancelled)- 3. (Cancelled).- U O 1 W - 21 -4. (Cancelled) -5. (Amended). A heat exchanger according to Claim 1, characterised in that the heat exchanger body comprises a said body member (111,211) or a plurality of such members fixed to each other end-to-end, a first cover member (154,254) defining an inlet chamber (128,228) and an outlet chamber (129,229) for said second medium, and a second cover member (113,213) defining at least one manifold chamber (144,145,265), said cover members being so orientated that the second medium can flow from the inlet chamber, through a first group of the said longitudinal passages (12) and thence partly through the said manifold chamber and partly through the second annular passage or passages (252) to a second group of the longitudinal passages (12 and 50) to the outlet chamber.6. (Cancelled). -22-7- (Cancelled).8. (Cancelled).9. (Cancelled).10. (Amended). A boiler according to Claim 15, characterised by a said fan (138) within the combustion chamber.11. (Amended). A boiler according to Claim 10, characterised by a cylindrical burner within the combustion chamber, the burner being arranged coaxially around the fan.12. (Amended). A boiler according to Claim 15, characterised by a said blower (373) the air inlet means (375) upstream of the combustion chamber.13. (Cancelled). 14. (Amended). A boiler according to Claim 15, characterised in that the heat exchanger body comprises a said body member (111,211) or a plurality of such membersOJ-.PI W1P0 fixed to each other end-to-end, a first cover member (154,254) closing one end of the body, and a second cover member (113,213) closing its other end, the second cover member having at least one water manifold chamber (144,145,265), the first cover member having.the water inlet means (140,240) and water outlet means (141,241) each leading into a separate one of two water manifold chambers (128,228; 129,229) of the first cover member, and the manifold chambers of the cover members being so interconnected through the longitudinal water passages (12) of the heat exchanger matrix that water flows from the water inlet to the water outlet in a double pass through the heat exchanger matrix. 15. (New). A boiler for producing hot water, said boiler comprising a heat exchanger, for indirect heat exchange between hot gaseous combustion products, the heat exchanger having a generally-cylindrical hollow body including a heat exchange matrix (118) and comprising at least one generally-cylindrical body member having a central bore (19) defining a combustion chamber (20), and a plurality of radial surfaces (25) defining annular gas passages (23) for flow of the combustion products therethrough, said annular passages being narrow in relation to their radial extent and leading radially from the bore towards combustion product outlet means in the form of an annular circumferential space (21) encircling the matrix, some of the said radial surfaces being the sides of at least one radial wall (22,250,251) separating one said annular passage from the next, the said radial surfaces and annular passages being intersected by transverse walls enclosing longitudinal water passages (12); a burner (35) associated with the combustion chamber for producing said combustion products; water inlet means and water outlet means communicating with the said water passages (12); air inlet means to the combustion chamber; and a fan or blower (138;373) for creating a forced draught in said air and combustion product, characterised in that at least one said radial wall (250,251) of the heat exchanger matrix is hollow by virtue of an internal annular water passage (252) therein, the or each said annular water passage being in communication with the longitudinal water passages (12) but not with the annular gas passages (23), so that water can circulate in the hollow wall or walls. 16. (New). A boiler for producing hot water, said boiler comprising a heat exchanger for indirect heat exchange between hot gaseous combustion products and water, the heat exchanger having a generally-cylindrical hollow body including a heat exchange matrix (118) and comprising at least one generally-cylindrical body member having a central bore (19) defining a combustion chamber (20), and a plurality of radial surfaces (25) defining annular gas passages (23) for flow of the combustion products therethrough, said annular passages being narrow in relation to their radial extent and leading radially from the bore towards combustion product outlet means in the form of an annular circumferential space (21) encircling the matrix, some of the said radial surfaces being the sides of at least one radial wall (22,250,251) separating one said annular passage from the next, the said radial surfaces and annular passages being intersected by transverse walls enclosing longitudinal water passages (12); a burner (35) associated with the combustion chamber for producin said combustion products; water inlet means and water outlet means communicating with the said water passages (12); air inlet means to the combustion chamber; and a fan (138) for creating a forced draught in said air and combustion product, characterised in that the fan is within the combustion chamber.κ WIP • 2517- (New). A boiler according to Claim 16, characterised by a. cylindrical burner (35) within the combustion chamber (20), the burner being arranged coaxially around the fan (138). STATEMENT UNDER ARTICLE 19By way of amendment of this Application under Rule 46, please cancel the existing pages 16 to 19 and substitute the new pages 16 to 21 enclosed herewith.The differences between the replaced pages 16 to 19 and the corresponding new pages are as follows.Claims 2,3,4,6,7,8,9 and 13 are cancelled.Claim 1 has been amended so that its characterizing portion is now that previously characterizing Claim 2. Consequent on the above amendment to Claim 1, the generic part thereof has been edited in the interest of brevity and to eliminate wording previously found in lines 6-10 and 23-26, such wording being implicit in the claim as now presented.Claim 5 is amended to state expressly that the second medium flows partly through the manifold chamber in the second cover member, and partly through the hollow walls via the passages 25 therein.Claim 6 is replaced by new Claim 15, which is written in independent form but which is directed to a boiler of the kind previously claimed in Claim 6, but whose heat exchanger is a heat exchanger according to the amended Claim 1. - Claims 10, 12 and 14 are amended only to make them dependent on Claim 5.Claim 11, now dependent on Claim 10, now incorporates the coaxial burner and fan in its characterizing portion. •New Claim 16 has a generic portion identical to that of Claim 15 but corresponds substantially to the previous (unamended) Claim 10.New Claim 17 corresponds substantially to the previous (unamended) Claim 11.IjUREAfT OMPI | BOYES M; STELRAD GROUP LTD | BOYES M |
WO-1979000732-A1 | 1,979,000,732 | WO | A1 | EN | 19,791,004 | 1,979 | 20,090,507 | new | C08G59 | null | C08F290, C08F299, C08G59, C09D155, C09D163 | C08G 59/42Y, C09D 163/00+B4B | WATER SOLUBLE EPOXY ESTER COPOLYMERS FOR SANITARY CAN USE | Water soluble epoxy ester copolymers adapted for sanitary can use comprise an hydroxy functional epoxy ester of a polyepoxide having an average molecular weight of about 300 to about 1100 and a 1,2-epoxy equivalency of about 1, 4 to about 2.0, esterified with an at least approximately stoichiometric proportion, based on epoxide functionality, of monocarboxylic acid selected from benzoic acid, C<u1>u-C<u8>u alkyl substituted benzoic acid, and C<u6>u-C<u10>u alkanoic acid, the esterification reaction being continued to provide an acid number of less than 20, this hydroxy functional epoxy ester is polyesterified with from 1.5-8%, based on the weight of the epoxy ester, of a monoethylenically unsaturated dicarboxylic acid which resists homopolymerization to an acid number of less than 20, and the polyester so obtained is copolymerized with from 15% to 70% of monoethylenic monomers, based on the copolymer, these monoethylenic monomers including carboxyl functional monomer providing an acid number of from 20-100 in the copolymer. The copolymers are dispersed in water by salt formation with an amine and aminoplast or phenoplast resin is incorporated to provide curing reactivity. | ATE SOLUBLE EPOXY ESTER COPOLYMERS FOR SANITARY CAN USE Technical FieldThe present invention relates to water soluble epoxy ester copolymers which are particularly adapted to sanitary can use where good resistance to extraction by hot water and good odor and flavor characteristics are essential. Background Art Water solution coating compositions have been employed for diverse purposes, but it has been difficult to obtain the good resistance to extraction by hot water and good odor and flavor characteristics which are important to enable application of the coatings to sanitary cans.Disclosure of InventionIn this invention, a relatively low molecular_ weight polyepoxide having -an average molecular weight of about 300 to about 1100 (by calculation) and a 1,2-epoxy equivalency of about 1.4 to about 2.0 is esterified with an at least approximately stoichio- metric proportion, based on epoxide functionality, of monocarboxylic acid selected from benzoic acid, a alkyl substituted benzoic acid, or a Cg-C-,0 alkanoic acid to produce an ester derivative substantially free of epoxy functionality. This esterification reaction is continued to an acid number of less than 20. The resulting hydroxy functional epoxy ester is then poly¬ esterified with a monoethylenic dicarboxylic acid which resists homopolymerization, preferably fumaric acid.From 1.5-8% of the diacid is .used in the polyesterifica- tion reaction, based on the weight, of the epoxy ester, so the hydroxy groups in the epoxy ester are present in stoichiometric excess, and the polyesterification is continued to an acid number of less than 20 to provide an ethylenically unsaturated hydroxy functional poly- ester. This unsaturated polyester is then copolymerized with from 15% to 70% of monoethylenic monomers, based on the weight of the copolymer, to provide a copolymer product. These monomers include monoethylenic carboxyl- ic acid, such as methacrylic acid or fumaric acid, to provide an acid number of from 20-100 in the final copolymer so that amine and water can be added to pro¬ vide a water dispersion which is either a solution or a colloidal dispersion. Reactive monomers, such as hydroxyethyl acrylate or N-methylol acrylamide or its ether, such as the butyl ether, may be used. -Alterna¬ tively, an aminoplast, such as hexamethoxy methyl melamine, or a water soluble or dispersible phenoplast, or a mixture thereof, may be used for -cure. The polyepoxides preferably have a 1,2-epoxy equivalency of about 1.4 to about 2.0 and the best properties are obtained using diglycidyl ethers of a bisphenol, such as bisphenol A. The preferred molecular weight of the polyepoxides, which may be provided by the use of mixtures, is from 350 to 800.The saturated monocarboxylie acid used to consume the epoxy functionality may be benzoic ac d or a C-,-C8 alkyl substituted benzoic acid or a Cfi-C,n alkanoic acid, but para tertiary butyl benzoic acid is particu- larly preferred. The Cg-C,Q alkanoic acids are less preferred and are illustrated by hexoic acid or pelar- gonic acid. These saturated monocarboxylic acids uniquely provide maximum impermeability in the combina¬ tion of this invention. The esterification reaction is wholly conventional, simple heating to a hot melt, desirably in the presence of a trace of amine catalyst, being all that is needed. The acid is used in at least approximately stoichio et- ric proportion and the reaction is continued to consume most of the acid, an acid number of less than about 20, preferably less than 10, being contemplated. Significant residual epoxy functionality yields instability and should be avoided. Some excess acid will simply react with the hydroxy functionality on the epoxy ester. It is here noted that polyepoxides fre- quently contain hydroxy groups, and even if they do not, the carboxy-epoxy reaction produces hydroxy groups, so the epoxy ester which is formed is hydroxy functional. Substantially stoichiome ric proportions are preferred. The onoethylenically unsaturated dicarboxylic acid should resist homopolymerization so that its acid¬ ity can be substantially consumbed in the production of a polyester with the hydroxyl functional epoxy ester without consuming the unsaturation. The preferred dicarboxylic acid is fumaric acid, but aleic acid or maleic anhydride can also be used. An acid number of less than 20, preferably less than 10, indicates the desired complete reaction.This polyester now contains .polymerizable unsat¬ uration and it is copolymerized with monoethylenic monomers, the bulk of which (at least about 50% by weight) are nonreactive. This means that, aside from their polymerizable unsaturation, they do not react under the conditions of polymerization and use which are contemplated. A similar statement is that there are no functional groups except the polymerizable ethylenic group. Styrene and vinyl toluene are particularly contemplated, though methyl methacrylate, methyl acryl- ate, ethyl acrylate, acrylonitrile and vinyl acetate will further illustrate the useful materials. Styrene and vinyl toluene are especially important for two reasons. First, they copolymerize better with the di¬ carboxylic .acids used for polyesterification. Second, they produce higher molecular weight copolymers which provide higher viscosity aqueous solutions at low solids content, and this provides spray solutions which better resist the formation of bubbles, blisters and foams. A monoethylenic carboxylic acid of any desired type should be employed to provide an acid number of from 20-100 in the final copolymer. Fumaric acid and maleic acid are preferred because these are F.D.A. approved, but acrylic acid, methacrylic acid, crotonic acid and itaconic acid are all useful, and one cannot know which acids will be a-proved for sanitary can use in the future. Maleic anhydride is useful at the smaller proportion of use. The preferred acidity should not exceed 60. While more acid polymers can be used, sanitary can use requires maximum water resistance and good resistance to water extraction, and these are best at low acid value. The copolymers herein are well adapted to disperse in water at low acid value. Other reactive monoethylenic monomers may be included in an amount up to about 20% of the total polymerizable monomers. These are illustrated by hydroxy monomers, such as 2-hydroxyethyl acrylate, amide monomers, such as acrylamide, N-methylol function- al monomers, such as N-methylol acrylamide or ethers thereof like the butyl ether.The copolymerization is itself conventional being carried out in organic solvent solution using a free radical generating polymerization catalyst. These are well known and are illustrated in the Example.The aminoplast and phenoplast resins which may be used for cure are also well known and will be illus¬ trated by hexamethoxyme hyl melamine. This class of water soluble and water dispersible materials useful for curing hydroxy functional resins is a matter of common knowledge in the art. They are used in an amount of 5-40% of total resin solids.An amine, including ammonia, is added to allow the acidic copolymer to be dispersed in water. This is again conventional, and is illustrated using dimethyl ethanol amine.'BUREOMPI. ^ WIPύ The resulting aqueous solutions cure to provide films characterized by superior resistance to extrac¬ tion and they resist absorbing odor and flavor compo¬ nents of the foods and beverages which are packaged. They can be applied to any metal can interior, such as aluminum, steel and tin plated steel. Spray appication and cure by baking at 400°F. for 3 minutes are particu¬ larly contemplated. Films of about 0.2-0.3 mil are formed. Good adhesion is obtained on all of these surfaces.Best Mode for Carrying Out the InventionThe invention is illustrated in the following example of preferred operation, all parts herein being by weight except where otherwise noted. • Example 1(1) Para tertiary butyl benzoic acid) 210 . CIBA 6010 ) 230Heat to 100 °C. to melt.(2) Dimethyl ethanol amine 1 Add (2) . Watch for exotherm which heats the mixture to 225°C. and hold for acid value less than 5. Then cool to 180°C.(3) Fumaric acid ) 15 Xylol ) 30Add (3). Heat to 225°C. and remove water of esteri- fication and hold for acid value less than 7. Gbol to 170°C.(4) Butyl cellosolve ) 460(5) Fumaric acid ) 40 Add (4) and (5). Hold 30 minutes to dissolve the fumaric acid and then cool to 125°C.(6) Styrene ) 160Cumene Hydroperoxide ) 25Premix (6) and add over 2 hrs at 125°C. and hold 1 hr. (7) Cumene hydroperoxideAdd (7) and hold 1 hr. (8) Cumene hydroperoxide ) 5 Add (8) hold 1 hr. , and cool to 70°C.(9) Dimethyl ethanol amine ) 75(10) Hexamethoxymethyl melamine )165 5 Add (9) and (10)(11) Deionized water )1400 Add (11) slowly over 30 minutes.The final product is a milky dispersion having the following characteristics: Nonvolatile solids - 10 30.1%,- Acid value of solids - 33.5.This dispersion has been successfully sprayed on aluminum and steel can interiors and cured by baking at 400°F. for 3 minutes. Extractables are low and good flavor and color properties are obtained. | 1. Epoxy ester copolymer soluble in water with the aid of an amine comprising the hydroxy functional epoxy ester of a polyepoxide having an average molecu¬ lar weight of about 300 to about 1100 and a 1,2- epoxy equivalency of about 1.4 to about 2.0, esterified with an at least approximately stoichiome ric proportion, based on epoxide functionality, of monocarboxylie acid selected from benzoic acid, C, - CQ alkyl substituted benzoic acid, and Cfi - C, -. alkanoic acid, the esterifi- cation reaction being continued to provide an acid num¬ ber of less than 20, said hydroxy functional epoxy ester being polyesterified with from 1.5-87o, based on the weight of the epoxy ester, of a monoethylenically unsaturated di¬ carboxylic acid which resists homopolymerization to an acid number of less .than 20, and said polyester being copolymerized with from 15% to 70% of monoethylenic mono¬ mers, based on the copolymer,_ said monoethylenic monomers including carboxyl functional monomer providing an acid number of from 20-100 in the copolymer. 2. Epoxy ester copolymer as recited in claim 1 in which said polyepoxide has an average molecular weight of from 350 to 800.3. Epoxy ester copolymer as recited in claim 2 in which said polyepoxide is a diglycidyl ether of a bisphenol.4. Epoxy ester copolymer as recited in claim 1 in which said monocarboxylie acid is para tertiary butyl benzoic acid.5. Epoxy ester copolymer as recited in claim 1 in which said hydroxy functional epoxy ester is poly¬ esterified with from 2.5-5%, based on the weight of the epoxy ester, of said unsaturated dicarboxylic acid.6. Epoxy ester copolymer as recited in claim 1 in which said polyepoxide and said monocarboxylic acid are used in substantially stoichiometric proportions. 7. Epoxy ester copolymer as recited in claim 1 in which said unsaturated dicarboxylic acid is fumaric acid.8. Epoxy ester copolymer as recited in claim 7 in which said carboxyl functional monomer is also fumaric acid.•9. Epoxy ester copolymer as recited in claim 1 in which at least 50% of said monomers are nonreaetive.10. Epoxy ester copolymer as recited in claim 9 in which said nonreaetive monomers consist of styrene and vinyl toluene.11. Epoxy ester copolymer as recited in claim 9 in which the functionality of any nonacidic reactive monomer is selected from the group consisting of hydroxy, amide and. N-methylol amide.12. Epoxy ester copolymer as recited in claim 1 in which said copolymer is present in admixture with from 5-40%, based on total resin- solids, of an amino- plast or phenoplast resin. 13. Epoxy ester copolymer as recited in claim 1 in which said copolymer has an acid number of up to about- 60.14. An aqueous dispersion comprising water having the acidic epoxy ester copolymer of any of claim 1-13 dispersed therein in the form of a salt with an amine. | SEKMAKAS K; SHAH R | SEKMAKAS K; SHAH R |
WO-1979000737-A1 | 1,979,000,737 | WO | A1 | EN | 19,791,004 | 1,979 | 20,090,507 | new | H01B3 | C03C3, H01B3, C04B23 | C03C10, H01B3, H02G5 | C03C 10/00M, H01B 3/08F, H01B 3/12 | UTILIZATION OF A GLASS-CERAMIC MATERIAL AS ELECTRICAL INSULATOR | Utilization as electrical insulator (16) of a glass-ceramic material made from blast furnace slag. The material has a content of a CaO which exceeds or is equal to 10 per cent by weight preferably amounting to approximately 22 per cent by weight, and contains also substances with the approximative values in per cent by weight stated hereinafter: 57 % SiO 6 % Al<u2>uO<u3>u 2,6% MgO 0,2% FeO 0,05% MnO 0,1% TiO<u2>u 0,2% S 0,01% P<u2>uO<u5>u 1,7% Na<u2>uO 5,0% K<u2>uO The electrical insulator constitutes a pin insulator (16) in a gas-insulated tube cable or tube capsule (10, 12) intended for high voltage. | Utilization of a glass-ceramic material as electrical i nsul ator .The present invention relates to utilization as electrical insulator of a glass-ceramic material made from blast furnace slag.It is desirable that an underground tube cable gene¬ rally has an effective service length of at least 50 to 100 years, and to realize this aim v e ry high demands must be put on all details forming .part of the cable, i.a. the required insulators which normally will not be replaced in the cable during the said period of time because of the highly complicated working moments associated with such a replacement. Therefore, in order to satisfy the high demands the insulators must have the following properties:- excellent electrical insulating capacity,- excellent mecha cal strength,- excellent shape permanence,- excellent corrosion resistance,- excellent resistance against ageing, and- excellent resistance against carbonizing.One of the reasons why underground tube cables have not yet been used to any greater extent as an alternative to conventional overhead power transmission lines is that the costs of manufacture are relatively high, which i .a. resides therein that there are no cheap insulators which to a desirable extent satisfy all abovestated demands.Hitherto, the insulators have been made mainly from ceramic materials such as porcelain, of glass and of various epoxy compositions. The insulators consisting of epoxy material have proved to be those which are best suited for util zation in tube cables and tube capsules. Such insu¬ lators of epoxy material are manufactured by moulding, but the manufacturing process is highly complicated.The high costs are also the sole overshading reason why insulators of conventional glass-ceramic material hav not at all been utilized in connection with -underground tube cables and tube capsules in spite thereof that this material has proved to possess the desired material pro- perti es .The main object of the invention is to provide an electrical insulator which satisfies the demands set for in the introductory part of this description, especial regard being taken to the requirement of resistance again ageing, simultaneously as the insulator is cheap to manu¬ facture. This is rendered possible, according to the invention, by utilization as electrical insulator of a gla ceramic material obtained from blast furnace slag, said glass-ceramic material having a content of CaO exceeding or equalling 10 per cent by weight, and preferably amounti to approximately 22 per cent by weight, the electrical insulator forming a pin insulator in a gas-insulated tube cable or tube capsule intended for high voltage. Glass- ceramic material or so-called glass-ceramics of the stat kind have proved to satisfy the aforestated demands on insulator material equally well as conventional glass- ceramic materials having a lower content of CaO and . produced from molten glass. As a starting material for glass-ceramic materials intended for insulators, there is thus utilized extremely cheap so-called low-grade blas furnace slag which is intermixed with a suitable quantit determinable in advance, of silica, Si0?, and treated in a controlled process utilizing high temperatur and high pressure. A material produced in this way and known unde the denomination Slaggsital has the fol lowing- particu- 1 ars :- weight by volume 2.6 - 2.75 gs/cπT 6- modulus of elasticity 0.75- 10u - 1.1 -10- bending transverse strength 650 - 1200 kgs/cm'- compressive strength 4500 - 6000 kgs/cm'- specific impact value (V-notch value) 2.8 4.0 kgcms/- microhardness • 600 - 800 kgs/mm longitudinal expansion coeffici ent 72-10 -- 95-10' water absorptionHeat resistance according toGO ST 11103-64 test piece30 x 30 x 4 m s 100 150 temperature of deformation under load 900 - 1000 ther al conductiv ty at20°C Cal/m, t, °C 0.9- melting point 1230 - 1270 UC- acid-resistance in 96% HO 99.15 - 99.98 %- dielectric strength in electric field at 50 c.p.s. 40 50 kVs/mm- tangential angle for dielectric losses at 50 c.p.s 0.07 - 0.0029- specific electric capacity at 50 c.p.s. 7 -7.7- electrical resistivity 1.7-10 12 Ohm/cmHereinafter two examples are given for a chemical analysis (values in per cent) relating to firstly the said Slaggsital material and secondly a glass-ceramic material of conventional type which at present is utilized for insulators.CaO Si0 A1203 MgO FeO MnO Ti02 S P205 Na20 K201 22 57 6.0 2.6 0.2<θ'.05 0.1 0.2^0.01 1.7 5.02 0.7 66 24.0 1.2 0.4<0.05 4.2 <0.05- O.01 0.2 0.2 In the Chalmers University of Technology the dielectric strength and the running spark limit have been compared for the Slaggsital material and epoxy materials containing various fillers. The tests were carried out in an atmos¬ phere of sulfur hexaf1 uori de , SFfi, and evidenced that the Slaggsital material was a material equivalent to the epoxy material with regard to utilization in insulators. In endurance tests insulators made of porcelain, epoxy mate¬ rial and glass-ceramic material were, in addition, while kept under voltage, subjected to an aggressive coastal atmosphere. The gl ss-ceramic insulator solely remained entirely unattacked by corrosion and showed to possess extremely high resistance against ageing, which indicates that this insulator is especially well suited for utili¬ zation in underground tube cables and tube capsules.The above-mentioned Slaggsital material has earlie been produced mainly in the shape of plates and discs and has been utilized as covering material in the building industry and as grinding material in the mining industry and the iron and steel industry and in the coal industry and also as acid-proof lining in the chemical industry.With reference to the accompanying drawing, there will now be described a tube cable containing insulators of the type envisaged by the invention.Figure 1 is a side view of a tube cable section whic is partly cut up for the purpose of improved illustrationFigure 2 is a sectional view on an' enlarged scale of the tube cable shown in Figure 1.The tube cable consists of a sleeve which may be composed of an exterior part 10 and a shielding interior part 12. Disposed within the sleeve are three tubular conductors 14 of aluminium for three-phase operation whic are applied symmetrically with a spacing from one another and the encasing sleeve, pin insulators 16 constructed in accordance with the principles of the invention and disposed in spaced relationship along the conductor units serving as spacing members. The ends of the cable section are closed by insulators- also made according to the inven tion in the shape of end discs 18. The prefabricated tube cable sections can already in- connec¬ tion with the fabrication be filled with insulating mediu up to operation pressure. When joining the sections together in the ground a minor quantity only of insulatin medium need to be added. Alternately, all insulating medium may, of course, be supplied in one operation in connection with the mounting of the tube cable.The pin insulators 16 are directly secured onto the cable sleeve or (not shown), they may be mounted on a ring member which is inserted into the said sleeve. The insulating medium between the conductors an t e con uctors an t e s eeve , may con¬ sist of e.g. sulfur hexafloride, SFβ, o.r gaseous nitrogen, N„, or a mixture of said gases. Oil may also be used in some cases. | CLAIMS1. Utilization as electrical insulator of a glass-cerami material made from blast furnace slag, c h a r a c t e r i z e d by the glass-ceramic material having a content o CaO exceeding or equalling 10 per cent by weight, prefer¬ ably 22 per cent by weight, and in addition containing the following substances with the approximative values in per cent by weight stated hereinafter: 57 % SiO 6.0 % A1203 2..6 % MgO 0.2 % FeO 0.05 % MnO 0.1 % Ti0 0.2 % S o.oi % P2O5 1.7 % Na205.0 % 20 and the electrical insulator forming a pin insulator in a gas-insulated tube cable or tube capsule intended for high voltage.2. Utilization according to claim 1, c h a r a c t e r ¬ i z e d by the insulating gas consi sting of sulfur hexaf1 uori de , SFβ .3. Utilization according to claim l , c h. a r a c t e r i z e d by the insulating gas consisting of a gas mixture containing nitrogen and sulfur hexaf1 uori de._ .vA.. '•• '■ | ORPANA V; SSAB SVENSKT STAL AB; WAERULF O; WISUR M | ORPANA V; WAERULF O; WISUR M |
WO-1979000739-A1 | 1,979,000,739 | WO | A1 | EN | 19,791,004 | 1,979 | 20,090,507 | new | A61F1 | A61F1 | A61F2 | A61F 2/38B, A61F 2/38K, A61F 2/42A, K61F 2/00T33R1, K61F 2/30L2S, K61F 2/30S1D, K61F 2/38P2, K61F 2/38U | IMPROVED JOINT ENDOPROSTHESIS | Joint endoprosthesis for the total replacement of degenerate joints such as the andle, knee, elbow, wrist and finger. When embodied as an ankle endoprosthesis (10), the device comprises a tibial component (11) which provides a first bearing surface (21a); a talar component (13) which provides a second bearing surface (34) which is at least a segment of a surface of revolution about a first axis (2); and a tibial insert (12) intermediate the tibial and talar components (11 and 13) which provides a third bearing surface (26a) which provides area contact with the first bearing surface (21a) to permit relative rotation between the tibial component (11) with respect to the tibial insert (12) and the talar component (13) about a second axis (1) that is substantially parallel to the shaft of the tibia and which relative rotation provides one of only two degrees of freedom of rotational movement of said tibia with respect to said talus, and wherein the tibial insert (12) is further provided with a fourth bearing surface (29) in area contact with the second bearing surface (34) that is in sliding engagement therewith to permit relative rotational movement of the tibial component (11) and tibial insert (12) with respect to the talar component (13) about the first axis (2) which relative rotation thereby provides the second of only two degrees of freedom of rotational movement of said tibia with respect to said talus. The joint endoprosthesis overcomes the problem of poor wear characteristics on parts due to high stresses and pressures resulting from normal joint loads and avoids bone fushion techniques. | IMPROVED JOINT ENDOPROSTHESIS TECHNICAL FIELD Broadly speaking, this invention relates to joint endoprotheses and more specifically to a joint endopros- thesis with area contact bearing engagement and only two degrees of freedom of rotational movement between a first bone and a second bone while the bearing surfaces are kept in area contact engagement under the action of the joint. BACKGROUND ART For the sake of brevity and convenience, the discuss- ion of the prior art here will be generally limited to the ankle, and prior art ankle prostheses with later discussion of the knee; accordingly: As is known to those sTilled in the art, until quite recently, fusion was the primary mode of treatment for the most disabling conditions of the ankle joint. The reason for this was that fusion of the ankle produces much less disfigurement and loss, of function than does fusion of any other major load-bearing joint. Thus, ankle fusion, even -with its attendant loss of function, remains a therapeut- ically acceptable procedure. Nevertheless, fusion, by its very nature, should be considered redical surgery—the last possible alternative in joint reconstruction. If effective prosthetic surfaces can restore normal ankle function, then such an alternative is certainly more desir- able than fusion. The article by Pappas, Buechel and DePalma entitled Cylindrical Total Ankle Joint Replacement which appeared in Clinical Orthopaedics and Related Research, No. 118, July-August 1976, pp. 82-92, surveys the various ankle prostheses which have been developed to date. All such prostheses are metal-to-plastic articular surface replace- ment types which essentially rely on ligamentous control for stability. The fundamental differences in the various designs lie in the nature of the articulating surfaces. Two basic types are found: those with theoretical line or point contact articulating surfaces and those with area contact articulating surlaces. The incongruent surface types all permit the normally observed axial rotation in addition to permitting flexion- extension. However, incongruent surface prostheses suffer from two basic defects: (1) relatively poor wear arid poor deformation resistance due to high local stress resulting from incongruent surface contact, and (2) relatively poor inherent stability. High local stresses and pressures resulting from normal walking loads, even with a relative- ly small amount of incongruity, result in permanent deform- ation of the ultra-high molecular weight polyethelyene (UHMWPE) used in all known current ankle prostheses, as well as a relatively high wear rate. In addition, since the human ankle joint possesses essentially congruent surfaces, one cannot expect an incon-. gruent replacement joint to approximate normal motion since the kinematic properties of congruent and incongruent sur- faces, are so different. Prostheses utilizing congruent or area contact sur- faces, on the other hand, have good pressure distribution and, thus, offer superior wear and surface deformation re- sistance when compared to incongruent types. Further, they provide nearly normal stability because, under compressive load, the surfaces are forced into conformity and therefore motion to a large extent is defined by the surface geometry, thus providing predictable motion characteristics. Four basic variations of the area contact surface prosthesis are known. These are (1) spherical (e..g. ball and socket) ; (2) spheroidal (e.g. barrel-shaped) ; (3) cylindrical; and (4) conical. The spherical prosthesis allows three independent axes of rotation but the joint surface geometry dictated by such a design tends to limit the flexion-extension range. Further, the spherical type ankle prosthesis is also less resistant to inversion-eversion injuries caused by sub- stantially greater than normal loading of the ligaments and also is unstable since it allows an inversion- eversion motion between the tibia and talus that is not normally present. This lack of stability has been observ- ed clinically. The spheroidal type of prosthesis provides two inde- pendent rotations, plantar and dorsiflexion and inversion- eversion but fails to provide axial rotation. Thus, spheriodal prostheses are undesirable since axial rotation is necessary for normal function and since the device is also unstable in the inversion-eversion mode. The conical type of prosthesis employs dual cones with a single horizontal axis. This design has an ample range of motion'but it obtains this motion by the use of a sub- stantially higher than normal rotation axis. Furthermore, this particular prosthesis requires significantly greater resection of bone than some other designs. The cylindrical prosthesis, described in the above referred to article by Pappas et al. overcomes many of the noted deficiencies of the other congruent surface devices. Briefly, the device described by Pappas et al. employs a cylindrical surface with a horizontal axis located at the center of curvature of the lateral border of the talar dome. The cylindrical surface uses a UHM PE talar compon- ent and a mortised cobalt-chromium alloy tibial component both of which are stabilized with methyl-methacrylate bone- cement and dual fixation fins. As previously mentioned, the advantages of the cylind- rical or conical configurations are internal stability, approximating that of the normal ankle, and good congruent contact producing low stress and wear. Unfortunately, a conventional cylindrical or conical joint does not provide for the axial rotation which is normally observed in ankle motion. Strictly speaking, this rotation is not needed to provide a normal gait since it is not present at all in about 3 to 5% of normal individuals. However, in most -4- individuals, the loading pattern and walk are such that axial rotation tends to be induced and if it is not provided for in the prosthesis, stress is imparted to the fixation means an on those components of the prosthesis which resist axial rotation, thereby introducing the possibility of loosening of the prosthesis or deformation or wear of the prosthesis. More specifically, deformation and wear associated . with the need for axial rotation have been found in a prosthesis that was removed from a patient after loosening of the prosthesis was encountered. It is believed that a major factor in this loosening was the failure of this early prosthesis to provide any degree of axial rotation. Furthermore, it is known when heavy loads are impress ed on a relatively thin plastic prosthesis the component tends to loosen. The explanation for this is that since a relatively weak and brittle substance is used to cement the plastic component to bone, when the plastic is deforme under load it easily bends transmitting this bending to the cementing material which is then subject to crac - ing, producing a loosening of the prosthesis. On the other hand, when this same brittle cement is used to fixture metal to bone, the metal is so rigid that bend- ing is inhibited and therefore the bending stresses which tend to produce cracking on the cement are reduced to a level where they are no longer of concern. Thus the metal protects the cement. Thus it is important that a prosthesis for a typical condylar type joint possess axial rotation and be f±x- tured to bone by use of a strong rigid material such as metal. This statement is supported by extensive clinical studies involving hundreds of patients with knee replace- ments which show that it is the plastic component, that most frequently fails by loosening or excessive deformation and that although these failures commonly occur in incongruent designs they are much more frequentOM■ ~ in congruent designs which restrain axial rotation. In view of the above, it is clearly desirable to affix a metal rather than plastic prosthesis to bone. Because metal-to-metal contact surfaces do not wear well and since the wear products cause adverse tissue reaction it is necessary to interpose a non-metallic bearing into the prosthesis. The instant invention is based on the discovery that since it appears necessary in any event to interpose a third part in the prosthesis, if this part is implemented as a non-metallic insert, designed in such a manner that it provides the desired axial rotation, the previously discussed objectives will be attained. Furthermore, axial rotation of the prosthesis also compensates for surgical malalignment. That is, the components of the prosthesis inserted into the ankle can be slightly rotated. The ability of the insert to rotate axially accommodates for this rotational error. SUMMARY OF THE INVENTION ' _ In a preferred embodiment of the invention, and when embodied as an ankle prosthesis, the device comprises a- tibial component for being secured to the tibia and providing a first bearing surface; a talar component for being secured to the talus and providing a second bearing surface which is at least a segment of a surface of revolution about a first axis, and a tibial insert intermediate the tibial and talar components and provided with a third bearing surface which provides area contact with the first bearing surface and engageable therewith to permit relative rotation of the tibial component with respect to the tibial insert and talar component about a second axis which is not parallel to the first axis and is substantially parallel to the shaft of the tibia and which provides one of only two degrees of freedom of rotational movement of said tibia with respect to said talus, and wherein the tibial insert is further provided with a fourth bearing surface in area contact with the second bearing surface which is no more that one half a complete surface of revolution and for area contact sliding engagement therewith to permit relative rotational movement of the tibial component and tibial insert with respect to the talar component about the first axis and which provides the second of only two degrees of freedom of rotational movement of the tibia with respect to the talus so long as these bearing surfaces are kept in area contact but allowing a third rotational motion by partial separation of these surfaces. τhe invention, and mode of operation will be more full comprehended from the following detailed description, when taken with the appended drawings in which: BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a partial cross-sectional view of an ankle joint prosthesis embodying the present invention; FIG. 2 is an exploded version of FIG. 1 showing the three major components of the prosthesis in greater detail; FIGS. 3-5 are respectively the top, cross-sectional and bottom views of the tibial component of the prosthesis shown in FIGS. 1-2; FIGS. 7-9 are respectively the top, side and bottom views of the tibial insert component of the prosthesis shown in FIGS. 1 and 2; FIG. 10 shows the. front and side of the snap ring used to unite the components shown in FIGS. 3-5 and 7-9; FIGS. 11-13 are respectively the bottom, side and cross-sectional views of the talar component of the prosthesis shown in FIGS. 1 and 2 ; FIGS. 14 and 15 are respectively the normal and exploded cross-sectional views of a second illustrative embodiment of the invention; FIGS. 16-18 are respectively the top, cross-sect- ional and bottom views of the tibial component of the ø-7- prosthesis shown in FIGS. 14 and 15; FIG. 19 is a side view of the tibial component shown in FIGS. 16-18; FIGS. 20-22 are respectively the top, side and bottom views of the tibial insert component of the prosthe- sis shown in FIGS. 14 and 15; FIGS. 23-25 are respectively the bottom, side and cross-sectional views of the talar component of the prosthesis shown in FIGS. 14 and 15; FIGS. 26-28 are respectively the top, cross-sect- ional and side views of an alternate embodiment of the tibial insert component shown in FIGS. 7-9; FIGS. 29-31 are respectively the bottom, cross- sectional and cross-sectional side views of a talar.dome replacement prosthesis for use with the tibial insert component shown in FIGS. 26-28; FIG. 32 is a cross-sectional view showing how the tibial insert component of FIGS. 26-28 can be mated with the talar dome replacement of FIGS. 29-31; FIG. 33 is a diagrammatic illustration showing the two and only two degrees of rotational freedom permitted b the joint prosthesis of the present invention; FIG. 34 is a front or anterior view of a knee joint prosthesis embodying the present invention; and FIG. 35 is a cross-sectional view taken along the line 35-35 of FIG. 34;. FIGS. 36, 37 and 38 are partial cross-sectional views showing an alternate embodiment of the present invention embodied as a tricompartmental knee prosthesis; FIGS. 39, 40 and 41, are, respectively, top, side and front views of the femoral component of the alternate embodiment of the present invention embodied as a knee prosthesis; FIGS. 42, 43, and 44 are, respectively, cross- sectional top, side and front views of the intermediate patella bearing component of the alternate embodiment of■ BUREAUOMPl the present invention embodied as a knee prosthesis; FIGS. 45,46 and 47 are, respectively, top, partially enlarged and front views of the patella fixturing comp- onent of the alternate embodiment of the present invention embodied as a knee prosthesis; FIGS. 48, 49 and 50 are, respectively, top, cross- sectional side and front views of the tibial fixturing component of the alternate embodiment of the present invention embodied as a knee prosthesis; FIGS. 51, 52 and 53 are, respectively, front, partial ' cross-sectional side and front views of the tibial intermediate component of the alternate embodiment of the present invention embodied as a knee prosthesis; FIGS. 54A, 54B and 54C are composite diagrammatic illustrations showing the various compressive forces present in a knee provided with the knee prosthesis; FIG. 55 is a view of the distal femur of a human bein FIG. 56 is a diagrammatic• illustration showing tipping loads on a patella prosthesis; FIG. 57 is adiagrammatic illustration comparing the overlap available between a prosthesis having congruent design and a prosthesis having incongruent design; FIGS. 58 and 59 and FIGS. 60 and 61 are, respectively back, side views of the femoral component embodying the present invention embodied as a bicompartmental knee prosthesis; FIG. 62 is a diagrammatic illustration showing the manner of rotation of the common generating curve of the present invention; FIG. 63 is a diagrammatic illustration showing the manner in which the common generating curve of FIG. 62 is rotated about the respective axes to generate the segments of surfaces of revolution defining the shape of the femoral bearing surface of the alternate embodiment of the present invention embodied as a knee prosthesis; an FIG. 64 is a diagrammatic illustration showing articulation between the patella prosthesis and the femoral component of an alternate embodiment of the present invention embodied as a knee prosthesis.OMPI DETAILED DESCRIPTION OF THE INVENTION FIG. 1 depicts an ankle prosthesis embodying the present invention in its intended environment, the human ankle. As will be shown later, however, the present inven tion is not so limited and with appropriate changes in dimension and configuration it may be used with equal facility in any other dysfunctional human joint of similar construction as noted above. As shown in more detail in the exploded view of FIG. 2, endoprosthesis 10 comprises a tibial component 11, a bearing insert 12 and a talar component 13. While the method by which prosthesis 10 is implanted forms no part of the instant invention and, indeed, may vary from surgeon to surgeon , it is instructive to briefly review the normal operative procedure. First, the surgeon osteotomizes the distal tibia to receive tibial component 11, but component 11 is not installed at this time÷. Next, the talus is slotted to receive talar component 13 which, after the surgeon is satisfied with the slot cut into the talus, is then cemented into place. Then, tibial component 11 is cemented into place and finally tibial insert 12 is snapped into tibial component 1-3. to provide the desired axial rotation and bearing surface. Advantageously, both the tibial and talar components are fabricated from a Co-Cr-Mo alloy while the bearing insert is fabricated from a non-metallic material such as ultra-high mole- cular weight polyethelyene (UHMWPE) . Of course, other materials may be substituted provided that they are biologically compatible and satisfy the stress- and wear requirements of the prosthesis. For example, ceramics and carbon-fiber filled UHMWPE have been considered for the bearing insert. Stainless steel or any of the known titanium, nickel, or titanium-vanadium aluminum alloys could similarly be used for the tibial and talar components. Ceramics could also be used to advantage forOM 1 these parts.2 FIGS. 3-6 depict tibial component 11 in greater3 detail. FIGS. 3-5 are respectively the top, cross-4 sectional and bottom views of the component while FIG. 65 is an alternate cross-sectional view of the component.6 Referring now to FIG. 3, it will be seen that tibial comp-7 onent 11 has a generally rectangular configuration with8 one pair ofrounded edges 14-14 and one pair of straight9 edges 16-16, the latter having a slight inward bevel 17 0 at one end. In the illustrative embodiment, the bevel 1 makes an angle of about 12° to the straight edges. The 2 upper portion 18 of component 11 is grooved in two 3 orthogonal directions to create a serrated surface which 4 serves to provide increased shear resistance. The 5 serrated surface supports a pair of upwardly extending 6 fins 19 which are tapered inwardly along all four sides *7 to lock the cement to the fins. The fins 19 have a 8 relatively low profile so that only a minimal resection 9 of the distal tibia is necessary. The low fin profile also greatly facilitates the insertion of the prosthesis 1 by the surgeon. 2 The overall shape of tibial component 11 closely 3 approximates the cross-section of the tibia into which it is to be fitted. This maximizes the prosthesis-to- 5 bone contact area which is important because a maximum 6 contact tends to minimize tipping effects resulting from *7 eccentric loads which tend to produce tensile loading 8 which may pull the cement away from the bone causing the 5 component to loosen and preventing bone growth adjacent 0 the cement. This arrangement also minimizes compressive 1 stress on the bone. As is well known, the closer that bone stress approaches that found in the average, 3 healthy subject, the healthier the bone will be because excessive bone stress can cause necrosis of the bone. 5 The tibial component shown in FIGS. 3-6 maximizes the 6 area over which 'the load is applied by making the compon- ent as large as possible given the limitations of the joint space which is available. As seen best in FIG. 6, note also that edges 16 are tapered inwardly which minimizes bone resection and the serrations on these surfaces help resist tension loads resulting from possible eccentric loads. As shown in FIGS. 4 and 5, tibial component 11 includes a conical recess 21 with an axis substantially parallel to the tibial shaft which receives the non-metallic bearing insert 12. The interior of recess 21 is accurately machined and highly polished to provide a bearing surface 21a. Thus, when insert 12 is positioned within the recess, the low- friction conical .bearing surface 21a permits the desired axial rotation of the ankle. Component 11 is further provided with an aperture 22 through which the ears 23 of a snap- ring 24 (FIG. 10) may pass. Recess 21 is further provided with a groove 25 which is slightly larger in diameter than recess 21. Groove 25 retains snap-ring 24 when non-metallic insert 12 is positioned within component 11. FIGS. 7-9 are respectively the top, side and bottom views of non-metallic intermediate bearing component or tibial insert 12. As shown, insert 12 is provided with an upwardly extending portion 26 having an upper bearing surface 26a which is congruent with bearing surface 21a of the tibial component 11 and which is for congruent rotational engagement therewith in the conical recess 21 of component 11- Upwardly extending portion 26 includes a groove 27 which aligns with groove 25 in tibial component 11 when insert 12 is mated with the component. The extreme upper edge of portion 26 of the cone spreads snap-ring 23 apart when tibial insert 12 is first posit- ioned in recess 21. As shown in FIGS, 8 and.9, tibial insert 12 has a downwardly extending portion 28 having a cylindrically concave bearing surface 29 which is less than one half a complete surface of revolution andO which is designed for area contact sliding engagement with a similarly cylindrical convex bearing surface 34 of equal, or substantially equal, radius on talar component 13 (FIG. 12). As will be noted from FIG. 9, the plan view of concave surface 29 approximates the dimension and shape of surface 18 in tibial component 11, but is slightly smaller to accommodate axial rotation. FIGS. 11, 12 and 13 are respectively, the bottom, side and cross-sectional views of talar component 13. As shown, talar component 13 comprises an upper portion 33 having an upper convex bearing surface 34 which is less than one half a complete surface of revolution and being provided with a centrally located, serrated, fixation fin 32 extending downwardly therefrom. Essentially, the upper portion 33 of component 13 comprises a segment of a cylinder. As previously discussed, the cylindrical, convex shape of bearing surface 34 is in area contact with the cylindrical, concave surface 29 of tibial insert 12 which, thus, permits low-friction, area contact, sliding relative rotational motion therebetween. This motion is constrained by the cylindrical nature of the bearing surface 34 to rotary motion about the axis of the cylinder of which upper portion 33 is a segment so long as these surfaces are kept in area contact. These surfaces may however be partially uncoupled to provide rotation about an anterior-posterior axis. Referring momentarily to FIG. 8, it will be noted that in the illustrative embodiment, concave surface 29 has a radius of about 0.85 inches and subtends an angle of about 64°. In like fashion, in the illustrative embodiment convex surface 34 also has a radius of about 0.85 inches and subtends an angle of about 128°. Thus, when pressed into engagement for congruent, sliding rotary motion, the prosthesis 10 permits a plantar- dorsiflexion range of up to 64° without loss of area contact between surfaces 29 and 34 although in practice the angle subtended by surface 34 could range from 100° to 140° and the angle subtended by surface 29 could range from 50° to 70°. It will be noted that the angle sub- tended by convex bearing surface 34 is asymmetric with respect to the vertical .axis being displaced 29° in the anterior direction but only 23° in the posterior direction This results in a plantar-dorsiflexion movement which closely approximates that found in the normal foot which allows more dorsiflexion motion. It is often extremely difficult to determine in advance what the overall height of a prosthesis should be, especially when dealing with a degenerate distorted ankle. It is thus an important aspect of the instant invention that non-metallic tibial insert 12 is removable from component 11. By providing a variety of tibial in- serts, e.g. of 2, 4, 6 . . . mm height, the surgeon can try out different tibial inserts until he finds one of the appropriate height. Of course, snap-ring 24 is not used to retain tibial insert 12 until the surgeon is completely satisfied with the trial fitting. The fact that insert 12 can be easily removed during the trial fitting means that the surgeon has excellent visibility of the implanted tibial and talar components and can, thus, check for and remove, if necessary, excessbone cement and/or correct other defects. Of course, non-metallic tibial insert 12 can also be removed after it has been locked into place by snap-ring 24 because ears 23 are accessible through aperture 22 in tibial component 11. It should also be pointed out that replacement of tibial insert 12 may also be effected during a second operation. This may be necessary to correct for excessive and unusual wear of the non-metallic component or where th surgeon feels, in retrospect, that he initially selected a tibial insert of inappropriate dimensions. The fact that neither the fixation to the tibia nor the fixation to the talus need be disturbed during the * -15-1 second operation demonstrates the significant advantage2 that the instant endoprosthesis possesses over prior art3 devices.^ It will also be appreciated that the radius of the5 bearing surface 34 of the talar component need not be as depicted in FIG. 12. In fact, the radius may be consider-7 ably larger or smaller than shown. In the illustrated8 talar component shown in FIG. 12, tibial insert 13 is9 thickest in the center, thinner in the anterior direction 10 and thinnest in the posterior direction.H This variation in thickness and radius of .curvature12 is intended tio accommodate talar domes of different radii 3 and the varying conditions that are typically experienced1 when dealing with degenerative bone. That is to say, l-5 while the shape of the talus is fairly well defined in16 the normal ankle joint, it is ill-defined in the patholog- l' ical or degenerate joint. Of course, the reason that the 8 endoprosthesis is needed in the first place is because 9 the bone, or bones associated with the joint have degener- 0 ated. For that reason, the surgeon needs a variety of x shapes to insure good, congruent, contact with the bone. Some incongruity can be taken up by the cement, which is typically methyl-methacrylate., but a large degree of4 incongruity is undesirable because the amount of cement used should normally be held to a minimum. It is, thus,6 another important feature of the invention that a large ' number of talar components can be made available to the0 surgeon although only one is shown in the drawings.The fixation fin used on the talar component is somewhat longer than the fixation fins used on the tibial component1 because access to the talus is no problem. That is, _ _ • because the talar component is generally implanted before the tibial component is inserted surgical access is excell¬ ent. Another reason that the talar fin is longer than the3 tibial fins is that the talus is typically degenerate and6 the use of a long talar fixation fin permits fixation of the talar component below the region of bone degeneracy. In fixation of the talar component, a slot is first made in the talus and the talar component is placed on th talus with the fin protruding into the slot which was priorly filled with cement. The cement does not act as an adhesive in the normal sense of the word; rather, it acts as a casting or grouting agent. It is thus necess- a j to mechanically interlock the talar component and talus in order to get fixation. To this end, fin 32 has. longitudinal channels 35 cut in its side to provide interlocking and tensile resistance. Anterior-posterior and medial-lateral resistance are offered by the basic shape of the component in the first instance, and by the fact that the sides of the fin 32 will impinge the bone i the second instance. As previously mentioned, surface 34 is tapered on its posterior aspect in order to extend down onto the posterior or rear aspect of the talus, thereby providing a normal anatomical range of motion. Most prior art ankle prostheses do not provide such a normal range of motion and as is known, such motion is necessary for many, normal activities, such as stair climbing. Certainly, no known prior art prosthesis provides this range of motion with a radius of curvature of the upper surface which approximates the normal ana- tomical curvature while at the same time providing con- gruent contact. FIGS. 14 and 15 depict a second embodiment of the invention which uses a cylindrical rather than a conical bearing surface. As before, prosthesis 10 comprises a tibial component 11', a non-metallic insert 12' and a tal component 13' respectively shown in greater detail in FIGS. 16-19, 20-22 and 23-25. A detailed discussion of this second embodiment is not believed, to be necessary. Suffice it to say that, as shown in FIG. 17, recess 21' is cylindrical rather than conical and, as shown in FIG. 21, the upper portion 26' of insert 12' is corresponding-^R OM 1 cylindrical. Also, in this second embodiment, edges 16'2 of tibial component 11' are not tapered, although there3 is no reason they couldnot be if the degree of bone4 resection is of concern.5 One of the more common defects found in prostheses6 using metal-to-non metal (e.g. plastic) bearing surfaces7 is deformation and flow of the non-metallic component 8 under load. This cannot occur in the instant invention for9 two reasons: (1) because tibial insert 12 is free to10 rotate in the tibial component, the ankle is free to rotate11 axially with respect to the tibia as it wants to do, thus12 the extreme loads present in the prior art prostheses 13 simply do not occur; and (2) the fact that the upper end 14 of tibial inserts 12 and 12' are respectively confined If) within conical or cylindrical recesses 21 or 21' prevents16 excessive deformation or flow.17 The two illustrative embodiments discussed so far18 provide unconstrained axial rotation in relation to the19 tibial component and unconstrained cylindrical rotation20 about the talar component. This novel arrangement allows21 physiological axial rotation of the tibia-talar joint22 without causing axial torque on the cement beds. Of the23 two metal components, the talar onlay geometry of compon-24 ents 13 and 13' provides a rotation center which is25 compatible with the lateral or constant geometry center26 of the normal ankle. This provides physiological loading27 on the lateral, or sprain prone, ligaments of the ankle.28 Since good ligamentous stability is a pre-requisite29 for ankle replacement, internal malleoli are not provided30 in the first two embodiments of the invention. This•31 allows medial-lateral thrust loads to be physiologically32 resisted by the ligaments and retained bony malleoli33 rather than by constraints of the device itself.34 In situations of talar dome loss, a metal talar dome35 prosthesis can be used in place of onlay components 13 and36 13'. In these cases, small non-metallic malleoli may be added to cylindrical inserts 12 and 12' to maintain medial lateral stability. These malleoli are angled to allow up to 10° of talar tilt before disengaging. Thus, normal talar tilt can occur for as long as ligamentous stability is maintained. With fracture or ligamentous rupture, the components can disengage to avoid tear out stresses on the talar component. Non-metallic inserts of differing dimensions may again be used to provide optimal component placement and ligamentous tension. More specifically, to aid the surgeon in height adjustment intraoperatively, the non-metallic component is made in various dimensions This allows precise ligament- ous loading by virtue of shimming and permits superior bone-cement-prosthesis contact, since the removed bone can be shimmed with components of the device rather than by increased amounts of methyl-methacrylate cement. Non- metallic components are removable to allow replacement or readjustment intraoperatively without disturbing components priorly fixtured to the bone. FIGS. 26-28 depict an illustrative non-metallic tibial insert 40 which is equipped with malleoli. As shown, insert 40 comprises a conical, upwardly extending portion 41 having a circumferentially extending groove 42 therearound. As was the case for the non-metallic inserts previously discussed, the lower portion of insert 40 comprises a concave bearing surface 43 which subtends, in the illustrativeembodiment , an angle of about 64°. As best shown in FIG. 28, insert 40 further includes a pair of malleoli 44-44 to maintain the medial-lateral stability of the prosthesis. The outer walls of the malleoli are substantially vertical but the inner walls make an angle of about 10° to the vertical. Thus, up to 10° of talar tilt is possible without disengagement. FIGS. 29-31 depict the talar dome component required y non-metallic tibial insert 40. As shown, talar compon¬ ent 46 comprises an upper, convex load-bearing surface 47 essentially similar in shape to surfaces 34 and 33' in FIGS. 12 and 24, respectively. The lower surface 48 depends a pair of fins 49-49 which are cut in half by an elongated slot 51 which extends upwardly into the body of the component. Slot 51 is intended to retain the cement used to fix component 46 to the remains of the actual talar dome. To that end, the upper portion of slot 51 expands inside the main body of the prosthesis to trap additional cement and, thus, further secure talar component 46 to the talus. The outer walls 52-52 of component 46 are tapered inwardly at an angle which matches the angle at which the inner walls 45 of malleoli 44 are tapered. Thus, as shown in FIG. 32, non-metallic tibial insert 40 mates exactly with talar component 46 providing the desired medial-lateral stability. As in the case of the previously discussed prosthesis, tibial insert 40 may be made in various thicknesses to accommodate various ankle situations. It should be noted that all the prostheses discussed above are symmetrical about the anterior-posterior axis. This means that the same prosthesis may be used in either the left of right foot , which greatly simplifies the task of the surgeon. This symmetry is best seen in FIGS. 3, 11 and 29. Referring now to FIG. 33, there is shown a diagram- , atic illustration of the manner in which the ankle pros- thetic joint 10 of the present invention provides only two degrees of freedom of rotational movement between the tibia and talus bones. More specifically, relative rotational movement is permitted between the tibial component 11 and bearing insert 12 with respect to the talar component 13 about Axis 1 and relative rotational movement is permitted between the tibial component 11 and bearing insert 12 with respect to' the talar component 13 about Axis 2. Still more specifically, it will be noted and understood that no other degrees of freedom of rotational movement are permitted and hence improved joint stability is provided. Still further, it will be noted, that in the context of only two degrees of rotational movement being permitted that Axis 1 and Axis 2 are not parallel. It will be further noted that in this embodiment that medial-lateral translational movement of the tibial component 11 and bearing insert 12 with respect to the talar component 13 is permitted within the bony confines of the ankle mortise. Referring nowto FIGS. 34 and 35, there is shown a total knee joint endoprosthesis 60 embodying the present invention. More specifically, the knee prosthesis 60 com rises a pair of separate femoral components 62-62 for being fixtured to the femur such as by the integrally for ed posts 64 and a suitable cement as discussed above with regard to fixturing. The femoral components 62-62 are provided respectively with condylar bearing surfaces 66-66 which jointly form a segment of a surface of revolution about the Axis 4 of FIGS. 34 and 35. The knee prosthesis 60 further includes an inter- mediate bearing insert 68 provided with bearing surfaces 70-70 which are congruent with bearing surfaces 66-66 and which jointly form a segment of a surface of revolution about Axis 4. The intermediate bearing insert 68 is further provided with bearing surface 72 which is cong- ruent with a bearing surface 74 provided on the tibial component 76 which may also be suitably fixtured to the tibia by integrally formed posts 78 and suitable cement a described above with regard to -component-to-bone fixturin The respective bearing surfaces 72 and 74 are congruent and permit relative rotation between the femoral componen 62 and the intermediate bearing insert 68 with respect to the tibial component 76 about the axis 5. It will be understood, as described with regard to t above embodiments, that the intermediate bearing elementBUOM 68 may be suitably retained in the tibial component 76 by a suitable snap ring. Such retention of the intermediate bearing insert 68 in the tibial component 76 prevents relat- ive axial movement of the intermediate bearing insert 68 with respect to the tibial component 76 and thereby provides increased stability of the joint. However, it will be understood that in certain embodiments the snap ring may not be necessary or desirable and therefore may be eliminated. It will be further understood by those skilled in the joint prosthetic art that the prosthesis of the present invention may be embodied as a finger joint, elbow joint, wrist joint, and as a patello-femoral joint by making appropriate dimensional changes all within the teachings of the present invention. Referring now further to prior art endoprostheses., •'. and in particular to the prior art knee prostheses with patello-femoral replacement, it has been observed that such prior art prostheses have poorly designed patello- femoral interfaces- in that they do not provide reason- ably congruent area patello-femoral contact or sliding engagement over any appreciable range of knee motion. More particularly, such prior art prostheses typically produce contact stresses which result in the yielding and fatigue of the plastic bearing surface typically present in such prostheses. This is caused by the fact that the bearing surface of the femoral component over which the patella prosthesis must pass generally has several regions or segments of differing shape. For example, there is typically a fairly long, singly curved segment blending into a doubly curved segment blending again into a still different doubly curved segment. These varying segments or regions provide the femoral portion of the femoral-tibial articulation and those segments or regions do not have a common generating curve. Thus, when the patella prosthesis goes through its excursion over the femoral articular flange, the patella prosthesis meets a variety of surface contact conditions, namely, substantial portions of line contact, portions of point contact, and perhaps limited portions of area or congruent area contact. As is known, such line contact and point contact conditions generally produce excessive contact stresses which produce yielding and substantial wear of plastic prostheses. Hence, the extended wear life needed for successful prosthetic implantation is not provided. Referring next specifically to typical prior art tibio-femoral knee prostheses, it has been observed that those prior art knee prostheses that allow axial rotation and medial-lateral motion in addition to flexion- extension motion have incongruent, usually theoretical point, contact between the femoral and tibial engaged bearing surfaces which produces excessive contact stress- es leading to deformation and/or early wear and undesir- ably short prosthetic life. Wear products have also been shown to produce undesirable tissue reactions which may help induce loosening of the prosthetic components. Those prior art knee prostheses that do provide congruent or area bearing contact fail to provide the needed axial rotation. This lack of axial rotation has been shown clinically and experimentally to result in deformation and loosening of tibial components and such prostheses no appear to be falling into disuse. However, as is known, a hinge type knee prosthesis does exist, i.e. the prosthesis shown in German Offenlegunsschrift 25 45 821, April 1976, which provides such axial motion by use of a trunion type tibial device and thereby provide both area contact and axial rotation. This prosthesis, however, is structurally distinct from the present invention in that it fails to allow unconstrained abduction-adduction by uncoupling of bearing surfaces associated with the flexion-extension action of the knee or by other means. Therefore, it fails to avoid the valgus-varus torque resulting from constraint of abduct- ion-adduction thereby inducing loading into the prosthesis which has been shown to produce undesirable prosthetic loosening. Current prostheses of both the hinge and dislocateable- type such as the Geomedic knee replacement shown in U.S. Patent No..3,728,742 issued April 24, 1973 to Averill et al. that produce area contact provide only one axis of rotation relative to the femur of the flexion-extension motion. Normal flexion-extension is however character- ized by a polycentric flexion extrusion motion where rotation relative to the femur occurs about many axes. This polycentric motion allows for more efficient utilization of muscle forces by providing a posterior shift of the pivot when effective quadriceps action is important and an anterior shift when hamstrings effective- ness is important. Furthermore, in the human knee this polycentric action and the shape of the posterior condyles which influence this motion and allow full flexion capability for the leg. Failure to provide this poly- centric motion thus tends to restrict muscle effective- ness and inhibit flexion. These restrictions tend to increase the prosthesis and increase wear or likelihood of deformation or breakage and loading between prosthesis and bone tending to increase the possibility of component loosening. It is further believed that loosening problems res.ult from the direct attachment of plastic prosthetic components to bone through the use of relatively brittle cement that is weak in tension. Specifically, it has been demonstrated that even relatively thick plastic components when loaded in a normal fashion produce undesirable tensile stresses in acrylic cement which is commonly used to fixture such plastic components to bone. Such tensile stresses tend to produce bending ofBUKEA > the plastic component which causes the ends of the plasti component to lift away from the bone as a result of the bending, thereby subjecting the bone-cement attachment to tension. As is known, cement has very poor tensile fatigue properties and the bone to which the plastic prosthesis is cemented appears to be adversely affected by tensile loads since normal bone loading is compressive Accordingly, it is believed that these combined effects contribute substantially to prosthetic loosening problems and, specifically, it has been noted where clinical failu due to loosening occurs that it is almost always the plastic prosthesis component which loosens. Another prior art prosthesis problem exists with regard to those knee endoprostheses for implantation in those cases wherein the cruciate ligaments are funct- ionally absent but where the collateral ligaments are functional or are reconstructable. In the absence of cruciate ligaments', the prosthetic replacement must provi anterior-posterior knee joint stability so as to replace that stability lost by the lack'of cruciates. Until recently most such cases were treated by a stable hinge- type knee prosthesis which, unfortunately, appears to suffer from the loosening problems described above and furthermore typically produces substantial bone loss as a result of the relatively reat bone resection required for implantation and necrosis of the bone caused by altered mechanical bone stresses. More recent attempts have been made to treat such cases with surface replace- ment prostheses such as the prostheses known as the Total Condylar and similar knee prostheses. However, these kne prostheses have theoretical point contact bearing surface with their above-noted attendant problems and, in addit- ion, such prostheses tend to have instability and dislocation problems partially as a result of these point contact bearing surfaces. Referring now to FIGS. 36,37 and 38 and to FIGS. 39 through 46, there is shown an endoprosthesis embodying the present invention which has been referred to as a tri- compart ental knee prosthesis which includes the femoral component of prosthesis 100 best shown in FIGS. 39, 40 and 41; the patella prosthesis 103 comprising the inter- mediate patella bearing component 109 best shown in FIGS. 42, 43 and 44 and the patella fixturing component 116 shown in FIGS. 45 and 47; and the tibial prosthesis or component 101 comprising the tibial platform component 148 best shown in FIGS. 48, 49 and 50 and the intermediate tibial bearing component 139 shown in FIGS. 51, 52 and 53. Generally, it will be understood that this tri- compartmental prosthesis includes three embodiments of the present invention, namely a first embodiment provid- ing the patello-femoral articulation and comprised of the femoral component 100, the intermediate patella bearing ° component 109 and the patella fixturing component 116.; a second, embodiment providing the tibial femoral articula- tion and comprised of the femoral component 100, the tibial platform .component 148, and the intermediate tibial bearing component 139; all as will be more fully under- stood as taught in detail below, and a third embodiment combining the other two embodiments. Additionally, the individual components are believed to be patentably novel. Referring now to FIGS. 39, 40 and 41, there is shown in detail the femoral component 100 which includes, in the counter-clockwise anterior or posterior direction, a flange 100 formed integrally with two condyles 104-104.' The femoral component 100 also includes a pair of fixtur- ing posts; only one fixturing post, post 104a, being shown. The outside surfact of the flange 102 provides most of the bearing surface for patella articulation. The condyles 104 are provided for replacing the condylar surfaces of the human knee. The bearing surfaces of 102 and 104-104 are referred to generally as the bearing surface 106. In accordance with the teaching of the present invention, the surface 106 in the counter- clockwise anterior to posterior direction is a smooth, continuous surface formed by a series of segments of surfaces of revolution the respective shapes of which are generated or defined by rotating a common generating curve (generally identified as F) around a plurality of generating axes at respective pairs of major generating radii (or each at a respective major generating radius where the radii of each pair are equal) and through resp- ective angles of rotation. This common generating curve F is a smooth contin- uous plane curve and as may be understood from FIG. 39, the shape of which is defined by (i) two arcs Kl and K2 struck, respectively, by two radii Al and A2 from resp- ective centers Hi and H2 separated by a distance X; (ii) two lines 107 and 108 respectively tangent to the arcs Kl and K2 and at angles <=><. 1 and σ< 2, respectively,' with respect to a line G tangent to arcs Kl and K2; and (iii) an arc K3 struck by radius B from center H3 and wherein arc K3 is also tangent to the tangent lines 107 and 108. Referring now to FIG.63, where a further understand¬ ing of the general teachings of the present invention is illustrated, it will be understood that the shape of the bearing surface 106 (FIG. 39) is defined or generated y a series of segments of surfaces of revolution each of which segments is defined or generated by rotating the common generating curve F around a respective generating axis at respective pairs of major generating radii (or each at a major generating radius where the radii of. each pair of major generating radii are equal) and through a respective angle of rotation. In generatin each segment of a surface of revolution, the common generating curve F is oriented with respect to a generating axis by a pair of major generating radii Dl and D2 which are the respective distances (shortest2 distances) . from points Ml and M2 where the common generat-3 ing curve F contacts tangent line G.4 Referring now to FIG. 63, it will be understood that5 this figure is a diagrammatic illustration showing the g manner in which the series of segments of surfaces of η revolution SI, S2,' S3 and S4 defining the shape of the g bearing surface 106 are generated and where the curve Q3 represents the trace of points Ml and M2 as viewed LQ along line G (FIG. 62) resulting from the rotations• about the respective generating axes generating the•^2 surface segments. It will be further understood that the■|_3 shape of the bearing surface 106 is defined by a series of 4 segments of surfaces of revolution where each pair of-^5 major generating radii Dl and D2 for generating each1 segment decrease in length respectively as rotation of17 the generating curve F proceeds about each generating18 axis in the counterclockwise anterior to posterior19 direction as viewed in FIG. 63. In the present embodi-20 ment and as illustrated in FIG. 62, the pairs of major 2i generating radii Dl and D2 are equal in each instance and22 roay in each instance be replaced by a single major23 generating radius R (i.e. Rl, R2, R3 and R4) as shown in24 FIG. 63. In this embodiment, the bearing surface 10625 consists of four segments of surfaces of revolution26 SI, S2, S3 and S4.27 Si is generated by rotating the common generating28 curve F through an angle 01 about generating axis Cl29 perpendicular to the plane of FIG. 63 at a major gener-30 ating radius Rl. In the present embodiment, Rl is equal31 to infinity and since only the patella intermediate32 bearing component 109 of FIGS. 30, 40 and 41 articulates33 with segment SI, it will be referred to as the patella-34 femoral bearing surface segment.35 Segment S2 is generated by rotating the common36 generating curve F through an angle Θ2 about generating axis C2 parallel to Cl at a major generating radius where R2 is equal to radius Al which is equal to A2 in FIG.39; since such radii are equal, it will be understood that segment S2 is a spherical surface of revolution. For continuity and smoothness of surface 106, axis C2 must lie on the ray Ll passing through Cl and defining the end of segment SI. This segment (S2) is of special import- ance since both the patella and tibial intermediate bearing components 109 and 139, respectively, articulate with this segment and since the greatest loads on these components during normal walking occur when they articulat against this femoral bearing segment. This segment (S2) will, therefore be referred to as the primary load bearing surface segment. Segment S3 is generated by rotating the common gener- ating curve F through an angle Θ3 about generating axis C3 parallel to C2 located at major generating radius R3 where R3 is less than R2. Again, for continuity and' smoothness of surface 106, axis C3 must lie on ray L2 passing through C2 and defining the end of segment S2. Finally, segment S4 is generated by rotating the common generating curve F through an angle 04 about generating axis C4 parallel to C2 located at major gener- ating radius R4 which is less than R3. Again for contin- uity and smoothness of surface 106, axis C4 must lie on ray L3 passing through C3 and defining the end of segment S3.' These latter two segments will be referred to, respectively, as the first and second posterior femoral bearing surface segments respectively. Referring again to FIG. 40, it will be understood that FIG. 40 is a side view of an actual embodiment of the present invention as shown if FIG. 39 and that the segments of surfaces of revolution SI, S2, S3 and S4 shown in FIG. 63 are also shown in FIG. 40 at their respect- ive locations. In one embodiment of the present invention, theOΛI WIP 1 respective angles θ and each respective major generating2 radius were as follows :3 SEGMENT 0 DEC ΪREES MAJOR GENERATING RADIUS 4 R/in 5 SI 0 co displacement .612 6 2 107 3/4 1.388 '7 S 3 62 1/4 .8018 S4 62 .5789 Referring again to FIGS. 40 and 63, it will be noted10 that the generating axes Cl, C2, C3 and C4 are parallel'11 with respect to each other and it will be understood that 12. the tangent line G is oriented substantially parallel to13 the generating axes, however, in accordance with the14 teachings of the present invention, such need not be the15 case and the generating axes may be oriented other than16 parallel with respect to each other and, as shown in the17 general case illustrated in FIG. 62, the tangent line G18 may be oriented with respect to the generating axes other19 than parallel.20 Referring again to the patella prosthesis and in21 particular to the intermediate patella bearing component22 109 of FIGS. 42, 43 and 44, it will be understood that in23 accordance with the further teachings of the present in-24 vention such intermediate bearing component provides a25 load bearing surface indicated by general numerical26 designation 110 for engaging the bearing surface 106 of27 femoral component 100 and which load bearing surface 11028 includes a primary load bearing surface segment 111, a29 pair of secondary load bearing surface segments 112 and30 114 and a pair of transition segments 112a and 114a31 between 111 and 112 and 111 and 114 respectively.32 Further, it will be understood in accordance with the33 teachings of the present invention that the shape of the34 load bearing surface 110 of the patella intermediate bear-35 ing component 109 is defined or generated by the common36 generating curve F used to generate the segments S1-S4 of the femoral bearing surface 106. Referring to FIG. 43, it will be understood that the common generating curve F is rotated through an angle Θ5 (in -one embodiment angle Θ5 equalled 20°) about generating axis C5 at the pair of major generating radii Dl and D2 shown in FIG. 62 where Dl and D2 are equal and are equal to major generating radius R2 shown in FIG. 63, to define the shape of the primary load bearing surface segment 111. Therefore, the patella primary load'bearing surface segment 111 congruently matches the primary load bearing surface segment S2 of femoral .bearing surface 106 and upon art- iculating therewith engages the primary femoral bearing surface segment S2 in sliding area contact. The secondary load bearing surface segments 112 and 114 of the patella bearing sur- face 110 of FIG. 43 likewise match the patella femoral bearing surface segment SI of surface 106 of FIG. 40 and hence their shapes are define or generated by rotating the common generating curve F about an axis at infinity parallel to axis C5 as was done in generating the shape of segment SI of femoral bearing surface 106. Therefore, the patella prosthesis secondary load bearing surface segments 112 and 114 congruently match the patello femoral bearing surface segment Si of femoral bearing surface 106 and upon articulating therewith engage the femoral bearing surface segment SI in sliding area contact The transition segments 112a and 114a defined by rotating the common generating curve F through angles Θ7 and θ8 abo axes C7 and C8 respectively at a pair of negative gener- ating radii (directed to opposite sides of common gener- ating curve F from those shown in FIG. 62) both about 0.30 ' in. in one embodiment. These transition segments 112a or 114a engage in line .contact segments S2 and SI of the femur near their interface as the contacts shift between segment S2 of the femur with the primary load bearing segment 111 to contact between femoral segment SI and the secondary load bearing segments 112 and 114. In another embodiment of the patella prosthesis of the present invention, the segments 112 and 114 are inclin- ed downwardly with respect to the horizontal as viewed in FIG. 43 to better accommodate the orientation of the pat- ella prosthesis with respect to the femoral prosthesis during full extension of the human knee as shown in FIG. 64 and therefore provides a more uniform load distribution on the secondary load bearing surface segment 112 or 114. The patella intermediate bearing element 109 is retained on the remnant of the human patella by use of the patella fixturing component 116 of FIGS. 45 and 47 which fixturing component may be suitably fixtured to the remnant human patella by use of an acrylic grouting agent or cement by crossed fixturing fins 117 and 118 on the dorsal side of the metal plate 120. Such fixturing fins resist tipping loads, as shown in FIG. 56, and, in addit- ion, provide a reinforcing effect which allows the use of a thin plate 120 which is desirable, since one wishes to minimize the-change in overall patella thickness resulting from prosthetic replacement so as not to adversely affect patella function, skin closure after surgery and cosmesis. The fins and metal plate reinforce and strengthen the patella remnant and minimize the possibility of its fracture. The opposite or ventral side of plate 120, FIG. 45, which comprises the bulk of the secondary fixturing component bearing surface which mates with the secondary bearing surface 128 on the patella intermediate bearing element 109, is provided with a button 122 which retains the patella intermediate bearing element on the patella fixturing component 116 with a snap fit. As shown in . FIGS. 45 and 46, the outer diameter of the button 122 is formed from a curve with two tangent radii which produce a smooth retaining male surface 122a when mated with a correspondingly shaped female surface 124 (FIG. 42) pro- vided on the patella intermediate bearing element 109. These shapes allow easy entry of the male into the female member without producing permanent deformation resultingOK from conventional snap-fit configurations. The mating conical sections provide additional secondary compressive and thrust bearing surfaces. The button 122 is provided with a generally conical shaped bearing surface 126 for rotatably engaging the correspondingly shaped conical sec- ondary bearing surface 128 of FIG.42 provided on the patell intermediate bearing element 109 in congruent or area rotational engagement to permit rotation of the patella with respect to femoral bearing surface 106 and the distal end of .the femur about axis A8 (^IG. 38) . Further, and referring to FIG.45, the patella fixtur- ing component 116 of FIG. 45 is provided with a pin 130 for engaging a corresponding, curved slot 132 formed in the intermediate patella bearing component .109 (FIG. 42) to limit the relative rotation between intermediate patella component- 109 and the patella fixturing component 116 and thereby prevent disorientation between the intermediate patella component 109 and the femoral component 100 during implantation and subsequently during actual use. Further this limited rotation has been found to be reasonably necessary since effusion (built up of blood) post-operat- ively may temporarily lift the patella primary bearing surface 110 of the patella intermediate bearing element 109 free of the restraining effects of the femoral component 100. It will be further noted, as shown in FIGS. 42-47 that the patella intermediate bearing component 109 and patella fixturing component 116 are made symmetrical about a plane passing through the center of the primary load bearing .segment 111 and through the generating axis C5 producing segment 111, so as to allow the use of the same patella prosthesis in either the right or the left knee. It is for this reason that two rather than one secondary load bearing segments (112 and 114) are provided on the bearing surface 110. Referring now to FIGS. 54A-54C, there is illustrated-BUROM 1 diagrammatically, the manner in which the patello-2 femoral portion of the tricompart ental prosthesis pro-3 vides area or congruent sliding contact between the bearing4 surface 106 of the femoral component 100 and the bearing5 surface 110 of the patella-intermediate bearing element 1096 over the important phases of the range of motion commonly7 experienced by the human knee and provides line contact8 between such bearing surfaces only during a brief trans-9 itional phase. Referring first to FIG. 54A, it will be10 noted that at full knee extension the quadriceps muscle11 group provides a quadriceps force F . which in normal12 activities is quite low at full extension and because of13 the orientation of the force F the resultant patello-Q14 femoral compression force R of FIG. 54A is only a small15 fraction of force F . During this phase of human kneeQ16 action there is area contact between the bearing surface17 segments SI and il2 and 114 of the femoral and patella 18. components, respectively, see FIGS. 40 and 43.19 Referring now to FIGS. 54B and 54C wherein the load20 bearing stance phase experienced during the normal walking21 cycle is illustrated diagrammatically, it will be noted22 here the quadriceps force Fn is greater and hence the23 resultant patello-femoral compression force R is much24 greater than at the full extension illustrated in FIG.25 54A by virtue of the greater quadriceps force F_. and the26 smaller included angle between the quadriceps force F27 and the patella ligament force Fn, . Of course, as is28 known, even greater flexion angles are experienced by the29 human knee during stair climbing and descent and hence30 at these times even greater patella bearing resultant31 forces R occur.32 It will be understood that during the short transit-33 ion phase in moving from segment SI to segment S2 that34 transition segments 112a or 114a of the patella bearing35 surface 110 is in sliding line contact with the femoral36 bearing surface 106. As is further known, during the mostOMPI common and hence most important human knee activity, namely level walking, there is no substantial quadriceps activity or force present until approximately 10° of knee flexion is achieved at which the patella articulation of the prosthesis of the present invention has just entered the primary load bearing surface segment S2 wherein there is sliding area contact between the femoral bearing surface segment S2 and the patella primary load bearing segment 111. Thus, the above-noted transitional and hence moment- ary line contact is not of serious concern since at this time the quadriceps force FQ is essentially negligible and even if it were substantial the resultant compression force R would still be quite low by virtue of the large included angle between forces FQ and F_, . Area or contact is only needed during the walking load bearing and other activity phases where compression forces R are significant. The regions SI and S2 on the femoral component and corresponding transition segments 112a or 114a and the primary and secondary load bearing segments 111 and 112 or 114 are needed to. produce anatomical patella femoral articulation wherein at full extension as the superior aspect of the patella lifts off the femur as in FIG. 54A and yet allow central area contact engagement at moderate and full flexion as shown in FIGS. 54B and 54C. Referring now to FIG. 54C, wherein deep knee flexion is illustrated diagrammatically, it will be seen that it is during deep knee flexion that the patello-femoral compression load R is highest. It will be understood, and as illustrated in FIG. 54C, the patella -bearing surface 11 (FIG. 43) articulates with the same surface segment S2 (FIG. 40) wherein the tibial femoral articulation occurs during full extension, thus, the primary load bearing surface segment S2 of surface 106 supplies the femoral bearing surface for both articulations (patello-femoral • and tibio-femoral articulations) at times of greatest loading during the walking yait cycle and this commonality is a significant feature of the present invention. Of course, as known to those famil ar with the anatomy of the human knee, this situation (common articulation between a portion of the human condyles and both the patella and tibial bearing surfaces) does not occur. As shown in FIG. 55, in the human knee the femoral anterior articular cartilege against which the human patella articulates is distinct from that which articulates with the tibia. Such natural structures adapt during devel- op ent of the human knee to produce precise mating of the structural and articulation elements of the knee but such precision of mating is not practical in replacement knee prostheses because of the large individual variations found in different human knees and the manufacturing and surgical difficulties involved in producing such precision. Thus, the use of a common femoral prosthesis primary load bearing surface segments S2 for both the patella and tibial articulations represents a significant feature in prov- iding the needed sliding area engagement or congruency of articulation for extended wear life. Referring again to FIG. 42, it will be noted that the depth of engagement of the patella bearing surface 110 into. the femoral bearing surface 106, distance T shown in FIG. 42, is substantial and hence allows substantial sublux- ation resistance to side thrust loads. It has been found that in individuals where this dimension is small or excessive knee valgus is present, subluxation of the patella is common. Yet in many known prior art devices, the corresponding depth of engagement provided is inadequate or non-existent. Further, and referring again to FIGS. 42 and 45, it will be noted that area rotatable mating fit (bearing surfaces 128 and 126) between the patella intermediate bearing insert 109 and the patella fixturing component 116 allows rotation therebetween and this rotation is highly desirable to accommodate possible 1 surgical misalignment during implantation and the small2 naturally observed patella rotation with respect to the3 human femur during flexion-extension movements.4 Referring now to FIGS. 51, 52 and 53, and to the5 intermediate tibial bearing component 139 shown therein,6 this component provides a primary load bearing surface 1407 on its superior side and a second bearing surface 142 on8 its inferior side. The primary load bearing surface 1409 is also formed as a surface of revolution and its shape is10 defined or generated by the common generating curve F11 used to generate the shape of segments S1-S4 of femoral12 bearing surface 106 and the shape of patella bearing surf-13 ace 110.14 Referring now to FIG. 52, it will be understood that15 the shape of the primary load bearing surface 140 is16 defined by rotating the common generating curve F through17 an angle θfi (in one embodiment of the present invention18 Of- equalled 70 degrees) about generating axis C6 at the19 same major generating radii Dl and D2 shown in FIG. 6220 where Dl and.D2 are again equal and equal to R2 shown in 21. FIG. 63.- Therefore, the tibial primary load bearing22 surface 140 congruently matches the primary load bearing23 surface segment S2 of femoral bearing surface 106 and24 upon articulating therewith engages the femoral primary25 bearing surface segment S2 in sliding area contact.26 Therefore, congruent articulation is provided at the27 tibial-femoral joint interface for approximately 36 degree28 of knee flexion wherein the greatest loads during the29 walking cycle are experienced as indicated in FIG. 54B.' 3-0 The 0 to 95 degree flexion-extension range includes31 almost all strenuous activities in which an individual32 with an endoprosthesis is likely to engage. Articula-33 tion in the 35-95 degree range occurs in the first34 posterior femoral bearing segment S3 of FIG. 40 and hence 35. there is line contact as indicated in FIG. 54C. Although 36 such line contact or incongruity is less desirable than sliding area contact, it produces acceptablylow contact stresses while allowing sufficient flexion necessary for normal activities since loads during walking in this phase of flexion are much less than in the 0-36 degree range or area contact phase. Heavy joint loading in this range of knee motion occurs much less frequently than in the 0 to 36 degree range and thus higher periodic or transitional stresses can be tolerated without producing fatigue or excessive wear. Flexion from 95 degrees to 140 degrees is accommodated by the second posterior femoral bearing segment S4 of the femoral prosthesis and expected, stresses at such flexion angles are such that serious permanent deformation is not anticipated except perhaps during deep knee bend exercises such as deep squats which should be avoided by anyone having any knee prosthesis. Fatigue is not of concern here (segment S4) since the expected fre- quency of occurrence of these stresses is low. Obviously, a patient with such knees should be strongly encouraged not to perform deep knee bend or similar exercises. It should be noted that few knee prostheses allow in excess of 90 degrees of flexion and those that do, while still allowing reasonable axial rotation, experience far greater contact stress than the present invention. The last region is provided to allow the extreme flexion range which is often needed during sitting where small loads on the knee are experienced. The two incongruent or line contact phases of contact associated with segments S3 and S4 are provided in order to provide nearly normal flexion and extension motion by providing a reasonable approximation to normal condylar geometry. Incongruency in these phases occurs only in one dimension rather than two dimensions as in most prior art prostheses. Thus, normal motion is provided while keeping contact stress within acceptable limits of most normal activity. The second bearing surface 142, FIGS'. 51, 52 and 53, is on the inferior side of the intermediate tibial bearing component 139. This bearing surface is comprised of a flat surface 143 and a projecting conical surface 144. The flat and conical bearing surfaces engage the superior surface 145 of the tibial fixturing component 148 shown in FIGS. 48, 49 and 50, and the conical surface 150 therein in area contact and provides rotation about a single axis, i.e. axis A7 of FIG. 38 to permit axial rotation of the tibia with respect to the femur. The shape of the plate section 152 of the tibial platform component 148 is contoured so as to engage, where practical, the outer cortical bone of the tibia so as to improve load bearing and to allow this component to be used for both right and left tibias. A short spike 153 which helps distribute joint loads and supplies additional load transfer to the cortical bone on its posterior aspect is used for improving load bearing. It will be understood that the double symmetry of both tibial components 139 and 148 eliminates the need to designate an anterior or posterior aspect of these compon- ents, as well as the right or left knee aspect, and thus eliminates the concern of the implanting surgeon with these matters during implantation. It will be further understood by those skilled in the art and referring again to the femoral component 100 and the patella prosthesis 103, that the bearing surfaces 120 and 126 of the patella fixturing component 116 and bearing surfaces 128a and 128 of the intermediate patella component 109 accommodate both axial surgical misalignment and normal rotation while ^permitting area contact between the bearing segments SI and S2 of the femoral component 100 and the bearing surface 110 of the intermediate patella component 109. Similarly, it will be further un- derstood that the bearing surfaces 143 and 144, respective- ly, of the intermediate bearing -component 139 and the bearing surfaces 145 and 150 respectively of the tibialOM platform component 148 accommodate both axial surgical misalignment and normal rotation while permitting sliding area contact between the primary load bearing segment S2 of femoral component 100 and the primary load bearing sur- face 140 of the intermediate tibial bearing component 139. This congruence is provided in the important stance phase of walking illustrated diagrammatically in FIG. 54B. This congruence or area contact also has an additional advantage, namely, it provides greater anterior posterior stability by providing greater overlap as illustrated diagrammatically in FIG. 57. It will be understood that the incongruity illustrated in FIG. 57 reduces the overlap dimension and thereby reduces anterior-posterior stability. in the case of congruity, this overlap is further reduced by rotation of the femoral component 200 with respect to the tibial component 201 as a result of normal walking or surgical misalignment. The present invention, as embodied for providing the tibio-femoral articulation, and as illustrated in FIG. 37, provides great anterior-posterior stability b virtue of its congruency or area contact which provides the greater overlap dimension shown by the arrows 202 and 203 of FIG. 37. and anterior-posterior stability if further provided by avoidance of rotation between the tibio-femoral bearing surfaces 140 and 106 (rotation being provided between the surfaces 143 and 145, respectively, of the tibial inter- mediate bearing component 139 and the tibial platform component 138) . Further, and as will be understood by those skilled in the art, greater medial-lateral shear stability is provided by the present invention due to the deep engage- ment between the femoral component 100 and the tibial prosthesis 101 as illustrated by arrow 205 of FIG. 36. Referring now to FIGS. 58 and 59 and FIGS. 60 and 61, there is shown a bicompartmental embodiment of the present invention utilizing a pair of individual femoral componentsOMPI 301 and 302 and, as illustrated diagrammatically in FIGS. 60 and 61 omits the use of the patella prosthesis 103. Referring specifically to FIGS. 58 and 59, there is shown therein a right individual femoral component 301 and it will be understood that the individual femoral component 302 shown in FIGS. 60 and 61 is the mirror image of the femoral component 301 shown in FIGS. 58 and 59. Tibial prosthesis 101 of this embodiment is the same as the tibial prosthesis 101 described above. It will be understood, and referring to FIG. 61, that the individual femoral components, e.g. 302, are provided with a load bearing sur- face 306 which is identical to the segments S4, S3, and a major portion of the primary load bearing segment S2 shown if FIG. 40. Thus, it will be further understood that segment S2 of these individual femoral components 301 and 302 are in area contact with the primary load bearing surface 140 of the tibial component 101 as taught above and thus provides the same tibio-femoral articul- • ation as described above. Referring again to FIGS. 51, 5.2 and 53, it will be still further understood by those skilled in the art that the intermediate tibial bearing component 139 may be eas- ily removed intraoperatively to allow replacement of this component with an intermediate tibial bearing component having a thickness providing proper ligamentous (collater- al ligaments) tension. Thus, a number of intermediate tibial bearing compon- ents of varying thicknesses may be provided so that the implanting surgeon may shim for proper ligamentous tension without disturbing fixtured components, e.g. tibial plat- form component 148 and femoral component 100. Further, such structure allowseasy replacement of the intermed- iate tibial bearing component 139 in the event of unusual or unexpected wear or deformation. Similarly, this is true with respect to the patella prosthesis 103 wherein the intermediate patella bearing component 109 may be of varying thicknesses and replaceable in the event of unusual or unexpected wear or deformation. It will be further understood that the femoral component 100, the patella fixturing component 116, and the tibial platform component 148 may be made preferably of a surgical metal such as cobalt-chromium alloy or titanium or stainless steel but may be made of any relat¬ ively rigid material (compared with the grouting agent) that is biocompatible, capable of withs'tanding the applied loads, and possesses adequate bearing properties against the intermediate bearing insert's, e.g. the intermediate patella bearing component 109 and intermediate tibial bearing component 139 may be made of any biocompatible material strong enough to withstand loads and adequate in bearing against the material with which it is engaged, but is' preferably made of a plastic such as ultra high molecular weight polyethylene or copolymer acetal.'BU EAU KNEE ENDOPROSTHESIS SURGICAL IMPLANTATION PROCEDURE The patient is placed in a supine position on the operating table. The knee is prepped and draped in a sterile fashion. A thigh tourniquet previously applied is inflated to 400mm Hg after elevation of the leg for one minute to allow for venous run-off. The knee is fully extended and a gently curved S- shaped incision is made oh the tibial tubercle up towards the medial border of the patella tendon, then curving posteriorly along the medial border of the vastus medialis The medial retinaculum, capsule and synovial layer are incised in line with the skin incision. The vastus medialis muscel belly is elevated free from its attachment to the adductor magnus tendon. The patella is reflected laterally exposing the entire tibio-femoral joint. If there is excessive tension in the quadriceps mechanism preventing complete- lateral displacement of the patella, then sharp detachment of the medial 1/4 of the patella tendon from the tibial tubercle may be necessary. In a similar fashion, further blunt disection of the medial attachment of the vastus medialis may be needed to mobilize the quadriceps mechanism proximally. These maneuvers will allow complete flexion of the knee to 110 degrees with complete anterior exposure of the joint. At this time, excision of hypertrophic synovium and redundant fat pad is performed. Medial and lateral menisectomy will facilitate exposure of the tibial plat- eau borders and should be performed. Examination of the intercondyler contents will reveal the condition of the cruciates. Redundant synovium should be excised from this region to prevent possible impingement or overgrowth onto the tibial component surface. With the proximal tibial and distal femur cleared of soft tissue debris, bone guards are slid posteriorly between the collateral ligaments and the posterior capsule to protect the posterior neurovascular bundle during resection of the articular surfaces. A 3/4 periosteal elevator may be used to develop the soft tissue planes for the bone guards, which also serve as knee retractors. The knee is flexed to 100 degrees and a drill hole at the intercondyler notch border is made with a 1/4 drill. The drill is taken down to the level of the post- erior femoral shaft. Next, a tibial resection jig is placed with a spike located on the posterior aspect of the femoral shaft and a distal limb of the instrument parallel to the tibia. With the collateral ligaments in tension during this flexion phase, a proper resection plane is insured by use of the parallel cutting slots available in the jig. The jig has an automatic 10 degree retro- version angle insured when the knee is flexed parallel to the distal limb of the jig. Using an oscillating saw, the tibial preparation is made. The resection planes are made at 5, 10, or 15 mm, depending upon the amount of bone stock available for perpendicular loading of the tibial component. Once the proper flexion tension has been achieved and the bone resection has been made, the tibial alignment jig is removed from the femoral shaft and the femoral shaper is next replaced into the same channel. The femoral shaper is situated such that the anterior and posterior cuts are symmetrically parallel to the femoral condyles. Using again an oscillating saw in these cuts, the anterior surface and posterior condyles of the femur are resected. The knee is then brought into full extension after removal of the femoral shaper and an extension fem- oral alignment jig is placed into the joint. With manual traction on the femur and aligning an adjustable -valgus guide into 5 to 10 degrees of physiologic valgus , l.the horizontal cut on the distal femur is made to insure adequate extension tension of the collateral ligaments. Once this cut has been made using the oscillating saw, the extension alignment jig is removed from the knee joint. The knee is again flexed and an oblique osteotomy jig is replaced into the fixturing hole and using a mallet impacted into the distal femoral bone stock. The anter- ior and posterior oblique cuts are then made in line with the jig surface and a central notch of the oblique osteotomy jig is used to trim away the boney surface for the anterior femoral flange. The oblique osteotomy jig is removed and the alignment holes made by the jig are curetted out to accept the fixturing pins of the femoral prosthesis. A trial fit of the femoral component is next made. Excessive bone stock is trimmed to insure proper contact of all surfaces. Next, the tibial preparation -is completed. A marking template is used to mark out the central spike position. Following marking with methylene blue, central spike channel is fashioned using a curette or gouge. A trial seating of the tibial component is next made and'proper bone resection is performed at this time to insure excellent metal to bone contact of the prosthesis. With resections of both bones now finished, the trial reduction of the tibial and femoral components is made as follows: The metal tibial component is placed in its central spike channel and the appropriate intermediate bearing component is inserted into place. Next, the femoral comp- onent is placed in its proper position and the knee joint is tested in both flexion and extension for proper liga- mentous tension. If resection cuts have been made prop- erly, there should be no gross instability. Should mild laxity exist in flexion and extension, then thicker bear- ing components may be used to tighten the collateral lig- aments. The bearing heights cofiaein 2.5 mm increments and may be used to finely adjust the ligamentous tension at- this stage. Once the tibial-femoral resections have been properly prepared, attention is given to the patella re- placement. Using a scalpel, the synovial tissue and re- tinaculum are freed from the periphery of the patella down to the level of the patella tendon. A reciprocating saw is then used to remove the articular surface. The plane of the cut should parallel the inferior surface of the patella tendon. A patella marking template is now centered over the horizontal and vertical axis of the patella with the long fixturing fin directed toward the lateral aspect. Methylene blue dye is used to mark the fin channels for the fixturing fins of the component. These channels are taken to a depth of 1/4 and undercut for mechanical locking of the cement. The trial patella replacement can now be seated to assess the fit. Any boney impingement is removed to insure proper seating. The patella is reflected to its anatom- ical position to check the alignment in the femoral track. A range of motion may now be tested with all three co pon- ent.s in place. The patella prosthesis should center in the femoral track and easily glide along the femoral flange without binding. Restricting adhesions or boney impingement should be completely corrected at this time. Th components are removed after a satisfactory trial fit and the wound is thoroughly irrigated with antibiotic saline solution. The first batch of methylmethacrylate is mixed and placed on the tibial surface with the knee in the flexed position. The tibial component is gently slid into its fixturing channel and firmly held in compression until complete polymerization has been obtained. During the setting phase, excess methylmethacrylate may be trimmed using a scalpel and curette from the edges of the tibial component. Next, the bearing component is placed into the tibial component and the femoral ^component is cemented in place. Excess methylmethacrylate is removed from around the femoral component to insure that the bearing surface will remain free of this abrasive agent. With a third batch of methylmethacrylate, or else using a portion of that cement used for the femoral component, the cancellous patella bed is covered. The patellar component fixturing fins are firmly pressed into their mating channels and the component is held tightly with a patellar component clamp. Excess methylmethacrylate may now be removed from the edge of the patella backplate. Upon complete polymerization of all cement beds, a range of motion is again tested after returning the patella to its anatomical position. Two medium sized hemovac drains are now placed in the joint space and brought to exit laterally above the incision line. A single layer closure of capsule and ret- inaculum is performed with #2-0 chromic suture with the knee flexed 30 degrees for the first several sutures', then to 60 degrees with the second set.of sutures, and finally, to 90 degrees for the remaining closure sutures. Subcutaneous tissue is closed with #3-0 plain suture, skin is re-approximated in a tension-free fashion with #3-0 nylon suture. Hemovac drains are hooked -to suction and a Robert-Jones compression dressing is applied. The leg is elevated and the patient is taken to the recovery room where ice packs are placed about the knee. I will be understood, by those skilled in the art that many modifications and variations of the present invention may be made without departing from the spirit and the scope thereof. | WHAT IS CLAIMED IS : 1. An improved prosthetic joint with congruent bear- ing surface engagement and for providing only two degrees of freedom of rotational movement between a first bone and a second bone, said first bone having a long axis; and said prosthetic joint periodically being under compressive load transmitted thereto by said bones; which comprises: a first component for being secured to said first bone and providing a first bearing surface; a second component for being secured to said second bone and providing a second bearing surface which is at least one segment of a surface of revolution about at least one first predetermined axis; an intermediate bearing component intermediate said first and second components and provided with:' (i) a third bearing surface substantially congruent with said first bearing surface and for substantially congruent area rotational engagement therewith to permit relative rotational movement of said first component with respect to said intermediate bearing and said second components about a second predeter- mined axis not parallel to said first predeter- mined axis and thereby providing only one of said two degrees of freedom of rotational movement, and where said second predetermined axis is 'substantially parallel to the long axis of the first bone, and (ii) ' a fourth bearing surface, comprised of less than half of a surface of revolution, substantially congruent with said second bearing surface .and for substantially congruent sliding engagement therewith to permit relative rotational movement of said first and intermediate bearing components with respect to said second component about said first predetermined axis and thereby providing said second degree of freedom of rotational movement and inhibiting rotat- ion about any axis but said predetermined first axis BURc'Λ^ upon said bearing surfaces being in engagement due to said compressive loads being transmitted to said prosthetic joint.2. An improved prosthetic joint according to claim 1 wherein said first bearing surface is a non-spherical bearing surface.3. An improved prosthetic joint according to claim 1 further including means for preventing relative lateral movement between said first component and said intermediat bearing component.4. An improved prosthetic joint according to claim 3 wherein said means for preventing said relative lateral movement comprises a recess formed in one of said first component or said intermediate bearing component and a protrusion extending from the other of said intermediate bearing component of said first component and wherein said protrusion is received within said recess.5. An improved prosthetic joint according to claim 1 wherein said prosthetic joint is a knee joint for provid ing.the patello-femoral articulation and wherein said firs component is a patella fixturing component for being secured to at least a remnant of the patella; wherein said second component is a femoral component for being secured to the distal end of the femur and wherein said second bearing surface is a smooth, continuous surface formed by a series of segments of surfaces of revolution the resp- ective shapes of which are generated by rotating a common generating curve around a plurality of predetermined generating axes at predetermined respective pairs of major generating radii and through predetermined respect- ive angles of rotation; one of said series of segments of surfaces of revolution being the primary load bearing segment; and wherein said intermediate bearing component is an intermediate patella bearing component and wherein the shape of said fourth bearing surface is defined by rotating said common generating curve through a predeter- mined angle about a predetermined generating axis at the same pair of major generating radii at which said common generating curve is rotated at to define said primary load bearing segment whereby said fourth bearing surface congruently matches said primary load bearing segment.6. An improved prosthetic joint according to claim 1 wherein said prosthetic joint is a knee joint for . providing the tibial-femoral articulation and wherein said first component is a tibial platform component for being secured to the proximal end of the tibia; wherein said second component is. a femoral component for being secured to the distal end of the femur and wherein said second bearing surface is a smooth, continuous surface formed by a series of segments of surfaces of revolution the resp- ective shapes of which are generated by rotating a common generating curve around a plurality of generating axes at respective pairs of major generating radii and through respective angles of rotation, one of said segments of surfaces of revolution being the primary load bearing segment; and wherein said intermediate component is an intermediate tibial bearing component and wherein the shape of said fourth bearing surface is defined by rotating said common generating curve through a predeter- mined angle about a predetermined generating axis at the same pair of major generating radii at which said common generating curve is rotated to define said primary load bearing segment whereby said fourth bearing surface congruently matches said primary load bearing segment.7. An improved endoprosthesis for providing the articular surfaces between a first bone and a second bone. comprising: a first endoprosthesis component for being secured to said first bone and providing a first articular surface; a second endoprosthesis component for being secured to said second bone and for providing a second articular surface for articulating with said first articular surface said first articular surface being formed by a series of segments of surfaces of revolution the respective shape of which are generated by rotating a common generating curve around a plurality of predetermined generating axes at predetermined respective pairs of major generating radii and through predetermined respective angles of rotation; and said second articular, surface being generated by rotating said common generating curve through a predeter- mined angle about a predetermined generating axis at the same pair of major generating radii at which said common generating curve is rotated to generate one segment of said first articular surface whereby upon said second articular surface articulating with said first articular surface, said second articular surface articulating with said one segment of said first articular surface in. substantially area sliding contact and articulating with said remaining segments of said first articular surface in substantially line sliding contact.8. A knee endoprosthesis having congruent engage- ment between engaged bearing surfaces comprising: A. A femoral prosthesis for being secured to the distal end of the femur and providing a femoral bearing surface the shape of which is a smooth, continuous surface formed by a series of segments of surfaces of revolution the respective shapes of which are generated by rotating a common 'generating curve around a plurality of predeter- mined generating axes at predetermined respective pairs of major generating radii and through predetermined resp--BϋRE ective angles of rotation, one of said series of segments of surfaces of revolution being the femoral primary load bearing segment; and B. A patella prosthesis including a patella load bearing surface for engaging said femoral bearing surface in substantially congruent sliding engagement to permit ro- tational movement of said patella round the distal end of the femur, said patella bearing surface including a patella primary load bearing surface segment the shape of which is defined by rotating said common generating curve through a predetermined angle about a predetermined generating axis at the same pair of major generating radii at which said common generating curve is rotated to define said femoral primary load bearing segment whereby said patella primary load bearing segment congruently matches said femoral primary load bearing segment.9. A knee endoprosthesis having substantially congruent area sliding engagement between engaged bearing surfaces upon said endoprosthesis being under heavy joint compressive loads, comprising: A. A femoral prosthesis for being secured to the distal end of the femur and providing a femoral bearing surface the shape of which is a smooth, continuous surface formed by a series of segments of surfaces of revolution the respective shapes of which are generated by rotating a common generating curve around a plurality of predeter- mined generating axes at predetermined respective pairs of major generating radii and through predetermined resp- ective angles of rotation, one of said series of segments of surfaces of revolution being the femoral primary load bearing segment; and B- A tibial prosthesis including a tibial primary load bearing surface for engaging said femoral load bearing surface in sliding engagement to permit rotational move- ment of the tibia around the distal end of the femur and 1 said tibial primary load bearing surface engaging said2 femoral primary load bearing segment in sliding engagement3 upon s aid endoprosthesis being under said compressive4 loads, the shape of said tibial primary bearing surface5 being defined by rotating said common generating Curve6 through a predetermined angle about a predetermined gener-7 ating axis at the same pair of major generating radii8 at which said common generating curve is rotated to define g said femoral primary load bearing segment whereby said 0 tibial primary bearing surface substantially congruently 1 matches said femoral primary load bearing segment and 2 engages said femoral primary load bearing segment in 3 substantially congruent area sliding contact upon said 4 endoprosthesis being under said compressive loads. 5 6 10. A knee endoprosthesis having congruent engage- 7 ment between engaged bearing surfaces comprising: 8 A. A femoral prosthesis for being secured to the dist 9 al end of the femur and providing a femoral bearing surfac 0 the shape of which is a smooth, continuous surface formed 1 by a series of segments of surfaces of revolution the 2 respective shapes of which are generated by .rotating a 3 common generating curve around a plurality of predeter- 4 mined generating axes at predetermined respective pairs 5 of major generating radii and through predetermined 6 respective angles of rotation, one of said series of 7 segments of surfaces of revolution being the femoral 8 primary load bearing segment; 9 B.A patella prosthesis including a patella load 0 bearing surface for engaging said femoral bearing surface- 1 • in substantially congruent sliding engagement to permit 2 rotational movement of said patella round the distal 3 end of the femur, said patella bearing surface including 4 a patella primary load bearing surface segment the shape 5 of which is defined by rotating said common generating 6 curve through a predetermined angle about a predetermined- U R generating axis at the same pair of major generating radii at which said common generating curve is rotated to define said femoral primary load bearing segment whereby said patella primary load bearing segment congruently matches said femoral primary load bearing segment; C. A tibial prosthesis including a tibial primary load bearing surface for engaging said femoral load bearing surface in substantially congruent sliding engagement to permit rotational movement of the tibia around the distal end of the femur, the shape of said tibial primary bearing surface being defined by rotating said common generating curve through a predetermined angle about a predetermined generating axis at the same pair of major generating radii at which said common generating curve is rotated to define said femoral primary load bearing segment whereby said tibial primary bearing surface congruently matches said femoral primary load bearing segment.11. A knee endoprosthesis having congruent engage- ment between engaged bearing surfaces, comprising: A. A femoral prosthesis for being secured to the distal end of the femur and providing a first bearing surface the shape of which is a smooth, continuous surface formed by a series of segments of surfaces of revolution the respective shapes of which are generated by rotating a common generating curve around a plurality of predeter- mined generating axes at predetermined respective angles of rotation, one of said series of segments of surfaces of revolution being the primary load bearing segment; and B. A patella prosthesis including: (i) a patella fixturing component for being secured to at least a remnant of the patella and providing a second bearing surface; (ii) an intermediate patella bearing component for being positioned intermediate said patella fixturing component and -said femoral prosthesis, said intermediate patella bearing component being received and supported rotatably by said patella fixturing component and provid- ing a third bearing surface for r'otatably engaging said second bearing surface provided on said patella fixturing component in substantially congruent area rotational engagement to permit rotational movement between the patella and the distal end of the femur and further provided with a fourth bearing surface provided on said patella prosthesis in substantially congruent sliding area engagement to permit rotational movement of said patella around the distal end of said femur, said fourth bearing surface including a primary load bearing surface segment the shape of which is generated by rotating said common generating curve through a predetermined angle about a predetermined generating axis at the same pair of major generating radii at which said common generating curve is rotated to generate said primary load bearing segment whereby said primary load bearing surface segment congruently matches said primary load bearing segment of said femoral prosthesis.12. A knee endoprosthesis having congruent engagemen between engaged bearing surfaces, comprising: A. A femoral prosthesis for being secured to the distal end of the femur and providing a first bearing sur- face the shape of which is a smooth, continuous surface formed by a series of segments of surfaces of revolution the respective shapes of which are generated by rotating a common generating curve around a plurality of pre- determined generating axes at predetermined respective angles of rotation, one of said series of segments of surfaces of revolution being the primary load bearing segment; B . A tibial prosthesis including : ( i) a tibial platform component for being secured to the proximal end of said tibia and providing a fifth0Λ1PI bearing surface; (ii) an intermediate tibial bearing component for being positioned intermediate said tibial platform compon- ent and said femoral prosthesis, said intermediate tibial bearing component being received and supported rotatably by said tibial platform component in substantially cong- ruent area rotational engagement to permit rotational movement between the tibia and the femur and further provided with a sixth bearing surface for substantially congruent area sliding engagement with said first bearing surface of said femoral prosthesis to permit rotational movement of the tibia around the distal end of the femur, said seventh bearing surface being a primary load bearing surface the shape of which is generated by rotating said common generating curve through a predetermined angle about a predetermined generating axis at the same pair of major generating radii at which said common generating curve is rotated to generate said primary load bearing segment whereby said seventh bearing surface congruently matches said primary load bearing segment of said femoral prosthesis.13. A knee endoprosthesis having congruent engagement between engaged bearing surfaces, comprising: A. A femoral prosthesis for being secured to the distal end of the femur and providing a first bearing sur- face the shape of which is a smooth, continuous surface formed by a series of segments of surfaces of revolution the respective shapes of which are generated by rotating a common generating curve around a plurality of predeter- mined generating axes at predetermined respective angles of rotation, one of said series of segments of surfaces of revolution being the primary load bearing segment; B. A patella prosthesis including: (i) a patella fixturing component for being secured to at least a remnant of the patella and providing a second bearing surface; (ii) an intermediate patella bearing component for being positioned intermediate said patella fixturing -comp- onent and said femoral prosthesis, said intermediate patella bearing component being received and supported rotatably by said patella fixturing component and prov- iding a third bearing surface for rotatably engaging said second bearing surface provided on said patella fixturing component in substantially congruent area rotational engagement to permit rotational movement between the patella and the distal end of the femur and further provided with a fourth bearing surface provided on said patella prosthesis in substantially congruent sliding area engagement to permit rotational movement of said patella around the distal end of said femur, said fourth bearing surface including a primary load bearing surface segment the shape of which is generated by rotat- ing said common generating curve through a predetermined angle about a predetermined generating axis at the sameI pair of major generating radii at which said common generating curve is rotated to generate said primary load bearing segment whereby said primary load bearing surface segment congruently matches said primary load bearing segment of said femoral prosthesis; C. A tibial prosthesis including: (i) a tibial platform component for being secured to the proximal end of said tibia and providing a fifth bearing surface; (ii) an intermediate tibial bearing component for being positioned intermediate said tibial platform com- ponent and said femoral prosthesis, said intermediate tibial bearing component being received and supported rotatably by said tibial platform component in substant- ially congruent area rotational engagement to permit rotational movement between the tibia and the femur and further provided with a sixth bearing surface for-BURtOMP substantially congruent area sliding engagement, with said first bearing surface of said femoral prosthesis to permit rotational movement of the tibia around the distal end of the femur, said seventh bearing surface being a primary load bearing surface the shape of which is generated by rotating said common generating curve through a predetermined angle about a predetermined generating axis at the same pair of major generating radii at which said common generating curve is rotated to generate said primary load bearing segment whereby said seventh bearing surface congruently matches said primary load bearing segment of said femoral prosthesis.14. A knee endoprosthesis according to the fore- going claims wherein said common generating curve is a smooth, continuous plane curve the shape of which is defined by (i) first and second predetermined arcs struck, respectively, by first and second predetermined radii from respective predetermined centers separated by a predeter- mined distance; (ii) two predetermined lines respectively tangent to said first and second predetermined arcs and at respective predetermined angles with respect to a predetermined line tangent to said first and second . predetermined arcs; and (iii) a third predetermined arc struck by a third predetermined radius from a third predetermined center and wherein said third predetermined arc is also tangent to said first and second predetermined tangent lines.15. A knee endoprosthesis, comprising: A. A femoral prosthesis for being secured to the distal end of the femur and providing a femoral bearing . surface the shape of which is generated by rotating a common generating curve around a first predetermined generating axis at a first predetermined respective pair of major generating radii and through a first predetermined respective angle of rotation; B. A patella prosthesis including a patella load bearing surface for engaging said femoral bearing surface sliding engagement to permit rotational movement of said patella around the distal end of the femur, said patella bearing surface generated by rotating said common generat ing curve around a second predetermined generating axis a a second predetermined pair of major generating radii and through a second predetermined angle of rotation; C. A tibial prosthesis including a tibial load bear ing surface for engaging said femoral load bearing surfac in sliding engagement to permit rotational movement of th tibia around the distal end of the femur, said tibial loa bearing surface generated by rotating said common generat ing curve around a third predetermined generating axis at a third pair of major generating radii and through a third predetermined angle of rotation; and D. upon said patella load bearing surface and said tibial load bearing surface engaging said femoral load bearing surface in said sliding engagement, said patella and said tibial load bearing surfaces engaging said femoral load bearing surface in at least line contact thereby reducing wear of said load bearing surfaces due to said sliding engagement. . 16. An endoprosthesis, comprising: A. A first prosthetic component for being secured t a first bone and providing a first bearing surface the shape of which is generated by rotating a common generati curve around the first predetermined generating axis at a first predetermined respective pair of major generat ing radii and through a first predetermined respective angle of rotation; B. A second prosthetic component for being secured to a second bone and providing a second load bearing surface for engaging said first load bearing surface inOM sliding engagement to permit movement of said first bone with respect to said second bone, said second load bearing surface generated by rotating said common generating curve around a second predetermined generating axis at a second predetermined pair of major generating radii and through a second predetermined angle of rotation; C. A third prosthetic component providing a third load bearing surface for engaging said first load bearing surface in sliding, engagement to permit movement of said third bone with respect to said first bone, said third load,bearing surface generated by rotating said common generating curve around a third predetermined generating axis at a third pair of major generating radii and through a third predetermined angle.of rotation; and D. Upon said second and third load bearing surfaces engaging said first load bearing surface in said sliding engagement, said second and third load bearing surfaces engaging said first load bearing surface in at least line contact thereby reducing wear of said load bearing surfac- e due to said sliding engagement.17. A three component prosthesis providing at least two articulations, comprising: a first component for being secured to a first bone and providing a first load bearing surface having a first predetermined shape; a second component for being secured to a second bone, said second component providing a second load bear- ing surface having a second predetermined shape and for engaging said first load bearing surface in sliding engagement to provide one of said two articulations; and a third component for being secured to a third bone said third component providing a third load bearing surface having a third predetermined shape and for engaging said first load bearing surface in sliding engagement to provide the second of said two articulations.•BUREAU 18. A knee endoprosthesis, comprising: A. A femoral prosthesis for being secured to the distal end of the femur and providing a femoral bearing surface the shape of which is a smooth, continuous surface formed by at least first, second and third seg- ments of surfaces of revolution the respective shapes of which are generated by rotating a common generating curve around at least three respective predetermined generating axes at three predetermined respective pairs of major generating radii and through three predetermined respective angles of rotation, said second segment of a surface of revolution being the femoral primary load bearing segment; B. (i) A patella prosthesis for being secured to at least a remnant of the patella and providing a patella load bearing surface the shape of which is defined by rotating said common generating curve through a predeter- mined angle around a predetermined generating axis at the same pair of major generating radii at which said common generating curve is rotated to define said femoral primary load bearing surface, (ϋ) upon said patella rotating around the distal end of said femur, said patella load bearing surface engaging said femoral bearing surface in -sliding engage- ment with said patella load bearing surface engaging said first segment of a surface of revolution forming said femoral bearing surface in at least line contact and engaging said second segment of surface of revolut- ion forming said femoral bearing surface in area contact; and C. (i) a tibial prosthesis for being secured to the proximal end of the tibia and providing a tibial load bearing surface the shape of which is defined by rotating said common generating curve through a predetermined angle about a predetermined major axis at the same pair of major generating radii at which said common generating curve is rotated to define said femoral primary load bearing surface; (ii) upon said tibia rotating around the distal end of said femur, said tibial load bearing surface engaging said femoral bearing surface in sliding engage- ment with the tibial load bearing surface engaging said second segment of surface of revolution forming said femoral bearing surface in area contact and engaging said third segment of surface of revolution forming said femoral bearing surface in at least line contact. | BIOMEDICAL ENG CORP; BUECHEL F; PAPPAS M | BUECHEL FREDERICK F; PAPPAS MICHAEL J; BUECHEL F; PAPPAS M |
WO-1979000740-A1 | 1,979,000,740 | WO | A1 | XX | 19,791,004 | 1,979 | 20,090,507 | new | B65D5 | null | B65D5 | B65D 5/54B1, B65D 5/54D, B65D 5/54F | FOLDING BOX | A folding box of the type having an openable end flap, the outer end of which is provided with a free olding flap which, when the end flap is closed, is put down along the inside of the box front panel opposite to the rear panel, to which the end flap is hinged, the closed ox being provided with a cover portion located at the outside of the said end flap and connected with opposed edge portions of the box opening normally closed by the end flap, such that the cover portion prevents opening of the end flap, said cover portion being connected with at least one of the said edge portions across a rupture line whereby, when said rupture line is broken or the cover portion is entirely tom off, the end flap is freely openable. | FOLDING BOXThis invention relates to folding boxes, e.g. pellet cartons, of the common type having an openable end flap, the outer end of which is provided with a free holding flap which, when the end flap is closed, is put down along the inside of the box front panel opposite the rear panel, to which the end flap is hinged. This carton type is very popular, because it is easy to produce at low costs and easy to handle by opening and re- closing, the said holding flap serving to stabilize the end flap in its closed position in a reasonably good manner. How- ever, since the carton is very easy to open it is often desi¬ red to provide the cartons with some kind of a breakable guarantee seal, but so far no practical seal means formed in¬ tegrally with, the carton have been proposed, and the most common solution has been to pack the filled and closed carton in a sheet wrapping which is closed about the carton and nor¬ mally provided with a seizable rupture strip.It is the purpose of the invention to provide a carton of the said type, in which, a guarantee seal means is provided in an advantageous manner as an integral portion of the carton blank.According to the invention this is achieved by the carton being designed as specified in the characterizing clause of claim 1. With the use of the said cover portion the end lap will be openable only after a breaking up, wholly or partly, of the cover portion, such that this will constitute a guarantee seal, which, however, will not prevent quite normal use of the carton once it has been broken the first time the carton is opened.The invention also comprises such carton blanks which are designed in such a manner that upon the erection and clo- sing thereof they appear as cartons having the said cover portion constituting a guarantee closure for the openable end flap. The invention is described in more detail in the following with reference to the accompanying drawings, in which:Fig. 1 is a plan view ofablankfor a carton according to a preferred embodiment of the invention,Fig. 2 is a perspective side view of the carton as partial¬ ly erected, andFigs. 3-5 a e perspective topviews of the carton illustra¬ ting the manner of opening of the carton.The blank shown in Fig. 1 is basically of well known design inasfar as it includes a front panel 2, a bottom panel 4» a rear panel 6, opposed inner side panels 8, opposed outer side panels 10, bottom corner flaps 12, top corner flaps 14 connected with the inner side panels 8, a top end flap 16 hinged to the top (outer) end of the rear panel 6, and a holding flap 18 forming an extension of the top end flap 16. Briefly, the blank is erectable into a well known box shape as illustrated in Fig. 5» which shows the carton top in opened condition. However, according to the present inven¬ tion the front panel 2 is extended into a second top flap 20, and the outer side panels 10 are correspondingly ex¬ tended int'o secondary top corner flaps 22 and 22' , respec¬ tively. Generally, the latter portions 20, 22 and 22' are joined to the respective panels 2 and 10 across a precut weakening or tear up line a., and the corner flap 22' has a half circular tab portion 24 generally cut out in the ma¬ terial of the adjoining side panel 10, at the other side of the line a..Fig. 2a shows an Intermediate erection position of the box member in which the rear panel 6 forms the bottom in an open box structure ready to receive the material to be fil¬ led into the carton, the box end walls being stabilized in their vertical positions by outer support means of the fil¬ ling machine (not shown), whereafter the lid structure shown in the left hand side of Fig. 2a is folded over the filled box, when the holding flap portion 18 has been folded inwardly as shown in dotted lines in Fig. 2b. Thereafter the panels 10 are folded down and secured to the outsides of the panels 8, by glueing, welding or otherwise, Fig. 2c. The cor¬ ner flaps 22, 22* are folded down at the same time, and there¬ after they are separately folded inwardly without being se— cured to the outside of the end flap 16 (Fig. 2d). Finally the flap 20 is folded down and secured to the outside of the corner flaps 22, 22', while not being secured to the surface of the end flap 16 which may remain exposed'between the ends of the opposed corner flaps 22, 22*. The detailed manner in which the box is erected should need no further description here.By the folding in of the secondary corner flap 22' the tab 24 will be brought to project from the regular box structure as shown in Figs. 2 and 3» the latter illustrating the final shape of the top end of the carton in its final shape.In order to open the carton it is now necessary - and pos¬ sible - to lift the tab 24 and pull off the entire top pa¬ nel 20, as illustrated in Fig. 4» The first result of the lifting of the tab 24 is that the weakening line a, between the corner flap portion 22' (as rigidly joined to the cover flap or top panel 20) and the adjoining outer side panel 10 will be broken, whereby the flap 22' is freely li able, and by the further lifting the top panel 20 will be torn up.along the side line a., it being entirely free along its opposite side edge. By the end of the lifting of the panel 20 also the corner flap 22 will be torn off along the line a., since it is joined to the panel 20, and consequently the entire strip shaped assembly 20, 22, 22' will be completely torn off. Thereafter the user will have free access to the ordinary end flap portion 16, and he or she may now open and reclose the carton (Fig. 5) in a fully conventional manner.It will be appreciated, however, that before tearing off the said strip 20, 22, 22' there will be' no possibility to open the carton, so this structure, which is an integral portion of the carton blank, will constitute the desired guarantee seal.Of course the invention is not limited to the embodiment shown in the drawing. Thus, instead of the front and rear panels 2 and 6 being hinged to each other through the bot- ■ • torn panel 4 they may be side hinged through one of the side panels, and the guarantee top strip 20 may be constituted by a prolongation of one or both of the corner flaps 22 or 22', i.e. without this strip being connected with the panel 2 at all. On the other hand the strip 20 would not need to be joined to any corner flaps 22 if it is provided with a projection 26 as shown in dotted lines in Figs. 1 and 3» when such a projection is caused to be secured, by glueing, wel- ding or otherwise, to the top edge area of the rear panel 6 and is connected with the end strip 20 through a breakable weakening line.Obviously, the desired guarantee sealing will be obtained whenever the cover flap member 20 extends between two op- posed edge portions of the top opening of the carton, but it should be observed that a corresponding effect is obtainable if the member 20 is made e.g.. as a triangular member joined to the edges of the opening along two orthogonal edge por¬ tions only.Moreover, the invention is of course not limited to a car¬ ton member which is erected and filled exactly as described, since it will be clear to any expert that the final and de- sired result is not depending of the detailed manner of erecting the carton.In a preferred embodiment both sides of the carton blank are coated by a layer of artificial material, whereby the joints between the panels and the corner flaps may be heat actuated in a very simple manner, and when even the inside of the carton is thus coated, it will no longer be neces¬ sary to make use of a separate internal sheet lining as otherwise conventionally used in pellet cartons. | CLAIMS1. A folding box of the type having an openable end flap, the outer end of which is provided with a free holding flap which, when the end flap is closed, is put down along the inside of the box front panel opposite to the rear panel, to which the end flap is hinged, characterized in that the clo¬ sed box is provided with a cover portion located at the out¬ side of the said end flap and connected with opposed edge portions of the box opening normally closed by the end flap,, such that the cover portion prevents opening of the end flap, said cover portion -being connected with at least one of said edge .portions across a rupture line whereby, when said rup¬ ture line is broken or the cover portion is entirely torn off the end flap is freely openable.2. A box according to claim 1, in which the cover portion is a flap member projecting from the free edge of said front panel and held in its end flap covering position by way of a corner flap connection with the two opposed box panel edge portions, normally the narrow box sides, which interconnect said front and rear panels.3» A ox according to claim 2, in which one of the corner flaps hinged to said box panel edge portions has a tab por¬ tion projecting beyond the flap folding line so as to con¬ stitute a protruding tab when the corner flap assumes its folded position, both of said corner flaps being' secured to the inside of the cover portion by glueing or welding and being hinged to their respective box sides by weakened fol¬ ding lines enabling the cover portion and both end flaps to be torn off as a unitary element.4. A box according to claim 1, 2 or 3» in. which the cover portion is a panel member constituting an integral prolon¬ gation of the box panel opposite to the panel edge from which the openable end flap projects. 5. A carton blank for a box according to claim 1, 2, or 3, characterized in that it includes a panel portion (20) which in the erected condition can constitute a tear up panel over the closed end flap (16). | LAMBACH H; SCHUR INT AS BRDR; SCHUR BRDR INT AS | LAMBACH H |
WO-1979000743-A1 | 1,979,000,743 | WO | A1 | EN | 19,791,004 | 1,979 | 20,090,507 | new | A61B6 | null | A61B6, A61M5 | A61B 6/00D4, A61M 5/00R | RADIOPAQUE CONTRAST INJECTOR | A radiopaque contrast injector for use in angiography including a tubular case (1) connected to an arm (2) fixed to or proped against a support (3). The case (1) includes a longitudinal opening (5) in the side wall (6), and extending from outlet end of case is a small tap valve (7) having at least a pair of branches (8, 9) respectively connected to a gauge (11) and to a needle (13). Also, in communication with the valve (7) is a nozzle (14) which is connected to a hose (15) which is used to conduct heparinized serum. This structure overcomes the problem of injecting contrast medium under contrast pressure making use of a common syringe. | TITLE OP INVENTION. Specification on Sa δnt of Invention concerning RADIOPAQUΞ CONTRAST INJECTOR'* .This invention relates to a radiopaque contrast injector whose aim is to offer a contribution to the study of angiography.Angiography is a radiographic search in which the blood vessels are made evident by the injection in the bed thereof of an opaque. substance to X-Hays, such vessels being thus exposed to radiation for a short time , for pur¬ poses of recording a photographic film.The instrumental injector can be from a simple plastic or glass syringe to an automatic electrical or air- ■compressed device. A good arterial angiography demands the injec¬ tion of an uniform contrast stream that can only be achieved if the pressure exerted over the contrast inside the injec¬ tor be a constant one.The system of contrast injecting by means of a simple syringe shows no accuracy. The operator has to firm the syringe with his own hands, besides having no means of how to guide himself in order to maintain an uniform pres¬ sure thereon, resulting from this the inaccuracy of angiog- raphies, mainly arterial ones. The automatic system is far more exact, based on the principle of contrast injecting under constant pressure. This method has , however , the inconvenience of demanding an extremely complicated equipment, more sophis¬ ticated in handling and very expensive for being, in their majority, imported, what circunscribes its use.An object of this invention is to fulfill such a lack. It relates to an equipment that although being manu al and making use of a common syringe, enables the operator to maintain, on the embolus , a constant pressure , keeping thus during the injection an uniform contrast stream at the syringe spout.The aim of the invention is mainly to permit the maintainance of the syringe in a fixed position when in use, allowing the concentration of the operator exclusively on the embolus. ?or this purpose the equipment is provided with a tubular case 1 duly connected to a supporting arm 2 which, by its turn, is fixed to a support 3> being said case des¬ tined to lodge the syringe 4.Such case 1 is provided witha longitudinal open ing 5 in the side wall 6 in order to allow the visualizing of the syringe scale.The accompanying drawings (sheets 1 and 2), il¬ lustrate a constructive example of the invention, character ized furthermore, by the fact that the tubular case 1is pro vided, in the outlet end thereof, with a small tap valve 7, having at least a pair of branches 8, 9, being the first one connected by means of a hose 10 to a gauge 11 , mounted at the reach of the operator's eyes, preferably at the side wall β of the case itself, and the other one 9 , connected by means of another hose 12, to the punching needle 13. A noz-O .A. WI zle 14, destined to couple a third hose 15 , that conducts heparinized serum, can be optionally associated to said tap valve 7, that will permit the passage of the serum towards hose 12, when the syringe outlet spout 16 is shut by tap 17• In the drawings,figures 1 and 2 are non-limita tive constructive examples of the equipment, whose arm 2 can be. rigidly firmed to the fixed support '3 (figure 1) or sim¬ ply juxtaposed to it by means of a prop 13 as illustrated in •figure 2. In this example, as shown in the drawing, the as- se bly formed by the lodging syringe case 1 and by the sup¬ porting arm 2 is duly fixed at a upright rod 19 of adjusta¬ ble height.As a.bove mentioned, the invention frees the op-' erator from the additional effort of keeping the syringe in a fixed position with his own hands, and he can thus concen trate all his attention exclusively on the embolus 20, being thus in a better condition to inject, far more accurately, the radiopaque contrast. The proceeding is aided by a gauge 11 mounted preferably in the very case body, next to opening 5 , destined to permit the visualizing of the syringe scale, in such manner as to allow the operator, without moving the head, to follow with the eyes the movement of the gauge ne_e die and the embolus progression inside the syringe.As already said, the invention in which concerns case 1 or sustaining arm 2, is. not limited to a given con¬ structive structure, for these elements can be directly fixed to support 3 or just propped against the same as seen in fig ure 2, in which the referred supporting upright rod 19 is foreseen. Having thus described the invention , the main characteristics thereof are those set forth in the annexed claims.OMPΪ | CIAIFS 1. Radiopaque contrast injector provided with a tubular case (l) duly connected to s. supporting arm.(2) which by its turn, is fixed to a support (3)> being said ca.se.des- tined to lodge the (4).■2. Radiopaque contrast injector , as claimed in claim 1 in which case (1) is provided with a longitudinal _o per.ing (5) in the side wall (β), in order to allow the vis_u alizing of the syringe scale. 3. Radiopaque contrast injector , as claimed in claims land.2, in which case (l) is provided, in the outlet end thereof, with a small tap valve (7), having at least a pair of branches (8,9)? being the first one connected by means of a hose (10) to a gauge (11) mounted at the reach of the operator's eyes, preferably at the side wall (β) of the case itself, and the other one (9) connected, by means of another hose (12), to the punching needle (13)•4. Radiopaque contrast injector , as claimed from claims 1 to 3> in which tap valve (7) is optionally provided with a nozzle (14) destined to couple a third hose (15) that conducts heparinized serum to hose (12), when the syringe outlet s out (16) is shut by tap (17).BADORIGINAL | COZZUPOLI F | COZZUPOLI F |
WO-1979000745-A1 | 1,979,000,745 | WO | A1 | XX | 19,791,004 | 1,979 | 20,090,507 | new | H04N9 | null | H04N5, H04N7, H04N9 | H04N 5/45, H04N 9/64A | TV GRAPHICS AND MIXING CONTROL | A system employed in a television receiver for decoding and displaying graphics information such as may be encoded on a broadcast video signal. The system includes a graphics decoder (27) supplied with the encoded video signal, and a plurality of transmission ga (31-36) responsive to logic control signals derived from the outputs of the decoder (27). The gates (31-36) are coupled to inputs of video output stages (16) in the receiver, and operate in response to the control signals for interrupting normal video signals to the video output stages (16) and for enabling a voltage representative of a graphics display intensity level to be coupled to the video output stages (16) when graphics information is to be displayed. The system also includes a graphics level control network (25). The level control network (25) limits excessive graphics representative beam current levels to prevent image defocusing and kinescope screen burn. The level control network (25) also adjusts the graphics display intensity level in accordance with the level of image representative video signals in a mixed video plus graphics display mode, to preserve a desired contrast relationship between the displayed video and graphics information. | TV GRAPHICS AND MIXING CONTROLThis invention concerns an arrangement for displaying graphics or alphanumeric information by an image reproducing kinescope in a television receiver or equivalent video signal processing system. In particular, the invention concerns such an arrangement to facilitate coupling of graphics signals to video signal processing stages of the receiver, and to automatically adjust and limit the intensity of displayed graphics information.A color television receiver, for example, can be arranged to display either normal video information alone in a conventional manner, graphics information alone (e.g., video games or alphanumeric data displays) , or mixed video and graphics information (e.g., superimposed subtitles, weather, sports or road traffic information) . Graphics information signals can be advantageously provided in a Teletext system for example, which involves transmitting alphanumeric and other graphics information through conventional television transmitting equipment, and receiving, decoding and displaying the graphics information by means of a conventional television receiver. A Teletext graphics signal comprises coded digital information which is sent as a series of digital address codes, during two horizontal line periods, towards the end of the vertical blanking period of the composite video signal. In accordance with one such system, lines 17 and 18 in one field and lines 330 and 331 in another field are used.Additional details of such a Teletext system are contained in an article entitled Teletext Data Decoding - The LSI Approach by B. Norris and B. Parsons, published in IEEE Transactions on Consumer Electronics, pages 247-252, August 1976, and in a Broadcast Teletext Specification (September 1976) published by the British BroadcastingCorporation.In one graphics display system employing the TIFAX XM11 decoder available from Texas Instruments, Ltd. of Bedford, England, as described in application report No. B183 for this decoder, graphics information signals are supplied directly in amplified form as high level dri inputs to video output stages of the receiver. In contra to this approach, in accordance with the principles of th present invention, a plurality of digitally controlled transmission gates is employed for switching a bias volta representative of a graphics display intensity level to the video output stages when graphics information is to b displayed. This approach advantageously permits the graphics information to be supplied to standard video sig processing stages such as video output stages so that the number of required interfacing elements and circuit modifications are minimized, signal loss is minimized, an high frequency response is preserved to maintain good ima definition. ' -In a graphics display system, excessive kinesco beam current levels produced in response to kinescope dri signals can cause image defocusing which can distort or obscure small text or symbols, or which can cause screen -burn when stationary patterns are displayed. Also, in t mixed display mode when graphics information is displayed together with normal television picture information, the degree of contrast between the graphics and picture information can vary due to variations in the level of th television signal. Thus, displayed graphics information may appear too intense (e.g., when the displayed televisi picture is dark in the vicinity of the graphics informati or obscured (e.g., when the television picture is bright the region of displayed graphics information) . It is herein recognized as desirable to limit the intensity of displayed graphics information by limiting the signal dri to the kinescope, and to automatically maintain a pre¬ determined relationship between the intensity of displaye graphics information and the variable level of the television signal.Graphics signal display apparatus which &UR facilitates interfacing the graphics signal source with standard video signal processing circuits, and which includes provision for automatically controlling the level of intensity of the graphics display, is provided in accordance with the principles of the present invention in a video signal processing system including a video signal processing channel, an image display kinescope, and a network for coupling processed video signals from the video channel to intensity control electrodes of the kinescope. Signals representative of graphics information to be displayed are derived from a source of signals containing graphics information, and a local bias source provides a graphics intensity bias signal representative of a desired level of displayed graphics information. A first switching network has a signal input terminal coupled to the video channel, a signal output terminal coupled to the coupling network, and a switching control input terminal. A second switching network has a signal input terminal for receiving the graphics bias signal, a signal output terminal coupled to the coupling network, and a switching control input terminal. Switching control of the first and second switching networks is provided by output signals from a control circuit which responds to the derived signals. In a normal operating mode when video signals alone are to be displayed, the first switching network conducts video signals to the coupling network, and the second switching network inhibits conduction of the graphics bias signal to the coupling network. In a graphics display operating mode, the first switching network inhibits conduction of video signals to the coupling network, an the second switching network enables the graphics bias signal to be conducted -to the coupling network during graphics display intervals.In accordance with a feature of the .invention, the bias source is coupled to the video channel for monitoring the level of the video signals, and includes means for varying the magnitude of the graphics intensity bias signal'BUREAUO in accordance with the level of the video signals in a mixed graphics display mode, to thereby maintain a desired relationship between the intensity of displayed graphics information and the level of the video signal.In accordance with a further feature of the invention, the bias source includes means for establishing minimum and maximum levels of the graphics intensity bias signal, and for controlling the level of the graphics bias signal in a direction to reduce kinescope current conduction under conditions which would otherwise cause excessive kinescope current conduction.In the drawing: FIGURE 1 shows a portion of a color television receiver partly in block diagram form and partly in schematic circuit diagram form, including a graphics displ arrangement according to the present invention;FIGURE 2 shows additional details and features of the arrangement of FIGURE 1;FIGURE 3 depicts an additional circuit feature of the arrangement shown in FIGURE 2;FIGURE• 4 illustrates a displayed graphics symbol illustrative of a feature of the present invention; and FIGURE 5 shows waveforms illustrative of the timing relationships of signals utilized in the arrangemen of FIGURE 2.In FIGURE 1, a source of luminance signals 10 in a luminance channel of a color television receiver provide an output luminance signal Y, and a source of color difference signals 12 in a chrominance channel of the receiver provides output color difference signals R-Ϋ and B-Y. Sources 10 and 12 include conventional television signal detecting, amplifying and other signal processing circuits. The luminance and color difference signals are combined in a matrix 13 for -providing R, B and G color image representative output signals. These signals are applied to respective intensity control electrodes of a color kinescope 15 via a video output stage 16, and a switching stage 20. Video output stage 16 may comprise a plurality of cascode video amplifiers of the type described in U.S. Patent 4,051,512, for example.The graphics display system includes switching stage 20, a switching logic control unit 22, and a level control circuit 25, and a graphics signal source 27 which provides decoded graphics information signals and control signals. In this example, graphics signal source 27 corresponds to the TIFAX XM11 Teletext Decoder available from Texas Instruments, Ltd. of Bedford, England.Graphics source 27 receives Teletext encoded video signals at an input terminal 16 from a source of video • signals 28 (e.g., from the output of a video detector stage in the receiver) , and also receives horizontal line flyback synchronizing pulses such as may be derived from horizontal deflection circuits of the receiver at an input terminal 15. Source 27 provides digital output signals for ultimately determining the signals applied to kinescope 15 during' graphics display intervals. An output BLANKING control signal from a terminal 21 of source 27 is applied to logic unit 22, level control circuit 25, and also to video blanking circuits of the receiver. Analog video signals are absent or blanked when the receiver is used to display graphics alone in the graphics only mode. Digital R, G and B signals from output terminals 19, 18 and 17 of graphics source 27 are representative of the graphics information to be displayed, and are provided from source 27 either singly or in combination. A MONO digital control signal from an output terminal 20 of unit 27 is utilized to disable the transmission of the analog R, G, B color signals from matrix 13 to kinescope 15 in order to make display space available for graphics information in the mixed display mode. This signal exhibits a duration which corresponds to an interval during which the graphics information is present in the mixed display mode. The terminal numbers shown within block 27 correspond to the actual numbers of the external signal terminals of the TIFAX XM11 decoder. More detailed information concerning the TIFAX XMll decoder is contained in Application Report No. B183 for this decoder.The digital control signals from graphics source 27 are processed by logic unit 22, which in turn develops output digital control signals for controlling the operation of switching unit 20. Switching unit 20 comprise an array of analog signal transmission gates (electronic switches) 31-36 for switching the signal inputs of the video output amplifiers within output stage 16 between normal analog television signals and graphics signals. Eac gate is a three-terminal device having a signal input terminal, a signal output terminal, and a control terminal to which digital signals are applied for controlling the on/off operation of the gate.In the normal operating mode of the receiver when it is desired to display only analog television signals, gates 31, 32 and 33 are closed (i.e., rendered conductive to permit the analog R,.G, B signals from matrix 13 to be conducted to kinescope driver 16. This is accomplished in response to an enabling digital control signal from a terminal 41 of logic unit 22-, which is coupled in common to the control terminals of gates 31-33. At the same time, gates 34, 35 and 36 are opened (i.e., rendered non- conductive between the signal input and output terminals) i response to disabling digital control signals respectively applied to the control terminals of these gates from output terminals 42, 43 and 44 of logic unit 22. When grahpics information is to be displayed, digital signals from graphics source 27 and logic unit 22-cause gates 31-33 to open, thereby preventing analog television signals then present from being conducted to kinescope 15 during the graphics interval. Logic unit 22 provides one or more digital control pulses from terminals 42-44 during this interval, causing one or more of gates 34-36 to'close. Those of gates 34-36 which close couple the assocated R, G or B input of kinescope driver 16, and thereby theOMP associated intensity control electrode of kinescope 15, to a graphics intensity bias voltage which is supplied as a common input to gates 34-36 from level control unit 25, as will be discussed. The kinescope screen is then illuminated in response to this bias voltage during the graphics interval.Switching stage 20 and logic unit 22 are shown in greater detail in FIGURE 2, which will be discussed subsequently.Continuing with FIGURE 1, level control circuit 25 serves to automatically control the intensity of the dis¬ played graphics information in accordance with the level of the R, G, B signals from matrix 13 during the mixed display mode, since the legibility of displayed graphics characters is dependent on' television image content in the mixed mode. For example, white graphics characters would be difficult to discern against a light image background. ■ The R, G, B signals from matrix 13 are.combined by means of positive peak rectifier diodes 47, 48 and 49 to form a combined signal with a magnitude corresponding to the peak level of the R, G, B signals. The combined signal is coupled to an input of level control circuit 25 and serves to vary the base bias of a transistor 50 in accordance with the magnitude of the combined signal. Transistor 50 develops a corresponding emitter current (I_) which charges a storage capacitor 52. A time constant determined by the value of capacitor 52 and a bleeder resistor 55 is slightly greater than the time of one image scanning field so that a voltage developed on capacitor 52 closely approaches and tracks with the level of the combined analog signal. A bleeder resistor 55 provides a path to ground for capacitor discharge current IQ. A resistor 53 serves as a current limiting resistor for collector current of transistor 50.The voltage developed on capacitor 52 is translated via a D.C. coupled PNP follower transistor 57, series diodes 58, 59 and an NPN follower transistor 60, and appears across a resistor 63 in the emitter circuit of BU EAU transistor 60 as a graphics intensity bias control voltage V-. Voltage is coupled via a current limiting resistor 64 to the signal inputs of gates 34-36 in switching stage 20, for determining the intensity of displayed graphics information. Since voltage VA varies with the level of the combined R, G, B signals, the intensity of displayed graphics information also varies with the R, G, B signals. It is noted that the offset .voltage drop associated with diodes 47, 48, 49 and the base-emitter junction offset voltage of transistors 50, 60 are compensated for by the combined effect of the base-emitter junction offset voltage of transistor 57 arid the offset voltage across diodes 58, 59. Thus the peak-representative voltage level at the emitter output of transistor 60 is substantially equal to the peak value of the combined analog signal from diodes 47, 48 and 49, and is also compensated for temperature variations by means of the offset voltage drops noted above.When the television signal is representative of a dark scene with a low brightness level in the mixed display mode, it is desirable for the intensity of the displayed graphics information to exceed the low brightness level of the television image. In this instance, the charge on capacitor 52 is determined by a voltage divider comprising resistors 66, 68 and an adjustable resistor 69 coupled to a source of direct voltage (+12 volts) . Resist 69 is pre-set to establish a minimum level of graphics display intensity. When the television signal is repre¬ sentative of scenes of average or high brightness, a diode 70 is reverse biased (non-conductive) and resistors 66, 68 arid 69 are decoupled from transistor 50 and capacitor 52. Capacitor 52 then charges as discussed abov Under low brightness conditions, however, the base voltage of transistor 50 becomes sufficiently less positive so that diode 70 becomes forward biased into conduction, thereby permitting capacitor 52 to charge via resistor 66, diode- 70 and transistor 50 to a level greater than otherwisO would have occurred under low brightness conditions. Accordingly, voltage Vft and thereby the intensity of the'5 displayed graphics information are maintained at a desired minimum acceptable level in the mixed display mode. The intensity of displayed graphics information is less critical in the graphics only display mode, when there is no displayed analog picture information surrounding the 0 graphics information. The graphics intensity level in the graphics only mode is set by potentiometer 76 as discussed below.In the graphics only display mode, the BLANKING signal from source 27 comprises a fixed positive D.C. level 5 which causes the video blanking circuits of the receiver to inhibit the analog television signals, and which causes transistors 71 and 72 of circuit 25 to conduct with the result that a bias voltage is developed across potentiometer 76. In the mixed display mode, however, the BLANKING20 signal comprises a series of short duration positive pulses which correspond to' the conventional horizontal retrace blanking and vertical retrace blanking pulses. The BLANKING signal remains at a low level, during television image line display intervals, at which time the receiver25 blanking circuits permit the analog television signal to be processed normally and coupled to matrix 13. The blanking pulses developed in the mixed display mode are prevented from activating transistor 71 in level control circuit 25 by means of a low pass RC filter including a filter30 capacitor 29 coupled to a base input of transistor 71. This filter serves to filter out the mixed display mode blanking pulses, rendering transistors 71 and 72 nonconductive in the mixed mode, and thereby preventing a bias from being developed across potentiometer 76 during the mixed mode.35 The graphics display operating bias in the mixed display mode is obtained as explained above.In the graphics only display mode, the D.C. level blanking signal from source 27 causes transistor 71 to conduct. A PNP transistor 72 also conducts in response 40 to the conduction of transistor 71, and develops a collector voltage for biasing a voltage divider network comprising an adjustable resistor 75, potentiometer 76 an a resistor 77 arranged in series in the collector circuit of transistor 72. A diode 80 becomes forward biased in response to a voltage then developed at a wiper of potentiometer 76, and voltage V at the output of circuit 25 substantially equals the voltage appearing at the wipe of potentiometer 76. Resistor 75 is pre-set to limit the intensity of the displayed graphics information and there the magnitude of kinescope beam current to a level which is not expected to damage the kinescope display 'screen (i.e., due to burn-in effects). Potentiometer 76 is an optional control to permit a viewer to adjust the maximum graphics intensity to some other level if desired.Kinescope beam current associated with the displayed graphics information must be limited at a safe long-term average level, and also at a substantially high short-term peak value. The peak value chosen typically represents a compromise between a current. level associate with a desired peak level of graphics display intensity, and a level which does not produce objectionable spot blooming with attendant loss of image definition. Level control circuit 25 is arranged so that the open circuit value of voltage V corresponds to a desired peak graphics drive level to the input of video output stage 16. Short duration graphics representative current peaks into video stage 16 are supplied from a charge storage capacitor 65, which is regularly being recharged from circuit 25 throug a resistor 64. The average 'graphics representative curre is normally significantly less than the peak current and, therefore, the normal charge on capacitor 65 closely approximates the open circuit level. However, if a large amount of graphics information is displayed, the average beam current will be high. The graphics representative current then supplied to video output stage 16 will also large, and a significant voltage drop is developed acrossW1 resistor 64. The value of resistor 64 is chosen so that this voltage drop reduces the effective value of voltage VΔ to a level which produces a safe level of average kinescope beam current.In practice, a color television receiver typically includes provision for adjusting the video output stage for a desired threshold conduction level (black level) , and for adjusting the signal gain (white balance) of the output stage in a service or set-up operating mode of the receiver. This is typically accomplished by means of variable resistors or potentiometers (not shown) associated with the video output stage. The graphics control system may also include provision for setting the normal white level or intensity of displayed graphics information in the graphics mode to correspond to the normal white level of the video signal as determined by adjustment of the video output stage during the service mode. This adjustment can be accomplished by means of optional adjustable resistors(not shown) respectively connected between the signal inputs of gates 34-36 and output voltage V. of level control circuit 25.It is noted that the described graphics display system advantageously utilizes the signal outputs of the graphics signal source (e.g., the XM-11 or other decoder) as transmission gate control or enabling signals only. This is in contrast to graphics display systems which employ the graphics information signals in amplified form as a direct high level video drive to the video output stages, which results in added capacitance at the video ouput stage and an attendant loss in high frequency response. The described system also avoids the use of long video signal and return connections to the output stages, and therefore avoids problems due to spurious radiations of video frequencies in sensitive areas of the receiver. Interference due to signal frequencies generated with the receiver (e.g., due to deflection signals and power supply operation) is also minimized.OMPI The input of the video output stage is an attractive interface point, since circuit impedances here are relatively low and stray capacitance is less of a problem. The interface transmission gates simply enable or disable the analog television signal and, in the latter case, the input to the video output stage is switched between two bias levels. High frequency response and timing accuracy are preserved, and undesired signal cross coupling effects are minimized. All of this can be accomplished in close proximity to the video output stage to minimize the likelihood of spurious signal interference If the outputs from decoder signal source 27 were used directly to provide low level video drive signals, it may be difficult to maintain a precise white or black level balance of the graphics information because of tolerance effects or drift in the R, G, B decoder outputs. . These difficulties are avoided in the present system, since the output signals from signal source 27 are used as logic control signals rather than as direct drive video signals. Since in the described system the decoder output signals are not amplified to an appropriate level for driving either the kinescope directly or preceding video processing circuits, the graphics video drive level can be determined from within the graphics display system or from an appropriate source of bias potential within the receive This facilitates the use of various types of decoders, since the level.of the decoder output signal is not critical.Referring now to FIGURE 2, there is shown additional details of switching stage 20 and logic unit 22 of FIGURE 1. Corresponding elements in FIGURES 1 and 2 ar identified by the same reference number. Logic unit 22 includes a logic AND gate 210 responsive to the MONO signal, and to an inverted BLANKING signal supplied from an output of an inverter 212. TheMONO signal is present whenever R, G or B graphics signals are present, and is utilized to open gates 31-33 for theW duration that graphics information is to be displayed. The output from AND gate 210 is coupled to the switching control inputs of gates 31-33 for controlling the conduction status of gates 31-33. Gate 210 and inverter 212 are arranged so that a positive output level (logic 1 or +12 volts, for example) is provided from AND gate 210 only when the MONO signal input to gate 210 is at a positive logic 1 level and the BLANKING signal input to inverter 212 is at a significantly less positive level (logic 0 or 0 volts, for example). A positive output from AND gate 210 causes gates 31-33 to close so that the analog R, G, B signals are transmitted to video output stage 16 in normal fashion. For all other conditions of the MONO and BLANKING signals, AND gate 210 produces the less positive logic 0 output level which causes gates 31-33 to open, thereby interrupting the transmission of signals R, G, B during the graphics interval. It is noted that the BLANKING signal remains at a high D.C. level in the graphics only display mode. Gates 31-33 remain permanently open in this mode, since an inverted ( low ) blanking level is applied to the control terminals of gates 31-33 from the output of inverter 212 via gate 210.Also during the graphics display intervals, one or more -R, G, B digital output signals (logic 0 levels)« are supplied from graphics control source 27 to logic unit 22. These signals are inverted to a more positive logic 1 level by inverters 214, 216 and 218, and as such are respectively applied to the switching control terminals of gates 34-36 for rendering one or more of these gates conductive to develop the graphics display by permitting graphics bias voltage VA to be coupled to one or more of the R, G, B inputs of video output stage 16, as mentioned in connection with FIGURE 1.When the graphics display interval ends, gates34-36 return to the open condition and, if the receiver is operating in the mixed display mode, gates 31-33 return to the closed position so that signal and bias levels for R, G, B video output stage 16 comes under control of the output signals from matrix 13. However, when the receiver is operating in the graphics' only mode, all of gates 31-3 are open when the graphics interval ends. Gates 31-33 remain open in response to the BLANKING and MONO signals from source 27 to prevent the analog television signals or noise from reaching video output stage 16. The time between the end of the graphics interval(when the bias voltage supplied via one or more of gates 34-36 is decoupled from the video output stage) , and the time when the bias level appearing at the R, G, B inputs to video output stage 16 diminishes to a level corresponding to black level, depends on a time constant formed by the input resistance and stray capacitance associated with the input circuits of video output stage 16 which were operativ during the graphics display interval. .If this time constan and the associated fall time to black level are too long, the trailing edge of the graphics display will appear to persist beyond the graphics information interval (e.g., as a gray-scale smear) . This effect distorts the desired contrast of the graphics display, and is eliminated by mean of auxiliary gating stage 250 including transmission gates 252, 255 and 257 in cooperation with logic NOR gates 224,230 and 233 within logic unit 22. Gates 252, 255 and 257 are connected between the R, G, B input lines to video output stage 16 and a source of low D.C. voltage V_ a, (i.e., a black reference level such as ground or a source of reference bias potential for output stage 16) . The outputs of NOR gates 224, 230 and 233 are respectively coupled to the ^witching control terminals of transmission gates 252, 255, 257..Gates 252, 255, 257 operate only in the graphics only mode and close when the display screen should be dark (i.e., immediately after the graphics display interval ends) in response to the BLANKING signal from source 27, which in this mode is a D.C. level. When gates 252, 255, 25 close (i.e. ,conduct), the input lines to output stage 16 are0M rapidly connected to voltage Vn so that any residual charge associated with the input capacitance of the video output circuits is rapidly discharged to the level of voltage Vβ, Which preferably corresponds to a desired black level.More specifically, the auxiliary gates are closed when the output of the associated NOR gate is at a positive level, corresponding to a logic 1 level in this example. This condition is produced when both inputs to a given NOR gate are at a logic 0 level at the end of the graphics information display interval, when the inverted BLANKING signal at the output of inverter 212 is at a 0 logic level, and when the inverted R, G, B signals at the outputs of inverters 214, 216, 218 are also at a 0 level. The trailing edge of the graphics information pulses is fast due to the low impedance path provided by the auxiliary gates between the video inputs of stage 16 and voltage V_.. The required low impedance path for black to white graphics information pulses is provided through gates 34, 35, 36.The timing of the switching of transmission gates 31-36 is important, since an image dot interval associated with small graphics characters (e.g., Teletext characters) can have a duration of approximately 180 nanoseconds, and observations indicate that timing errors of the graphics display control signals should be less than approximately fifty nanoseconds to avoid undesirable graphics edge effects. In addition, it is desirable to enhance the appearance of the displayed graphics information when operating in the mixed display mode by surrounding each displayed graphics character with a narrow black outline. In this regard it is noted that a displayed graphics character is contained within an area sometimes referred to as a blanking box , designating an area which is blanked or at black level except for the graphics information displayed within this area. The image areas immediately preceding and following each displayed graphic symbol are particularly significant for the purpose of providing a desired amount of graphics contrast to permit the graphics information to be more easily seen. A black outline of a graphics character can be produced as described below with reference to FIGURES 2-5.With regard to FIGURE 2, it is noted that the R, G and B switching control signals which enable (close) one or more of gates 34-36 during the graphics interval are first passed through inverters 214, 216 and 218. These inverters introduce a small signal propagation delay (D, in FIGURE 5) of approximately twenty-five nanoseconds such that the time at which gates 34-36 are closed is delayed by this amount relative to the time at which gates 31-33 open. Since video gates 31-33 open before graphics gates 34-36 close, video, information otherwise transmitted via gates 31-33 is absent or blanked for a short interval before the graphics display information is transmitted via gates 34-36 to output stage 16. The leading edge of the displayed graphics information therefore appears enhanced due to the small blanking or black level interval which precedes the leading edge of the graphics information.The trailing edge of displayed graphics information can also be enhanced with a black outline by slightly delaying the low (disable) to high (enable) switching transition of the digital control signal applied from AND gate 210 to the switching control terminals of video gates 31-33. By slightly delaying the time when gates 31-33 are enabled to conduct video signals from matrix 13 after the graphics information has been displayed, the image area immediately following the trailing edge of the displayed graphics information will be at the blanking or black level, thereby resulting ,in a narrow dark outline of the trailing edge of the graphics information. This result can be obtained by employing an auxiliary delay circuit 310 as shown in FIGURE 3.Delay circuit 310 includes a diode 312, a resistor 313 and a capacitance 315 arranged as shown between the output of AND gate 210 and the switching control input terminals of gates 31, 32 and 33. Network 310 provides a JU REOMPI propagation delay D as shown with respect to switching control or masking waveform A in FIGURE 3 (see also FIGURE 5) , as follows. Capacitor 315 is normally charged to the operating supply (+) but is rapdily discharged to a low potential through diode 312 and gate 210 when gate 210 is activated. Gates 31-33 are then disabled (nonconductive) . Capacitor 315 slowly recharges through resistor 313 when gate 210 is inactivated. After a time delay D, the voltage on capacitor 315 is sufficient to cause gates 31-33 to close.FIGURE 4 illustrates a displayed graphics symbol with edge enhancement as discussed above, and also shows the timing relationship between waveform A and the enhanced trailing edge of the displayed symbol. FIGURE 5 is self- explanatory and illustrates the timing relationships between the R, G, B signals, the MONO signal, and the switching control output signal from AND gate 210, in the mixed display mode.The circuit of FIGURE 2 comprises standard CMOS logic components and can be constructed from presently available integrated circuits. Illustratively, CMOS integrated circuit type CD4066 can be used to provide transmission gates 31-36 and 252, 255, 257. Integrated circuit type CD4049 can be employed to provide inverters 212-218, while AND gate 210 and NOR gates 224, 230, 233 can be provided by integrated circuit types CD4081 and 4001, respectively. These integrated circuit types are available from the Solid State Division of RCA Corporation,Somerville, New Jersey. The circuit of FIGURE 2 is capable of being fabricated in a single integrated circuit, as is level control circuit 25 with the possible exception of capacitors 29, 52 and 65. Although the invention has been described with reference to particular embodiments, various additional modifications can be made within the scope of the invention.Additional analog input signals (e.g., from theR, G, B outputs of a color camera or other local video information source) can also be displayed in the graphics mode, instead of digital graphics information as discussed. In this alternative use, the respective signal inputs of gates 34, 35 and 36 can be switched to receive voltage V common (as discussed) , or to receive the additional analog signals. In the latter instance, voltage V would be de¬ coupled from gates 34-36, and each of these gates would be separately driven by separate ones of the additional analo signals. Also, the R, G, B signal inputs of inverters 214216, 218 and the MONO signal input of AND gate 210, and th BLANKING signal input of inverter 212 (FIGURE 2) would be connected to ground, for example,, when the additional anal signals are utilized in the graphics mode. An appropriate switching mechanism can be employed for this purpose.The described system is not limited to decoding and displaying Teletext encoded video signals. The syst can also be used for displaying alphanumeric information derived from, other signal sources, such as a personal hom computer , such as the RCA VIS personal computer system. The described graphics display system is attractive for th purpose since the only external signals required are digit in nature and the signal levels are not critical. The required graphics bias signals for the video output stages are generated internally by the system, and image resoluti is high since connections to narrow signal bandwidth portions of the receiver are not required.The MONO signal can also be employed in conjunc- tion with a monochrome receiver, as described in Applicati Report B183 for the TIFAX XMll Teletext Decoder, and can also be derived from the R, G, B signals from source 27 by means of suitable logic switching circuits. In addition, the level of intensity of displayed graphics information also can be controlled in response to a conventional kinescope beam current control signal, such as can be derived by monitoring the resupply current supplied to the kinescope via the high voltage supply circuit of the receiver as is known.'jlJROM | WHAT IS CLAIMED IS:'1. In a video signal processing system including a video signal processing channel, a kinescope for displaying images derived from processed video signals, and means for coupling processed video signals from said video channel to intensity control. electrodes of said kinescope, apparatus comprising: a source of signals containing graphics information to be displayed by said kinescope; means coupled to said source of signals for deriving therefrom signals representative of graphics information to be displayed; bias means for providing a graphics intensity bias signal representative of a desired intensity level of displayed graphics information; first switching means having a signal input terminal coupled to said video channel, a signal.output terminal coupled to said coupling means, and a switching control input terminal; second switching means having a signal input terminal coupled to said graphics bias signal, a signal output terminal coupled to said coupling means, and a switching control input terminal; and control means responsive to output signals from said deriving means for providing switching control signals to said switching control input terminals of said first and second switching means, for (a) enabling said first switching means to conduct video signals to said coupling means, and disabling said second switching means to prevent conduction of said graphics bias signal to said coupling means in a normal operating mode of said system when video signals alone are to be displayed, and (b) disabling said first switching means to prevent conduction of video signals to said coupling means, and enabling said second switching means to conduct said graphics bias signal to said coupling means during graphics display intervals in a graphics display operating mode of said system. 2. Apparatus according to Claim 1, wherein: said source of signals provides composite video signals including encoded graphics information; and said signal deriving means includes means for decoding said graphics information contained in said encod video signal.3. Apparatus according to Claim 1, wherein: said first and second switching means comprise signal transmission gates operable between conductive and nonconductive states.4. Apparatus according to Claim 1, wherein: said coupling means comprises a video output amplifier stage for supplying amplified signals to said intensity control electrodes of said kinescope.5. Apparatus according to Claim 4, wherein: said signal output terminals of said first and second switching means are coupled in common to a signal input of said amplifier stage.6. Apparatus according to Claim 2, wherein: said decoding means provides an output blanking signal including a first blanking level in a first graphic display mode when graphics information is to be displayed exclusive of video information, and a second blanking leve in a second graphics display mode when graphics informatio is to be displayed together with video image information; and wherein said blanking signal is coupled to said video signal processing channel for inhibiting video signals processed by said channel in said first graphics display mode, and for enabling processing of video signals by said channel during image line display intervals in said second graphics display mode.O P 7. Apparatus according to Claim 6, and further comprising: third switching means coupled between said signal output terminal of said second switching means and a point of reference potential corresponding to a desired black level of a displayed image, and having a switching control input responsive to said blanking signal in said first graphics display mode, for rapidly connecting said output terminal of said second switching means to said reference potential at the end of graphics display intervals in said first graphics display mode.8. Apparatus according to Claim 1, wherein: . said bias means is coupled to said video channel for monitoring the magnitude of video signals processed by said channel; and wherein said bias means further includes means for varying the magnitude of said graphics intensity bias signal in accordance with the magnitude of said video signals.9. Apparatus according to Claim 8, wherein said bias means further includes: means for establishing a minimum level for said graphics intensity bias signal; and means for establishing a maximum level of said graphics intensity bias signal.10. Apparatus according to Claim 9, and further comprising: means coupled to said bias means for controlling the magnitude of said graphics intensity bias signal in a direction to reduce the magnitude of currents conducted by said kinescope in response to the magnitude of said graphics intensity bias signal, when currents associated with said bias signal exceed a level otherwise sufficient to cause excessive currents- to be conducted by said kinescope. 11. In a color television receiver including a plurality of video signal paths for conducting a pluralit of color image representative video signals derived from composite television signal, said composite television signal subject to inclusion of encoded graphics informati to be displayed; a kinescope for displaying images derive from said video signals and having a plurality of intensi control electrodes; and a video output amplifier stage having a plurality of signal inputs, for coupling said plural video signals to respective intensity control elec trodes of said kinescope;- apparatus comprising: means, including graphics signal decoding means, for decoding said television signal to derive therefrom decoded output signals representative of said graphics information to be displayed; bias means for providing a graphics intensity b signal representative of a desired intensity level of displayed graphics information; a plurality of video signal switching means, ea having a signal input terminal coupled to a separate one said video signal paths, a signal output terminal coupled a separate one of said video amplifier inputs, and a switching control input terminal; a plurality of graphics signal switching means, each having a signal input terminal coupled to said graph bias signal, a signal output terminal coupled to a separa one of said video amplifier stage inputs, and a switching control input terminal; and control means responsive to output signals from said deriving means for providing switching control signa to said switching control input terminals of said video a graphics signal switching means, for (a) enabling said plurality of video switching means to conduct video signa to said video amplifier, and disabling said plurality of graphics switching means to prevent conduction of said— CONTINUED ON NEXT PAGE'BU O Claim 11 (continued) :graphics bias signal to said video amplifier in a normal operating mode of said receiver, and (b) disabling said plurality of video switching means to prevent conduction of video signals to said video amplifier, and enabling said plurality of graphics switching means to conduct said graphics bias voltage to said video amplifier during graphics display intervals in a graphics display operating mode of said receiver.12. Apparatus according to Claim 11, wherein: said bias means' is coupled to said plurality of video signal paths for monitoring the magnitude of video signals conducted by each of said signal paths; and wherein said bias means further includes means for varying the magnitude of said graphics intensity bias signal in accordance with the magnitude of video signals conducted by said plurality of signal paths.13. Apparatus according to Claim 12, wherein said bias means further includes: means for establishing a minimum level for said graphics intensity bias signal; and means for establishing a maximum level of said graphics intensity bias signal.14. Apparatus according to Claim 13, and further comprising: means coupled to said bias means for controlling the magnitude of said graphics intensity bias signal in a direction to reduce the magnitude of currents conducted by said kinescope in response to the magnitude of said graphics intensity bias signal, when currents associated with said bias signal exceed a level otherwise sufficient to cause excessive currents to be conducted by said kinescope. | BART T; MILLS R; RCA CORP | BART T; MILLS R |
WO-1979000753-A1 | 1,979,000,753 | WO | A1 | EN | 19,791,004 | 1,979 | 20,090,507 | new | B66F3 | null | B66F3 | B66F 3/35 | A BREAKING OR LIFTING DEVICE | A breaking or lifting device (1) incorporating an expanding member (2) arranged to form an integrated unit with a gas holder (10) arranged for introduction of pressurized gas into the interior of the expanding member (2) and control means (11) being arranged in the unit for controlling the supply of gas in said expanding member (2). | A BREAKING OR LIFTING DEVICEBackground of the inventionThe present invention refers to a breaking or lifting device incorporating an expanding member i.e. a cushion, a bladder or the like, in which -pressurized gas can be introduced.Breaking or lifting devices are today used in a plurality of different working moments such as wood felling, building works and as lift jacks for cars and for building struc- tures etc. Such devices are for instance described in Swedish patent specification 391.109, US patent specifications . 2.609.177 and 3.822.861 etc. and all of these devices incorpo¬ rate an inflatable member designed as a cushion, a bladder or the like which is connected to an inflating device e.g. a combustion engine, a compressor or a hand operated pump. Such devices however are bulky and clumsy and each one of ' them is intended for a specific limited work purpose. Those devices which are inflated automatically, i.e. without the requirement that a manual work must be excerted, have further- more a complex design and they are therefore expensive to manufacture. The designs hitherto known are furthermore not suited for use where the space available for breaking or lifting devices is limited and where rapid operation is required e.g. at car accidents, accidents with collapsing buildings, or in other emergency situations.Summary of the inventionThe purpose of the present invention is to eliminate the abovementioned drawbacks at a reasonable cost and to provide a small-dimensioned breaking or lifting device which is easy to carry and which can preferably be used by the crew in different types of emergency vehicles at breaking or lif operations e.g. for freeing persons who have got stuck in car accidents or at other breaking or lifting operations where the space for the breaking or lifting device is limit This problem is solved thereby that the expanding member via at least one control valve is connected or connectable to a rechargeable and/or exchangeable gas holder arranged to form an integrated unit with the expanding member.Brief description of the drawingsThe invention will hereinafter be further described with reference to some embodiments shown in the accompanying drawings.Figure 1 shows in an axial section a breaking or lifting device according to the invention,Figure 2' shows a mounting bar in a section along line A - A in figure 1, Figure 3 shows a modified breaking or lifting device .with a preset inflation pressure,Figure -i shows a further embodiment of a breaking or liftin device equipped with a rechargeable gas holder, Figure 5 shows a filling central for the breaking or liftin device shown in figure *.,Figure 6 shows another embodiment of a breaking or lifting device having a laterally mounted, rechargeable gas holder, Figure 7 shows an expanding membemore in detail, Figure 8 shows another embodiment of an expanding member and a clamping device for the gas holder, andFigure is a section along line B - B through the gas holde and the clamping device shown in figure 8.Description of some preferred embodimentsAn expedient embodiment of a breaking or lifting device1 according to the invention incorporates an expanding membeOM 2 which by means of bolts or screws 3 at one of its ends is fixedly mounted in a mounting bar , which is also shown in cross-section in figure 2. The internal expandable space of the expanding member 2 communicates via a tube 5 with a control valve 6 provided with a control member 11 and located in a handle-like casing 7 encasing a connecting element 8 with a bayonet joint to which is connected a knob- provided 9 gas holder 10.When the breaking and lifting device shall be used the expanding member 2 is introduced in evacuated state between the parts which are to be separated, e.g. in a back cut at wood felling, whereupon the control member 11 is pushed down to a first active position. Pressurized gas thereby will pass from the gas holder 10 via the connecting element 8, the control valve 6 and the tube 5 into the expanding member 2 whereby this is expanded. The control member 11 is pushed further downwards to its second active position when the desired effect has been reached and the gas contained in the ex- panding member 2 will thereby be evacuated via the outlet 12 and the breaking and lifting device can be removed from its working position.In figure 3 is shown an alternative breaking or lifting device in which an exchangeable gas holder 20, provided with a screw joint 13 is connected to a support and control unit 1 , in which is mounted a (not shown) pressure reduc¬ tion valve which via a setting device 15 is adapted to limit i.e. to maximize the pressure to be excerted by the gas in the expanding member 2 to a desired level. An operating member lβ is adapted during hand-operation to allow supply of gas under pressure to the expanding member 2 and an evacuation member 17 is adapted during manual actuation to evacuate the gas present in the expanding member 2. The control unit 1*4 is connected to the mounting bar 4 in a manner similar to that described hereabove and it is therebv also connected to the expanding member 2. It is also possible to use with advantage a fixed, rechargeable gas holder such as shown in figure k. The handle-shaped casing 21 is thus incorpora a rechargeable gas holder 22 provided with a filling valve 19, which is of course also equipped with a (not shown) no return valve, and a control valve 23 which communicates with the gas holder 22 and is equipped with a control memb 2k ., The control member 2 k can by manual actuation be put in two active positions (not shown), one first active positio where the control member 2 is acted upon in the direction of arrow 25, whereby gas from the gas holder is allowed to pass into the expanding member 2, and a second active p'osition when the actuation .takes place in -the direction of arrow 2β, whereby the gas is evacuated from the expandi member 2. In cases where the breaking or lifting device according to figure k is filled with compressed air is it possible to use a filling station according to figure _. . A compressor 27 is via a conduit 30 connected to a panel 28 equipped with a plurality of filling sockets 29, throug which compressed air can be supplied to several breaking or lifting devices simultaneously.In figure 6 is shown an alternative embodiment of a breaki or lifting device with a rechargeable gas holder 21. The gas holder 31 is fixedly mounted perpendicularly to the handle-shaped casing 3β, which is provided with a filling valve 33, a non-return valve 3*4 and a control valve 35« The control member 37 is hereby controlling the supply and evacuation of gas to/from the expanding member 2.The expanding member 2 shown in figure 7 preferably compri a supporting base 38 made from a rigid material, which has been provided with ducts 39 and openings k0. A pliable or flexible material, such as a rubber compound covered with nylon cord, forms the side portions kl t k 5 of the expandin member 2, whereby mounting bars k 2 , k ~5 delimit the expandi member 2 longitudinally. Compressed air or another gas und_OM . IP pressure is supplied to the expanding member 2 from the gas holder k k via the ducts 39 and the openings 0 whereby is obtained an expansion of the internal expanding member space between the mounting bars 42, 43 and the side portions kl , 45. A force mainly proportional to the pressure excerted by the compressed air or the gas will thereby be obtained perpendicularly to the side portions 2.1, 5 of the expanding member 2 and a breaking or lifting moment will result.Another embodiment of an expanding member is shown in figure 8 whereby a gas holder kβ will supply gas under pressure to a bellows-formed expanding member 7, provided with two legs 48, 49, which are pivotably supported relative to each other in a pivot 58. The leg-s 48, 49 can be provided with grooves or jags 50 intended for giving a good grip against the work surfaces. An exchangeable gas holder .46 is retained in a clamping device 59 made for instance from thermoplast and it is safely retained in place via springy side elements 51, 52. A quick-coupling which is supported rotatably about a shaft 53 connects the gas holder via a duct 55 and a (not shown) control valve to the expanding member 47. At exchange of the gas holder 46 the. handle 56 of the breaking or lifting device is manually pushed downwards to make the side elements 51, 52 of the clamping device 59 to release their grip about the gas holder 46. The gas holder 46 and the σuickcoupling 54 are thereupon turned upwards/outwards about the shaft 53 until the rearward wall 57 will not hamper the pulling out of the gas holder 46 from the quick-'coupling 5 k . A new, fully charged gas holder 46 can thereupon be placed in the quick-coupling 54 to be pushed down and be fixed in the clamping device 59. | AMENDED CLAIMS(received by the International Bureau on 23 July 1979 (23.07.79))1. A hand-operated breaking or lifting device incorporating an expanding member i.e a cushion, a bladder or the like, which in its inactive position is disc-shaped and thin and which can be connected to a pressure source, c h a r a c t e r i z e d h e r e b , that the expanding member (2) is provided with a mounting bar (4) having connecting elements (8,13) for a rechargable ancYoiexchangeable gasholder (10,20,22,31, kk _.46) and that at least one control valve (11,14,23,35) is arranged in the m'ounting bar (4), said control valve having a cut-off function in a first position, establishing communication between the expanding member and the gas holder in a second position and connecting the expanding member with the atmosphere in a third position.2. A breaking or lifting device according to claim 1, c h a r a c t e r i z e d t h e r e b y, that the gas holder is designed and arranged as a handle.3- A breaking or lifting device according to claim 1 or 2, c h a r a c t e r i z e d t h e r e b y, that the gas holder is connected to or connectable to a carrier or a clamping device designed as a handle.4. A breaking or lifting device according to one or more of the preceding claims, c h a r a c t e r i z e d t h e r e b y, that the gas holder is equipped with a filling valve (19) and/or is intended for connection to a filling central.5. A breaking or lifting device according to one or more of the preceding claims, c h a r a c t e r i z e d t h e r e b y, that the gas holder can be placed in a clamping device having at least two springy _-- ' l'i • | JONSEREDS FABRIKERS AB; RONNFORS L; STROEM H; JONSEREDS AB | RONNFORS L; STROEM H |
WO-1979000760-A1 | 1,979,000,760 | WO | A1 | XX | 19,791,004 | 1,979 | 20,090,507 | new | C08L33 | null | C09D11 | C09D 11/16 | WASHABLE NON-SPLATTER INK | A washable non-splatter ink for use in oscillographic type pen recorders is disclosed. The ink is characterized by being stable at room temperature for extended periods of time, thus not requiring refrigeration for the maintenance of stability. The ink contains a high molecular weight polyacrylamide rather than polyethylene oxide as a pituity agent to stop splatter of the ink at fast writing speeds. The polyacrylamide allows the use of washable acid dyes. The inclusion of an unsaturated alcohol, such as butyne diol acts to retard the oxidation of the pituity, thus stabilizing the pituity against aging degradation. | WASHABLE NON-SPLATTER INKBackground of the Invention The present invention relates to ink used in recording instruments and more particularly to non-splatter¬ ing inks used in oscillographic type pen recorders and the like.An inking system and ink therefore typical of the environment as wherein the present invention is applicable is set forth in the United States Patent No. 3,906,513 to Siegelman et al. which is assigned to the common assignee of this application- In such apparatus, an oscillograph pen, comprising a metallic capillary tube connected to a supply of ink, is biased against a paper recording medium which is moved slowly and continuously under the pen tip. As the paper is thus moved under the pen tip, an electrical signal is applied to the oscillographic pen motor which drives the capillary tube type pen from side to side thus producing a permanent marking of the electrical waveform being applied at the input to the oscillograph. Such apparatus is prone to a number of problems. As the pen terminates its excur¬ sion in one direction toward the side of the recording paper and reverses direction to move in the opposite direction, the ink contained therein has a tendency to continue in the first direction as a result' of the force of -inertia on the ink. Additionally, as the pen tip is traversing the paper at a high rate of speed in response to a rapidly changing electrical signal of high frequency and amplitude, there is a tendency for the ink to discontinue marking on the surface of the paper for periods of time. The former problem is referred to as splattering and the latter as skipping . Considerable research has been conducted by manufacturers of such oscillographic type pen recorders and their suppliers to find a workable solution to both the splattering and skipping problems. Unfortunately, the solutions often tend to be mutually exclusive. That is, a highly viscous ink would not tend to. splatter but, on the other hand, would be highly prone to skipping. By contrast, a low viscosity ink that would not skip would have a high tendency to splatter. In the aforementioned patent to Siegelman et al., as well as the patents to Forsyth, Jr. (3,477,862) and Packer (3,692,548), a high molecular weight (about 500,000 to 5,000,000) polyethylene oxide is incorporated into the ink. The polyethylene oxide is one of certain polymers which, when in solution, exhibit the property of filament formation, or the tendency to pull out into long threadlike structures, as when a stirring rod is withdrawn from a container of the solution, for example. This ability to form filaments is believed to be a manifestation of the high elongational viscosity of polymer solutions. The tendency to form filaments is known as pituity. One way that pituity is measured is via a drop technique whereby a fixed quantity of solution is ejected from a microliter syringe. The time from when the drop of solution falls to a watch glass at a fixed disance below the syringe to when the thread of solu¬ tion trailing from the watch glass to the top of the syringe, breaks is taken as a measure of pituity.. The property of filament formation in an ink used in an oscillographic type recording system has two benefits. First, there is a tendency to reduce drag. This is because of the tendency of each particle of ink to pull the next adjacent particle through the capillary and for that ink on the surface to draw the next adjacent particle from the pen tip. The result is a tendency not to skip. At the same time, the filament formation tendency tends to prevent the disassociation of adjacent particles. It is the disassocia- tion of adjacent particles which causes splattering. Thus, the inclusion of the polymer having the property of filament formation in the ink tends to solve both the skipping and splattering problems heretofore identified.While the inclusion of high molecular weight poly¬ ethylene oxide into the ink has bestowed the desired bene¬ fits of non-splattering and nonskipping desired, it is not without attendant drawbacks. Under normal circumstances, other additives to the ink, including the dye thereof, have a tendency to oxidize the polyethylene oxide thus destroying its long chain molecules and attendant filament forming qualities. This is particularly noticeable with the sulioner groups of an acid dye. The presently known formulations of non-splatter ink incorporating polyethylene oxide require dyes with amine, (-NH2) or dimethyl amine, [-N(CH_)2], groups or basic dyes such as basic violet 2, basic violet 3, or basic green 4, in order not to oxidize the polyethylene oxide. The basic dyes do not exhibit the tendency to rapidly oxide the polyethylene oxides as do the acid dyes. On the other hand, the basic dyes stain the users hands and the instrument badly while the acid dyes are water soluble and stain very little. Thus, to the user, ink incorporating acid dyes are preferred for cleanliness. Additionally, it is often desirable to have a single dye component black ink which is available only as an acid dye.'With the use of a pituity agent that is easily oxidizable, a washable ink that is stable at room tempera¬ ture for more than approximately two months is not possible. The ink can be refrigerated to stop the deterioration pro¬ cess, but such refrigeration facilities are often not avail¬ able at the sites wherein the recorders are desired to be incorporated.Thus, it is the object of the present invention to provide a washable non-splatter ink incorporating a pituity agent which is not prone to oxidation when used in conjunc¬ tion with acid dyes.• SummaryThe object of the present invention has been met by the ink of the present invention wherein a polyacrylamide pituity agent has been added in place of polyethylene oxide. In the preferred embodiment, polyacrylimide is used as a pituity agent along with an acid dye, a bacterial agent incorporated in a water based solvent, and 2-butyne-l,4-diol is used as an antioxidant.Description of the Preferred EmbodimentA typical batch of the preferred embodiment of the ink of the present invention is prepared as follows: -4-Component uan ity Function Water 50 πuT Ethylene Glycol 4 ml SolventMethyl Ether (100 ml total) Ethylene Glycol 45 ml Glycerine 1 ml_ Polyacrylamide 10 mg Pituity Agent Formaldehyde 20 mgm Antibacterial AgentProducing Preservative 2-butyne-l,4-diol 20 mgm Antioxidant Acid Black 2 7 g DyeIn the ink according to the foregoing composition, the acid black 2 (or, alternatively, Nigrosine) dye is soluble to .12 grams of dye per milliliter of solvent in water, .07 grams per milliliter in ethylene glycol methyl ether, and .035 grams per milliliter in ethylene glycol. Water alone as a solvent has too high a surface tension and evaporates too quickly to make a good ink solvent. Ethylene glycol methyl ether and ethylene glycol are used to reduce the. surface tension. Glycerine, ethylene glycol, Polyglycol 200 or a solvent with a very low vapor pressure and properties as a humectant is needed to prevent rapid clogging at the pen tip or in the polyvinyl chloride tube from the pen to ink bottle. The polyacrylamide, preferably Separan AP 273 made by Dow Chemical Company, is used as a pituity agent to- stop splatter of the ink at fast writing speeds. A formaldehyde producing preservative, preferably Dowacil 75 also made by Dow Chemical Company, is used to keep bacteria from consuming the pituity agent. An antioxidant 2-butyne-l,4-diol is also added to retard oxidation of the pituity agent.- The result is an ink with a pituity of 2 ±1 second, a viscosity of 10 ±5 centi- poise as measured with a Brookfield LVF Viscosimeter operat¬ ing at 60 RPM with a No. 1 spindle, and a pH equal to 10 ±1.While the disclosed embodiment uses a black dye, this was chosen as being a worst case . The polyacrylamide pituity agent should be useful in inks of other colors in addition to black. Likewise, the proportions of 10 mgm attributable to the polyacrylamide component of the ink can vary within tolerance limits of ±50% without adversely0WΪP -5- *' affecting the quality of the ink.One should note when preparing ink according to the present invention that the polyacrylamide pituity agent employed more commonly functions as a floculant used in settling solid wastes suspended in water. Thus, in the ink mixing process it is important to have all dyes in solution before any floculant (pituity agent) is introduced. Such floculants are usually biodegradable so that a bacteriacide (such as the Dowacil 75 incorporated in the preferred embo¬ diment) should be included if the pH is near neutral, which favors bacterial growth. Additionally, filament forming compounds such as polyacrylamide have a tendency to be destroyed by stirring. It has been found by the applicant that the preferred method of producing solutions of poly¬ acrylamide for subsequent incorporation into the ink solu¬ tion comprises sprinkling -crystals of the material over shallow water such as in a cookie tin or the like, covering and letting the covered water set overnight. Any lumps can be taken out of the resultant solution by pouring through a small funnel. When the resultant solution is put into the ink, it should be done through a small funnel, about 4 millimeter, and the ink should be stirred slowly while the solutions are flowing together. The ink should then set for a day so that extruded cord of solution can diffuse out and mix with all the ink.Having thus described my invention, I claim: | - -.;: '■■ ':_. .1. An.-.ink for use in oscillographic pen recor¬ ders comprising.: . a) solvent being about 50% water, 4% ethyl¬ ene glycol metyL.ether, 45% ethylene glycol, and 1% glycerine; . b) about 10 mgm of polyacrylamide for every 100 ml of said solvent; c) about 20 mgm of an antibacterial agent for every 100 ml of said solvent; d) about 20 mgm of an antioxidant for every 100 ml of said solvent; and e) about 7 gm of dye for every 100 ml of said solvent.2. In washable ink for use in oscillographic pen recorders having a water base solvent, and an acid dye, the improvement for decreasing the splattering of the ink while increasing its non-refrigerated shelf life comprising: between 5-60 mgm of polyacrylamide added as a pituity agent for every 100 ml of the solvent.3. The washable non-splatter ink as claimed in claim 2 and additionally comprising: approximately 20 mgm of a formaldehyde pro¬ ducing antibacterial agent for every 100 ml of the solvent.4. The washable non-splatter ink as claimed in claim 2 wherein: said polyacrylamide is in an amount of about 10 mgm per 100 ml of said solvent.5. A washable non-splatter ink particularly suited for use in oscillographic pen recorders comprising: a) a water based solvent; b) about 60 mgm of polyacrylamide pituity agent for every 100 ml of said solvent; c) about 20 mgm of an antibacterial agent for every 100 ml of said solvent; d) about 20 mgm of an antioxidant for every 100 ml of said solvent; and, e) about 7 gm of dye for every 100 ml of said solvent. 6. _ The washable non-rsplatter, ink .as claimed in claim 5 wherein said water based solvent σp pxl± s.:-: _■-;_<_- a) about 50% water;: b) about -4% .ethylene. glycol .rqcethyl ether; c) about 45% ethylene glycol;: and, d) about 1% glycerine, i .O PI A - WIP0 | BECKMAN INSTRUMENTS INC; BECKMAN INSTR INC | CORWIN W |
WO-1979000764-A1 | 1,979,000,764 | WO | A1 | EN | 19,791,004 | 1,979 | 20,090,507 | new | F16L21 | null | F16L21 | F16L 21/02 | A SEALING RING | An annular sealing ring arranged to be mounted between the mutually facing wall surfaces of the ends of two pipe-like elements, one of which is inserted in the other. Figure 6 illustrates an annular seal having a rectangular cross-section such as to present two broad sides (14 and 15). Arranged closely adjacent one another are two parts (8' and 9'), one being for the supply of a hardenable substances to the internal cavity of the seal, and the other for the evacuation of air from said cavity. To prevent the hardenable substance from flowing in both directions around the cavity of the seal, a partition wall is formed between said parts, by pinching together the parts (19', 19'') of the annulars located therebetween, by means of a suitable tool (27). In this way, all air present in the cavity is evacuated therefrom without impeding the flow of said substance therearound. | A SEALING RINGThe present invention relates to a sealing ring arranged to be mounted between two pipe ends of which one is inserted in the other, said sealing ring comprising a continuous, flexible and resilient hose-like element having an internal cavity which is arranged to be filled with a hardenable pressure medium through means connected with said cavity.Such a sealing ring is well known, and one such sealing ring is described in the German Auslegeschrift 1 475 890. The internal cavity of the sealing ring according to this publication is connected to two mutually diametrical¬ ly located valves , of which one is arranged to be connected to a pressure source for injecting a hardenable pressure fluid into said cavity, and the other is intended for the evacuation of air from the cavity when the pressure fluid, which may comprise a hardenable epoxy resin, is injected into said cavity. One problem encountered with such sealing rings is that it is practically impossible to distribute the pressure fluid inifor ly in amanner such that the two branch lines connected to the inlet are filled at the same speed. Normally, one of said branch lines is filled more quickly than the other, and consequently the air outlet is blocked before the other branch line has been completely filled. Consequently' air is enclosed which gradually causes the abutment pressure between the part of the ring filled with air and the pipe surfaces abutting said part to be excessively low, therewith resulting in a leakage, which may have serious consequences if the pipes are buried in the ground. Consequently, it is a main object of the present invention to provide an annular, continuous sealing means of the kind mentioned in the introduction, in which the risk of air inclusions is completely eliminated.Accordingly, this invention consists in a sealing ring arranged to be mounted between two pipe ends which are._ ___ inserted one within the other, said ring comprising a continuous, flexible and resilient hose-like means having an internal cavity, which is arranged to be filled with a hardenable pressure fluid through means connected to said cavity, wherein there is arranged in the cavity, at least during a filling operation, a sealing partition wall, where a fluid inlet discharges into said cavity adjacent one side surface of the partition wall, and wherein a fluid outlet communicates with the cavity adjacent the other side surfac of said partition wall.So that the invention will be more readily understood and further features thereof made apparent, exemplary embo- dyments of the invention will now be described with referen to the accompanying schematic drawings, . in which Figure 1 illustrates an embodiment of a sealing ring accord ing to the invention in sectional view in a plane through the common axis of the two pipe ends, Figure 2 is a view taken in the axial direction of the ring in Figure 1, said ring being shown here in reduced scale,Figure 3 is a sectional view taken on the line III-III ofFigure 2, said view being in an enlarged scale, Figure 4 illustrates a partially cut away portion of the sealing ring taken at the inlet and the outlet of the seal,Figure 5 is a sectional view of a modified embodiment, and Figure 6 illustrates the manner in which the partition wall is formed by squeezing the hose-like element. Figure 1 illustrates a wall 1 of a pipe 2 whose end is inserted in a sleeve or pipe end 3, the wall of which is referenced 4. Located between the two pipes 2 and 3 is a gap 5 in which a sealing ring 6 according to the invention is arranged. This sealing ring 6, which is described with reference to Figure 1 to 4, is continuous and is made of a resilient material, such as silicone rubber or natural rubbThe ring 6 has an internal cavity 7 which communicates with an inlet opening 8 and an outlet opening 9. In the illu- εtrated embodiment, a hose 10 is connected to the inlet opening 8, while a hose 11 is connected to the outlet opening. Each of the two hoses 10, II has a respective closing valve 12 and 13. As will be seen from Figure 2, the sealing ring has a rectangular cross-section with two broad side surfaces 14,15 and two narrow side surfaces 16,17. The two broad side surfaces 14,15 form sealing surfaces against the walls 1,4 of the pipes. The thickness of the material 18 between the cavity 7 and respective narrow ring surfaces 16,1-7 shall be of such magnitude that a pressure above ambient pressure in the cavity 7 will only result in a compression and expansion of the sealing side surfaces 14,15. As illustrated in Figure 4, there is arranged in the cavity 7 a partition wall 19 which is sealingly connected to. the inner wall 20 of said cavity. The outlet 9 is connected on one side of the partition wall 19 adjacent said wall, while the inlet 8 is connected on the other side of said partition wall adjacent said wall. The- partition wall 19 of the illustrated embodi¬ ment of Figures 1 to 5 has the form of a resilient, bellow- like structure,', or any other suitable structure which will permit the broad side walls of the sealing ring to be moved away from each other, and is conveniently bonded or vulcanized between the end parts 21,22, of the hose which has been connected to the illustrated continuous sealing ring. The openings 8 and 9 should lie as close as possible to the sealing partition wall 19,. for example at a distance of less than 10-20 mm.When the sealing ring has been mounted in the gap 5, as illustrated in Figure 1, the two valves 12,13 are opened, and a hardenable fluid, for example an epoxy resin, is injected into the cavity 7 through the hose 12 and the opening 8. The resin will only flow to the left as seen in Figure 1, since the sealing partition wall 19 prevents the resin from flowing to the right in Figure 4. The relative- ly sluggishly flowing or viscous resin will progressively fill the cavity 7 whilst flowing clockwise in Figure 2, and will therewith expell air in the cavity 7 out -through the outlet 9. The resin will subsequently reach the outlet 9 flow out therethrough. The cavity is thus completely fill and no deleterious air inclusions will be left. The valve is then closed and the pressure built up in the resin in the cavity 7, this pressure forcing the wall surfaces 14,1 of the ring against the pipe walls 1,4. Subsequent to the requisite pressure having been built up in the cavity 7, t valve 12 is closed and the resin hardened to form a solid 23 which holds the wall material of the sealing ring in co stant and intended contact with said pipe walls.Figure 5 is a sectional view of a modified embodimen of the invention. In this embodiments, the internal cavity comprises a slot 7' in which the hardening pressure medium is forced, and arranged on the sealing surfaces are peri- pherally extending ridges or flanges, such as 24,25,26, wh may, in certain cases, improve the seal against the pipe e and penetrate into irregularities in the pipe walls.Figure 6 illustrates a particularly example, and pre¬ ferred embodiment of the invention. Instead of providing a permanent partition wall as with the Figure 4 ambodiment, the partition wall of the Figure 6 embodiment is formed by pinching temporarily the hose-like element between the inl 8 ' and the outlet 9'. The hose-like element may be pinche by means of a pair of tongs or a like tool, having two jaws 27 and 28, the portions 19' and 19 being pinched firmly to gether to form the necessary partition wall. Subsequent t filling the hose-like element, the pressure on the jaws is removed, that space created by the said portions 19' and 19 quickly being filled. As will readily be understood, pinching of the said section of the hose-like element may also be effected by placing the said element against, for example, a flat suppo surface and by applying a force to said element substantial perpendicularly to said surface, thereby to provide a part tion wall between said inlet and said outlet.Instead of the flexible lines or hoses 10,11 which a connected to respective inlet and outlet on one of the non-OMPI sealing side surfaces 16 or 17 of the ring, valves can be arranged directly in the openings 8,9. When using hoses 10,11 or comparable conducting means, said hoses or means may be closed by means of plugs or the like. The pressure fluid may comprise any suitable hardenable material wyich will contract only slightly when hardening.OMPI | C L A I M S :-1. A sealing ring arranged to be mounted between two pipe ends which are inserted one within the other, said ring comprising a continuous, flexible and resilient hose¬ like means having an internal cavity which is arranged to be filled with a hardenable pressure fluid through means connected to said cavity, wherein there is arranged in the cavity, at least during a filling operation, a sealing par tition wall, wherein a fluid inlet discharges into said cavity adjacent one side surface of the partition wall and wherein a fluid outlet communicates with the cavity adjace the other side surface of said partition wall.2. A sealing ring as claimed in claim 1, wherein the hose-like means has a substantially rectangular cross-sec¬ tional shape, with the broad rectangular sides of said mea being arranged to abut the walls of the pipe ends.3. A sealing ring as claimed in claim 2, wherein the cavity of the hose-like means has the form of a thin slot.4. A sealing ring as claimed in any one of claims 2 to wherein the fluid inlet and the fluid outlet are arranged on one of the narrow sides of the hose-like means.5. A sealing ring as claimed in claim 4, wherein flexib lines, for supplying fluid to and removing fluid from said cavity are connected to the fluid inlet and to the fluid o let respectively. 6. A sealing ring as claimed in any one of claims 1 to wherein the partition wall is permanent and made of a resilient material7. A sealing ring as claimed in any one of claims 1 to wherein the partition wall comprises at least a part of th hose-like means, which has been pressed in by an external force.OMPI | BLOM H; PANDATA AB | BLOM H |
WO-1979000771-A1 | 1,979,000,771 | WO | A1 | EN | 19,791,004 | 1,979 | 20,090,507 | new | B28D1 | B28D1 | B08B1, B28D1 | B08B 1/00, B28D 1/26B | SCABBLER BITS | A bit (1) for a scabbler comprises pointed tips (2) separated by chisel shaped cutting tips (3) projecting a smaller distance than the pointed tips. The tips are preferably in straight rows ending in pointed tips. The tips may be of tungsten carbide and brazed into position. The pointed tips make indentations into the surface, and the chisel shaped tips then break the intermediate weakened area. The bits are used for abrading hard ground surfaces. | TITLE: Scabbier Bits Description; TECHNICAL FIELDThe invention relates to bits for scabblers, that is percussive machines for roughening, abrading, or removing projections from hard surfaces, for example walls or ground surfaces such as roads or concrete constructions.BACKGROUND ART Scabblers are known from Patent Specifications such as U.S. 2,553,435 of Briese, G.B. 709,904 of Metropolitan, and G.B. 1,056,011 of MacDonald, but these give little detail of scabbier bits. However, generally speaking, a scabbier bit comprises a head having a number of tips mounted thereon and means for attachment to a scabbier.The tips may be of hard cutting material such as tungsten carbide and brazed into apertures in the head.DISCLOSURE OF INVENTIONA scabbier bit according to the invention has a number of pointed tips separated by chisel shaped cutting tips projecting from the head a smallerdistance than the pointed tips. In use, the pointed tips make indentations in the surface under treatment, and the chisel shaped tips then break the area weakened between indentations, removing a large amount of material per unit of energy of impact. In a preferred arrangement, the tips are in straight rows, preferably parallel to each other, preferably wi a pointed tip at the end of each row, and preferably with the pointed tips and chisel shaped tips in adjacent rows off-set with respect to each other. If the scabbier head is circular,, the rows can well be along and/or parallel to a diameter of the head. The bit can be mounted on the scabbier so that the rows ar transverse to the direction of advance of the scabbier10 in use.The means for attachment of the scabbier bit to a scabbier may comprise a shank for reception in a cylinder of the scabbier, or a recess for a piston rod orshank projecting from the cylinder. A taper may be 15 provided between the piston rod end and the bit, the recess possibly comprising a tapered skirt optionally with a cross-hole for securing the rod.BRIEF DESCRIPTION OF DRAWINGS Figure 1 is a face view of a bit? and 0 . Figure 2 is a corresponding side elevation with the centre row of pointed tips and chisel-shaped tips in section.BEST MODE OF CARRYING OUT THE INVENTION The bit shown in the drawings comprises a head 1 of 5 steel having five parallel transverse slots (shown inOMPI Figure 2 only) each with a number of tungsten carbide pointed tips 2 and tungsten carbide chisel shaped tips 3 brazed therein. The head 1 is provided with an integral shank 4 and a spiral circumferential groove 5 whereby the head 1 can be attached to a scabbier.INDUSTRIAL- APPLICABILITYIn use, the shank 4, enters an end of a cylinder (not shown) of a scabbier, a coil spring (not shown) is engaged with one end in the groove 5, and'the other end on the end of the cylinder, to retain the head in position. A piston slidable under motive fluid pressure in the cylinder strikes the free (left hand.) end of the shank 4 and drives the head 1 against the surface under treatment. | • CLAIMS 1. A scabbier bit having a number of tips mounted thereon and means for attachment to a scabbier characterised by a number of pointed tips (2) separat by chisel shaped cutting tips (3) projecting from the head (1) a smaller distance than the pointed tips (2)2. A scabbier bit according to claim 1 in which -the tips are in straight rows.3. A scabbier bit according to claim 2 in which the is a pointed tip at the end' of each row.4. A scabbier bit according to claim 1 with the pointed tips and chisel shaped tips in adjacent rows off-set with respect to each other.5. A scabbier bit as herein described with referenc to the drawings. | FURBY J; JOAD ENG LTD | FURBY J |
WO-1979000778-A1 | 1,979,000,778 | WO | A1 | EN | 19,791,018 | 1,979 | 20,090,507 | new | C04B31 | B24D3, C04B21, C22C29 | C09K3 | C09K 3/14C | PROCESS FOR THE MANUFACTURE OF ABRASIVE PARTICLES | Procedure for the manufacture of abrasive particles (1) of abrasive grains (3) in particular grains of diamond or cubic boron nitride kept together by a metal phase (2) which may be used for instance in resin bonded grinding wheels. A blank is made of the abrasive grains and a bonding agent consisting of metal or a metal alloy whereby a continuous network is formed in the blank by addition of a pore forming material (4). The abrasive particles are then obtained by disintegration of the blank. | Process for the manufacture of abrasive particlesTools for grinding, sawing, filing and similar purposes can use in their active parts abrasive grains of very hard materials like diamond, cubic boron nitride, oxides, carbides, nitrides,borides, etc. These abrasive grains are arranged in a bond which is a continuous phase of metal, plastic, ceramic materials, glass etc. The simplest embodiment is here a uniform distribution of the abrasive grains in the active zone of the continuous phase.There are, however, more complicated distribution patterns . The individual grains may thus be kept to¬ gether in aggregates by means of a special aggregate bond. These aggregates are then arranged in a continuous bond which makes up the active zone of the tool. Diffe¬ rent types of such aggregates with widely varying pro¬ perties are described in the literature. It has thus been suggested -(American patent 2216728) to build up aggregates containing fine diamond grains by means of a small quantity of a special binding material for the aggregates. These aggregates, it is hoped, should have the same grinding properties as individual abrasive grains of the same size as the aggregates. It has been suggested to use metals like nickel with embrittling additives (U.S. patent 2216728) for the bond of these aggregates. The structure of a resin bonded grinding wheel containing such aggregates may be described in this way: diamond grains in simultaneous direct con¬ tact with each other and the metallic aσqreαate bond in its turn surrounded by a resin phase.Another distribution pattern, which has gained a large industrial acceptance, is the use of metal coated abrasive gains, in particular metal coated 5 diamonds, particularly in plastic bonded grinding wheels. At a suitable thickness of the metal coating, life of these grinding wheels is much better than with resin bonded wheels with diamonds with no metal coating (Swedish patent 306271) . When the thickness 10 of the metal coating increases, however, life will be¬ come reduced, sometimes below figures which are re¬ ported for naked diamonds. The structure may in this case be described as one diamond grain contained in a metal phase in its turn contained in a resin phase.15 According to a third invention (Swedish patent 326122) the ratio between metal and diamond can be increased further with an increased positive effect on a life as a result,by means of the feature that every particle o metal contains several abrasive grains which are sepa-20 rated from each other by a metal phase. The abrasive grains exert a strengthening and stiffening up action on the abrasive particle while retaining a certain elasticity of the same. This embody ent might at first . be considered as a combination of the two earlier25 mentioned inventions. This is, however, not the case. Properties of the abrasive particles according to the Swedish patent 326122 cannot be derived from the pro- perties of abrasive grains or abrasive particles accor ding to the two earlier inventions. Also there is a30 marked difference between the structures of the abra¬ sive particles according to these inventions.The two most important differences between the aggrega according to the U.S. patent 2216728 and the Swedish patent 326122 is that the abrasive grains according to -35 the American patent are in direct contact with each other at adjacent points with no intermediate material whereas the abrasive grains according to the Swedish patent are separated by a metal layer. Therefore the amount of binding material in the elastic aggregates according to the American patent' is much smaller than the quantity which is used in the abrasive particles according to the Swedish patent. These differences are due to the main difference bet¬ ween the abrasive particles according to the two in¬ ventions. The object of the American patent is abrasive. particles with the same properties as single abrasive grains of the same size a3 the aggregates whereas the object of the Swedish patent is elastic abrasive par*- ticles for increased life thanks to a better retention of the grains.Abrasive particles according to the two patents may be produced by means of for instance powder metallur¬ gical methods or by means of casting methods. Hereby (1) the quantity of metal (5-10 %, or alternatively more than 20 % counted on the quantity of abrasive grains) , (2) the mechanical properties of the metal phase (brittle or alternatively good mechanical strength and elasticity) and (3) the surface condition of the abrasive grains (naked or alternatively metal coated) will determine whether the process of manufacture will give abrasive particles of the kind' hich are aimed at in the American resp. in the Swedish patent.The present invention refers to a particularly aάvan÷-'-'-' tageous procedure for the manufacture- of abrasive par¬ ticles of the various kinds which have been described above. In the manufacture of these particles, which t \-- contain two or more abrasive grains which are kept to¬ gether by a binding material, most frequently sintering or casting processes are being used. Frequently one then first makes a kind of blank which is then crushed • and ground down to desired particle size. The crushingOft,PI and grinding mome s are difficult operations particu¬ larly in the manufacture of particles according to the Swedish patent 326122 since here the metallic componen is elastic and tough. Abrasive particles according to 5 the 7unerican patent 2216728 can on the other hand be crushed down more easily because of the minimum quanti of binding material and because of the embrittling additions to the metallic binding material in this casAbrasive particles of aggregate type should gain exten 10 sive use in grinding technology since the aggregate re presents a new dimension with respect to product adjus ment compared to a single grain. Aggregates are, howev not much in use in spite of this feature which is due to the fact that one also has to consider the method t 15 be used for the production of the aggregates in the specification of the aggregate bond which ther-efore cannot be optimized solely for its function as aggrega bond. The present invention solves in a suprisingly simple manner the problems which have been discussed 20 above and the result is that the binding material for the aggregates can be formulated with the sole conside ■ tion of it's function in the finished abrasive particl In the same time the manufacture of abrasive particles is simplified and becomes cheaper. A further advantage 25 is that the invention makes it possible to control the structure of the abrasive particles in a simple and straightforward manner to give the particles a structu shape and size which is optimized for each particular application and each type of abrasive grain.30. The characteristic feature of the present invention is that a continuous net-work of holes (cavities) is arranged in the blank from which the abrasive particle are to be made by disintegration of the blank. The hol in the blank which demarcate massive elements which ;*35 correspond to the desired abrasive particles, are pro¬ duced by means of pore forming materials added to the mixture of abrasive grains, metal and the other nents from which the blank is made by sintering, by casting or by means of other known processes to make coherent materials. These pore forming materials should preferably be present in the solid state at the tempe- rature at which bond of the blank is being formed since this gives good possibilities to control the pore struc¬ ture of the blank. Pore forming materials in the liquid state can, however, in certain cases be of advantage, in particular when there is a possibility to govern the structure at sintering by means of a suitable shape and size of the particles ofothe powder mix. Liquid pore forming materials which leave as vapour during sintering can also produce a coherent net-work of holes in^the blank because of the mobility of the liquid state' when used in comparatively small quantities.It is also. possible at least in principle for the pur¬ pose of systematization to talk about performing materials which are present in a gaseous state already before the sintering operation. This corresponds to what in • the practice is called loose sintering with no special spacers. The powder-mix is packed loosely in the sinte¬ ring mould in order to achieve a large open porosity in the goods. This is, however, in general !no & very' suitable method since the strength of the abrasive particles will be fairly small because only moderate pressure can be applied for the compaction of the powdet mix. It is thus not possible to control the structure by means of - if the nomenclature is permitted - gaseous spacers.In the following description of the invention we shall restrict ourselves to pore forming materials which are present in the solid state at the temperature at which the forming of the blank is performed by pressing, rolling or by means of other known and suitable methods for compaction, including casting- Such pore forming materials are of two kinds. Cne kind of pore forming material disintegrates or evaporates at the sintering temperature and leaves the blank as a gas . Holes appea in the blank where the particles of the pore forming materials have been present and where the produced gas has taken its way out of the blank. The o.ther kind of pore forming material remains in the blank during the process of it's formation and'is then removed by dissolution or in a mechanical way.Examples of the first kind of pore forming materials are ammoniumbicarbonate, urea, cellulose derivates, camphor, fine powders of organic materials like poly- ethen etc. This kind of pore forming materials should in general not be used with casting processes where at least one of the metallic components in.the mix mel • since the holes may then to a large extent become eli¬ minated when the pore forming material has escaped out - of the blank when the latter a€ least partly is presen as a melt.The second kind of pore forming materials can be used both with sintering processes as well as with casting processes etc. In the casting processes it is of ad¬ vantage to use pore forming materials which are presen in the solid state during the whole casting process.In sintering processes on the other hand it may someti be of advantage to make use of pore forming materials which melt during the last phase of the sintering and which then again solidify during the- cooling of the sintered blank. - -It is often particularly advantageous to choose a pore forming material which itself is sintering together to a coherent structure which serve as a matrix for th ' sintering .of the metallic components of the blank. The spacer may also simultaneously serve as a sintering activator for the metallic components. Additives may also be used for this purpose e.g. nickel chlorides for the sintering of nickel based aggregate bonds. Such pore forming materials should preferably be removed by ■ leaching and should therefore be soluble preferably in • water solutions. Examples of such suitable pore forming materials are among other -the halides of the alkali- metals. These materials may also serve as a sintering activator thanks to pyrohydrolytic production of hydrogeα chloride in reaction with present water vapour.Some pore forming materials remain inert during the sintering of the blank for instance refractory oxides like MgO, and do not sinter or melt together to a co- herent structure during the sintering process. These spacers cannot in general be removed by leaching but have to be removed by mechanical means or by sedimen¬ tation in liquids, flotation, sifting or by means of ' other procedures after the blank has been crushed up into the abrasive particles.Irrespectively of which method is used to remove the pore forming material it is often of advantage to have the pore forming material present in the blank during the mechanical disintegration. This facilitates the disintegration and helps to disintegrate the blank in the desired way with only a minimum production of abra¬ sive particles out of specification.In certain cases it is possible to control the compo¬ sition of the blank to the effect that it disintegrates by itself into abrasive particles after the bonding of the metallic phase. This can be done by means of shrinkage flaws generated in the weak parts between the abrasive particles to be or by using a large quantity of a non-sintering pore forming material with large particles so that the abrasive particles to be are c :ocmpletely separated from each other in the After this description of the spirit of the invention we shall now in some detail describe some particularly important applications of the invention. Manufacture of abrasive particles in principle according to the Swedish patent 326122 is suchπa particularly important field of application. Abrasive particles of this kind frequently contain very expκnsj?ve and qualified abrasi grains like diamond or cubic boron nitride. Long life of tools with such abrasive grains is therefore a nece ity. The invention is, however, not limited to abrasi particles with the structure covered by the Swedish patent 326122. Abrasive particles for instance accordi • to the American patent 2216728 may also be manufacture according to the present invention. Other binding materials than metal, for instance glass or ceramic materials may also be used as a binding material. Ther are no limitations regarding the chemical composition of the abrasive grains. Furthermore the abrasive parti can be utilized in many different kinds of tools. For simplicity we shall, however, exemplify our descriptio by means of resin bonded wheels with metal bonded abra sive particles containing diamond or cubic boron nitriIn this example the pore 'forming material is composed particles of sodium chloride v/hich after crushing the blank can easily be removed by leaching with water. The structure of the blank, which can be shaped as a circular disk, a band, balls or be of other shape, is shown schematically in Figure 1. The circled parts (1) constitute the elements which after the disintegration of the blank and the removal of the pore forming material' will constitute the abrasive particles. Such an element contains for instance nickel-coated diamond whereby the thickness of the metal-coating may be for instance between 0.0001-0.02 mm and where the diamonds have a size of for instance about 0.07 mm. The coheren metallic phase (2), hich in this case can.be made by powder of carbonylnickel with a particle size of a couple of μm has been sintere together with the nickel-coating of the diamonds (3). he particles of the pore forming materials (4) form a continuous net-work which partly embrace the abrasive particles to be (l) .The latter ones are, however, connected to each other by means fo bridges of sintered nickel powderΛ.(5) -When the blank is crushed or subjected to a similar treatment these bridges will break up so that the abrasive particles to be become free from each other. After the removal of the pore forming material by mechanical means, leaching or in other ways the abrasive particles are ready for the brushing treatment.The structure is in this case governed by the amount and size of the pore forming particles. When the particfe size of the pore forming material is about 0.2 mm, the volume fraction amounts to 50-70 percent by volume cal- culated on the total dilatometric volume of the compo¬ nents, every abrasive to be will contain on the average about five abrasive grains.The powder-mix is compacted to a green blank at a2 pressure of 1.5 ton/cm . The blank is sintered in hydro- gen 45 minutes at 780 C. After cooling in the protec¬ tive gas the blank is crushed and ground for instance in a ball mill so that the abrasive particles become free. After leaching, screening and for instance after- sinteriήg at 900 C in a protective .atmosphere in a fluidized bed the abrasive particles can be used for the manufacture of a grinding wheel for instance according to the Swedish patent 326122. It is sometimes of advantage to use bronze bond containing about 20 % tin for the aggregate. In this case the blank may first be sintered at 230 °C with after-sinterihg at 430 °C for another hour. ^Q\ E 7 -MPI If the fraction of pore forming materials in these examples is increased to about 90-95 % by volume or more the abrasive particles to be will become almost completely separated from each other in the blank and can therefore be very easily separated from each other by leaching. With non-leachable pore forming material like refractory oxides the abrasive particles can easily be separated from the spacer by means of mechanical or methods of sepat±on.The characteristic feature of this invention is, as has been pointed out above, the holes which are gene¬ rated in the blank. It is an easy task for the expert to find a most suitable method for generation of these holes in the blank from case to case depending on the size, shape and kind of abrasive grain and the size, shape and concentration of the abrasive grain and binding material in the abrasive particles. As a general rule special pore forming materials are used for this purpose. There are several alternative routes also when the speci- fication of the abrasive particles is quite firm. It is therefore not possible and also not necessary to report specific rules for the choice of the pore forming material. The suggestions which have been given above in the description should be sufficient for the expert to find a suitable pore forming material in each sepa¬ rate case with no difficulty. The volume fraction of the pore forming material in the blank-can also be varied between wide limits among other things depending on the size and the shape of the pore forming particles. A _ sufficient amount of holes can be generated already at such low concentrations as 3-10 % by volume (dilato- metiric volume-) particularly at low pressures of com¬ pactions. An upper limit can also hardly be specified when thinking of the possibility, with this invention, to manufacture abrasive particles which are completely separated from each other in the blank as has been0Λ1P1 described above. It is, however, not economic to work with larger amounts of pore forming materials than about 95-98 % by volume. Very frequently a good working region is, with pore forming materials which leave as gas, 10-40 % by volume and, with pore forming materials, which are leached away, 40-80 % by volume and, with pore forming materials which are removed by mechanical means, 80-95 % by volume.The size and shape of the holes or in other words the structure of the net-work which the holes produce in the blank is, with solid pore forming materials, to a large extent determined by the shape of the pore forming particles and their size relative to the other structure forming components which are present in the blank during its formation. The holes have two functions, they define the abrasive particles to be and they con¬ tribute to an efficient and defined disintegration of . the blank.In the formation of the blank there are three different kinds of components present namely, abrasive grains, binding material and pore forming materials.- The particles of the binding material are in general about the same size or smaller than the abrasive grains. In certain cases when the ratio between the volumes of the binding material and the volume of the abrasive grains is large, say 10-1 or even 20-1 the particles of the binding material may be much larger than the abrasive grains, however. The volume of a particle of the binding material can in such cases be as much as 10 times larger than the volume of one abrasive grain.OMPl It should, however, in this connection be mentioned that formation by means of casting is a special case since the particles of the binding materials in this case are present.in the molten state during the for- ation apparently, are of atomic dimensions.It is of course as difficult to define the structure of a hole as to define the structure of massive element in a porous body. Quite generally it can, however, be said that the holes in hte blank should frequently be of at least the same size as the abrasive particles to be. If a hole is thought to be produced at the site of particle of a pore forming material the conclusion must be drawn that the pore forming particles on the average should be larger than the.average size of the largest one of the other components which are present in the blank during its formation. The pore forming particles may, however, in their turn often be aggregates of much smaller particles. This size ratio, measured as a volum ratio, should exceed 2 to 1. A figure which is frequent of advantage is between 5 and 20 to 1. In the case of abrasive particles containing many abrasive grains, say 50 to 100, and particles of binding material which are smaller than the abrasive grains it can, however, be necessary to use such large particles of the pore for- - ming material that the ratio mentioned above is aslarge as between 100 and 500 to 1.In the case of most .common abrasive particles the pore forming particles will be smaller than- 1 mm in the longest tip-to-tip direction. A frequently suitable region is 0,1-0,5 mm. There is seldom reason to go below about 0,05 mm. (An exception to this, however, is additions of smaller fractions of the pore forming materials which can frequently be of advantage since these small particles may serve as bridges of connectio' between the larger particles and thereby contributes to the creation of coherent net-work.) As mentioned above the particles of the pore forming material may be composed of small particles which may be as small as about 1μ or below. Also the particles of the binding material may be present as -aggregates. Tarticles of carbonylnickel powder may thus be considered as aggre¬ gates of very small crystallites.The desired shape of the pore forming particles is governed by the desired shape of the abrasive particles. It is frequently desired that the latter one should have a fairly symmetrical structure. From this follows that the pore forming particles in this case should also have a symmetrical structure, that is have about the same measures in all directions. A certain addition of dendritric character to the structure is sometime to advantage since this helps the development of connec¬ tions between the larger holes. Abrasive particles of another shape, -for instance strongly dendritic struc- tures, needles or flakes necessarily require corre¬ sponding special forms of the pore forming particles. | Claim 1Procedure for the manufacture of abrasive particles containing two or more abrasive grains kept together by a binding material whereby said abrasive particles are produced by the disintegration of 'blank character - ized thereby that a continuous network of holes is arranged in said blank which holes demarcate elements of the blank -which elements after the disintegra¬ tion of the blank constitute the abrasive partic- les.Claim 2Procedure according to Claim 1 whereby the binding material is a metal or a metal alloy.Cla. 3 Procedure according to Claim 1 whereby diamonds are used as abrasive grains.Claim 4Procedure according to Claim 1 whereby grains of cubic boronnitride are used as abrasive grains.Claim 5Procedure according to Claim 1 whereby a water soluble salt is used as the pore forming material. | LINDSTROEM O | LINDSTROEM O |
WO-1979000779-A1 | 1,979,000,779 | WO | A1 | EN | 19,791,018 | 1,979 | 20,090,507 | new | A61B6 | null | A61B5, A61B6 | A61B 5/103, A61B 6/00D, A61B 6/04 | DEVICE USED IN X-RAY EXAMINATION OF DISTAL JOINTS' EXTREMITIES | A device used for examining distal joints of extremities. It is especially applicable in x-ray examination of finger and toe joints deformed by rheumatism. To set and maintain fingers and toes in an optimal position allowing the taking of radiographic pictures, the device comprises a model piece (1) having corresponding surfaces (3) for undersides of fingers and toes and with separating means (5) which keep fingers and toes separated from each other. | A device used im X-ray diagnosies of distal joints' extremities.This invention relates to a device used in diagnosing distal joints of extremities. It is especially applicable in X-ray diagnosies of finger and toe- oints deformed by rheumatism.It takes a lot of time to put arms and legs in such a position which gives a good and reliable X-ray film, especially difficult and time consuming is to get de¬ formed fingers and toes in a right position for example to patients with rheumatoid orthrities.These patients often have so deformed fingers and toes that it is impossible to keep them in an optimal posi¬ tion due to reliable films.There exists some devices used in X-ray exposure which are used from material penetrating well X-rays and which help to get the part of the body in a position optimal for exposing. All these devices have the defect that the use of them slowers greatly the X-ray film exposure and most of them give to the developed X-ray film so big sha¬ dows that diagnosing is difficult.The intention of this invention has been to develop such a device with the aid of which X-ray diagnosis and filming is greatly speeded up and at the same time succesful films are received with greater probability with the result that new filmings are unnecessary.Most typical feature of the invention is that the device is composed of a suitable odelpiece in which there are corresponding surfaces for undersides of fingers as well as corresponding things of toes and different things put between those surfaces so that fingers corresponding toe are kept separate from each others.It has been evaluated that when the device is correctly planned and used in conventional cases, it gives twice as many films compared to what is nowadays received; if it is a question of rheumatoid orthrities, X-ray diagnos is three to two fold. It is clear that this is of great economical importance, since capital and salary costs ar reduced greatly.«A more detailed account of the invention, with the aid o the enclosed drawings, is as follows:Figure 1 presents a device used in axonometrical X-ray diagnosis ef a left hand.Figures 2-5 present examples for the device used in axon metrical X-ray diagnosis of toes.Figures 6-7 present a heelsupport in the device used for X-ray diagnosis ©f toes.In Figure 1 is presented the modelpiece no.1 for the lef hand supplied with deep cavities. in which fingers are The hand is presented in such a optimal position to enab a successful and easy X-ray diagnosis between the embras 4 for fingers there remain ridgelike heights 5 which keep and force the fingers apart from each others. The angle shown by arrow a is approximately 140° and so the hand can be exposured automatically from two different angles by twisting the hand on the table of a X-ray machine and these different angles form the standard angle or the angle required. Modelpiece 1 is naturally prepared of a material which well penetrates X-rays. For example foamed plastics suit well for this purpose. It is profitable that the ma¬ terial density of modelpiece 1 is as small as possible, so that it does not make any shadow on the X-ray film. This matter can also be improved so that the lower part of the model is made concave so that the wall thickness of the model is almost constant. There exists also so cheap ma¬ terials adapted to this purpose that the device concerning this invention can be made for one-use only.The surfaces of the modelpiece 1 facing the table of the X-ray machine can be supplied with suction cups or perma¬ nent magnets, which prevent the moving of the model and of the hand which causes trembling of the extremitiy during X-ray filming. Similar kind of result is also obtained when the surfaces of the model facing the table are really smooth, or when the model is coated with some kind of emulsion which increases friction with the result that the hand ©r extre¬ mitiy stays well, partly gummed, on the modelpiece and it stays in a similar way on the table. According to one use¬ ful example, the modelpiece 1 is connected with a propor¬ tionally great weight for example,when made of lead, which is attached to the wrist of the patient like a splint. In ad¬ dition these solutions give more easily succesful films and relieve the work of the nursing personnel. They also relieve greatly the well-being of the patient since the muscles of the extremitiy are proportionally relaxed during filming. The device presented in Figure 1 has to be made in dif¬ ferent sizes due to different sizes of hands. Similarly the models for left and right hands are needed separate X-ray exposing is speeded so that the modelpiece 1 is fi to the hand of the patient with the aid of suitable ban when the patient is waiting for his turn for filming.In figures 2-5 is performed a device for the leg in whic the idea of the invention is applied. The modelpiece 1 i here in the form of a shβesole. According to the adaptat of Figure 2 tees are able to be got separated into the holes 2 with the aid of the studs 2, which are made of molding material. According to the adaptation ef Figure the studs 2 are made of tube. According to Figure 5, ia upper end of the studlike organs there can be a stable o twisting disclike broadening 6 correspondingly 6' with t aid of which a pressure is caused on the upper surface o toes. The same result is achieved so that it is put agai the surface 3, which also of course can be done with the aid of laces or corresponding.According to the adaptation in Figure 4 the separating devices are done of plate-like preformates 7 by folding this into the form presented in the picture.The separating devices can also be done of plate-like pr formates and studs also when it is a question of X-ray e posures-of the hand. Since fingers are longer than toes, codes 2 are to be used between each finger, though each can be supplied with disc-like broadenings 6 or 6'.In figures 6 and 7 there are two different heel pieces 8 and 9 which can be attached to corresponding holes 8'an In the modelpiece 1 presented in Figure 2. With the aid of these heel pieces, which at the same time regulate the ef¬ fective length of the sole formed modelpiece, this model- piece can be tightened to the leg in question and at the same time press toes with a little ferce te separating de¬ vice 2 or between corresponding during exposing.According to the device presented concerning this invention also other kind of modifications can be developed, and this invention is by no means limited to the sample presented in the preceding. Many individual features concerning the modelpiece can be changed by various methods and can be modified so that the invention is still valid.So for example the density of the modelpiece can be changed either continuously or stepwise so that the shadow formed is equal to the sufficient accuracy and does not disturb the diagnosis. This is also obtained by concaiving the modelpiece from underside or innerside so that the addi- tioned thickness of the walls are about the same looking from the exposing direction. | WHAT WE CLAIM IS:1 ) A device used in X-ray diagnosies of distal joints of extrimities, the device being especially applicab for the use of X-ray diagnosies of deformed finger a toe joints due to rheumatoid orthrities, characterize that it comprises a suitable model piece (1) and rid separators (2,5,7), which have the surfaces (3) for the undersides of fingers correspondingly toes and separating devices in order to keep fingers corres¬ pondingly toes separate from each others.2) The device of Claim 1 wherein the model piece (1) has corresponding grooves (4) for the fingers with a shor distance from each others, the bottoms of the grooves forming corresponding surfaces (3) for the undersides of the fingers, and between those bottoms there are ridges (5) which function as separating devices.3) The device of Claim 1 wherein the separating devices comprise of studs (2) which are placed between the corresponding surfaces (3).4) The ridge separators of Claim 3 wherein the upper end of the studs there exists a stable disclike broadenin5) The ridge separators of Claim 3 wherein at the upper of the studs (2) there is a separating disclike broa¬ dening (61).6) The device of Claim 1 wherein the separating ridges a made of platelike preformaties (7) folded into a sui¬ table form.J_!Α_. 7) The assisting device of Claims 1-6 wherein the device is provided with suitable attaching devices for attaching it to the leg or arm.8) The assisting device of Claim 2 wherein the modelpiece (1) is provided with an adhesive, friction emulsion or a corresponding coating which increases the adhesive friction.9) The assisting device of Claims 2-3 wherein the under surface of the modelpiece (1) is connected with two such planes which form together a V-angle (a) which is preferably about 120-150°, so that two constant exposing angles are obtained with the same modelpiece (1) by tilting it suitably.10) The assisting device of Claims 1-9 wherein the density of the modelpiece i$ the range to be diagnostically investigated is changing so that the shadow formed in X-ray exposure in one or more exposing angles is cons¬ tant with sufficient accuracy.11) The assisitng device of Claims 1-9 wherein the model¬ piece is concaved so that the thickness of the ridge or ridges together in the area to be investigated about constant in one or more exposing angles so that the shadow formed by exposure is constant with a suf¬ ficient accuracy. | JUHA K; LARSSON V | JUHA K |
WO-1979000780-A1 | 1,979,000,780 | WO | A1 | XX | 19,791,018 | 1,979 | 20,090,507 | new | E03D3 | null | E03D3 | E03D 3/10, E03D 3/12 | WATER CLOSET | A water closet of the tank type in which air is entrapped in the tank creating pressure to assist in expelling flushing water to a bowl during the flushing cycle. The flushing cycle is activated by a disc valve (38) and piston (26) connected to a domestic water supply (12) for dislodging a float (18) and valve (20) from a valve seat. The water closet is constructed with a minimum of moving parts by employing a piston (26) for dislodging the float which temporarily cuts off the flow of water to the bowl and utilizes the water pressure for returning the piston to the static position. The system also employs a vacuum breaker assembly (52) having a ball (56) in an angled pipe maintained by gravity against a seat in the flushing water line. The force of the water flowing into the bowl forces the ball from the seat during flushing. The ball returns to the seat by the force of gravity on the completion of flushing, preventing back pressure from any vacuum in the domestic water supply. If back pressure occurs before the ball seats, air is drawn through a vent pipe in to the domestic water supply, preventing any siphoning from a bowl. | S P E C I F I C A T I O NWATER CLOSETTECHNICAL FIELD •This invention relates to water closets, and more particularly relates to an improved water closet utilizing a pressurized tank system having a minimum of moving parts. BACKGROUND ARTWith the advent and increasing concern for water conservation, the need for an efficient water closet using minimum water for efficient operation is evident. Such devices have been heretofore proposed, but have not been widely accepted because of the complexity of their construc¬ tion. Such systems employ pressurized tanks to reduce the overall space required for the system, while maintaining the same efficient operation. These systems are advantageous in that they require less water for flushing and produce effi- cient operation with a minimum of objectionable noise_ OMPI DISCLOSURE OF INVENTIONThe purpose of the present invention is to provide an improved water closet which has a minimum of moving parts and provides efficient operation with a minimum waste of precious water.The present invention is an improvement on U.S. patents 3,397,408, issued August 20, 1968, and 3,628,195, issued on December 21, 1972, to the same inventor of the device disclosed herein, and are incorporated herein by refer¬ ence.In those patents, there is illustrated a water closet in which air is trapped at the top of a tank and aids in expelling water into the bowl, along with the domestic water supply pressure during flushing operation. However, it was found that that device was not as efficient as possible because of its somewhat complex construction and the number of moving parts required to perform the flushing operation.The present invention provides an improvement in which the number of moving parts is reduced to a minimum. In the improved device the domestic water supply is connected to the tank through a check valve and also to the piston through a disc valve. The disc valve operatipn is on the same principle and is similar to that disclosed in U.S. patent 3,614,057, issued to Louis Hospe on October 19, 1971. The piston in theOMPI improved version is operated solely by the water pressure itself without the need for any type of biasing spring or complicated sealing arrangements. In the improved version the piston dislodges the float during the flushing operation opening the valve as before when the plunger on the actu¬ ating disc valve is pushed. However, in the present inven¬ tion, an extended shank on the piston closes off the flow path of water to the bowl temporarily until the float is completely dislodged from the valve seat. The pressure in the tank, as well as the pressure from the domestic water supply, is now applied to the end of the shank of the piston closing off the flow passageway to the bowl. This pressure begins to force the piston back to the static condition opening up the flow passageway to the bowl to begin the flushing operation. The piston, which is initially operated by the domestic water supply pressure, slowly drifts back to its static position with water bleeding off around the pisto into the bowl because of the imbalance of pressure between the tank and the domestic water supply pressure. The clear- ance around the piston head and cylinder wall is controlled to permit the pressure of the domestic water supply to initi ally drive the piston up to dislodge the float valve, thus slowly releasing the water by allowing it to bleed off aroun the piston as the flushing water forces it down.Simultaneously water flows through the float valve opening into the bowl through a unique vacuum breaker assemb which is adaptable to any present water closet by being f connected in the line between the tank and the bowl. The vacuum breaker operates by means of a gravity controlled ball resting on a valve seat in the path of the flushing water. The ball is retained in. a tube angled slightly upward and is forced from its seat by the flushing water. As the float •valve begins to recede and the flushing water reduces in volume, the ball by gravitational force returns to the seat, preventing a vacuum condition in the domestic water supply from drawing contaminated water from the bowl into the water supply. If the vacuum condition occurs prior to reseating of the ball, air to break the vacuum condition is allowed to flow through a vent or stand pipe around the ball into the domestic water pipes without creating any siphoning condition in the bowl. A grating in the tube containing the ball permits the flushing water to flow past the ball into the bowl.It is one object of the present invention to provide an improved water closet having a minimum of moving parts.Another object of the present invention is to provide a water closet having a flushing operation operated entirely by the domestic water supply pressure.Another object of the present invention is to provide an improved water closet in which a piston for dislodging the float from its seat temporarily excludes water from the bowl, thus causing the piston to be returned to its static condition by the flushing water. Still another object of the present invention is to provide an improved water closet having a unique vacuum breaker assembly.Still another object of the present invention is to provide an improved water closet having an improved vacuum breaker in the form of a gravity-operated ball engaging a seat in the flow line of the flushing water.These and other objects of the invention will become readily apparent from the following detailed description of the invention when considered in conjunction with the acco - panying drawings wherein like reference numbers identify lik parts throughout.BUKLATOMPI BRIEF DESCRIPTION OF DRAWINGSFIGURE 1 is a sectional side elevation illustrating the invention in the static condition.FIGURE 2 is a sectional view of the vacuum breaker section of the invention taken at 2-2 of Figure 1.FIGURE 3 is a sectional side elevation similar toFigure 1 illustrating the invention immediately after actu¬ ation of the disc valve.FIGURE 4 is a sectional side elevation similar to Figure 1 illustrating the invention in the flushing condition. BEST MODE FOR CARRYING OUT THE INVENTIONReferring now to the drawings, and in particular Figure 1, there is shown a tank 10 closed at the top and bottom connected to a domestic water supply by means of lin 12 through conduit 14 and an inlet in bottom plate 16. A deflector plate 17 adjacent to inlet in plate 16 acts as a turbulence arrester to stop the water from boiling during filling of the tank 10. The plate 17 smooths out the flo of water into the tank in much the same manner as the baffl shown in patent 3,628,195, providing very quiet operation. The tank 10 has a float 18 for operating the float valve 20 in the usual manner. The float 18 is controlled by a cage guide formed by rods 22.The float valve 20 is operated and dislodged from i seat 80 by a rod 24 on the piston 26 retained in a cylinder or chamber 28 of a housing or casting 30. The piston has a piston head 32 and an elongate shank 34 for closing off out 36, as will be more clearly described hereinafter. The pis head 32 is slightly smaller than the diameter of the chambe to allow water filling the chamber 28 to bleed off into the flushing system at a controlled rate, as will be more clear described hereinafter.The cylinder 28 is connected to a disc valve 38 by conduit 40. The disc valve 38 is also connected to the dom tic water supply 12 by another conduit 42 and a tee 44, and operated by a plunger 46.The piston housing 30 and float valve assembly is removably secured to the tank 10 by means of a coupling 48. Bore 50 in housing 30 provides a passageway from the tank 10 to the outlet 36 of a vacuum breaker 52.The vacuum breaker 52 is comprised of a pipe or tube 54 attached to a fitting 58 secured to the housing 30. The tube 54 may be secured to the fitting 58 by any suitable means, such as a coupling or by welding or an adhesive. In- side the tube 54 is a ball 56 which normally rests against the seat 60 on the end of the fitting 58. The ball is re¬ tained in the tubing 54 by a grating 62 providing a passage¬ way into the pipe 64 leading to a bowl. The pipe 54 has an opening 66 to permit air to flow around the ball when a suction or vacuum occurs in a domestic water supply 12 or in the tank 10. A vent tube 68 is secured by any suitable means to the end of the tube 54 holding the ball 56. An O-ring 70 pressed against lip 72 at the opening 66 in the end of tube or pipe 54 provides a seal when the ball 56 is forced to the end of the pipe 54 by flushing water.The float bulb 20 is secured by a number of rods 22 forming a cage secured in the end of housing 30. Thus, re¬ moval of coupling 48 permits removal of the piston housing along with the cage 21 and float. The supply of air 84 at the top of tank 10 is regulated by a bleed tube fitting 51 seated in the end of housing 30, adjacent to the opening of chamber 50. A properly selected vent or air tube 53 is seated in the bleed tube 51 having its height arranged to expel excess air prior to seating of the float 20. That is, the height of air tube 53 is selected so that when the leve of water in the tank falls below the end of the tube 53, excess air may bleed off through the tube into the mouth of the chamber 50 before the float 20 reseats. In this manner, the amount of air 84 above the water level in tank 10 can b regulated.Operation of the system is substantially similar to that described in patent No. 3,397,408 referred to above an is illustrated in Figures 3 and 4. In Figure 3 the operati of the system is depicted immediately after actuation of th disc valve 38 by pressing plunger 46. The pressing of plun 46 forces the end of rod 74 away from the valve seat 76 agai the action of the flexible disc 78 providing a flow of domes tic water supply through the disc valve 38 into the chamber through pipe 40. This action forces the piston 34 upward causing the rod 24 to dislodge the valve seal 20 from its se 80. This permits water to flow into the bore 50 in the pis housing 30, but no flushing is permitted at this time as the shank 34 of the piston has closed off the outlet 36 to the bowl. When the piston reaches the limit of its travel (i.e. the end of chamber 28) with the chamber 28 full, the disc valve 38 automatically closes. At this time the pressure from the water 82 and air 84 trapped in the tank 10, plus the pressure from the domes¬ tic water supply 12 through the deflector plate 17 on the bottom plate 16, is applied to the end 86 of the piston shank 34. This creates a pressure imbalance in which the pressure against the shank end of piston 26 exceeds the pressure at the opposite end on piston head 32, causing the piston to move downward in the chamber 28 until the outlet 36 is opened, as illustrated in Figure 4. As the piston is forced downward water bleeds off around the piston head into the outlet 36. Indentation or cutout 29 adjacent to the outlet 36 provides a bleed path around piston head 32 when the piston is at the top of chamber 28.Water immediately begins flowing through the outlet 36 through the tube 54 into the bowl through pipe 64. The force of the water forces the ball 56 in the vacuum breaker 62 against the O-ring seal 70, diverting substantially all of the flushing water into the bowl. Vent pipe 68 prevents any leakage of water which might flow around the ball 56 before it seals against the O-ring 70.When the piston 26 reaches the bottom of the cylinder 28 and the float valve 18 closes, the pressure of the domestic water supply causes water to flow into the tank 10 to sub¬ stantially fill the tank and create an air pressure head 84, returning the tank to the static condition illustrated in Figure 1. The tank stops filling when the pressure in theOMPI tank equalizes with the pressure in the domestic water supply. No shut-off valve is needed.The anti-siphoning or vacuum breaker 52 is unique in that it may be attached to any existing water closet by tap- ping into the supply line to the bowl with a fitting similar to 58. While fitting 58 is shown as secured or welded or otherwise fixed to the housing 30, it can be constructed for attachment in any number of ways. The vacuum breaker 54 allows the flow of water through outlet 36 into the bowl through pipe 64 by displacing the ball 56 to the end of the pipe 54 against the seal 70. The ball 56 remains in this position until the float valve sealing bulb 20 cuts off the flow of water to the bowl. At this time the ball rolls down the inclined tube 54 to reseat against the seat 60 of the fitting 58. If a vacuum should occur in the domestic water supply line 12 or tank 10 before the ball reseats, then air will be drawn through vent pipe 68 around the ball through the opening 66 and grating 62 into the domestic water supply, preventing any siphoning of water from the bowl through pipe 64. Alternatively, the ball 56 will be drawn tightly agains the end of fitting 58 sealing off the water supply.As described in U.S. patent No. 3,628,195, some means may be needed to compensate for absorption of air in the tank if the system is unused over an extended period of time. In most cases the domestic water supply is thoroughly aerated and no compensation is needed. However, one method of0MPI resupplying air would be to provide an aspirator in line 14 which would draw in a little air every time the tank is filled. Another method would be to float a buoyant disc 85 (shown in phantom) of styrofoam plastic or some other non- water-absorbing plastic, on top of the water in tank 10. Since the amount of absorption is directly proportional to the area of air-water interface, the float could reduce this area by better than 95%, thus reducing the air absorption. The sides of the float 85 would be suitably curved to prevent it from becoming wedged in the tank.Thus there has been disclosed an improved water closet in which all moving parts have been reduced to a minimum by simplifying valves and eliminating the necessity for springs or complicated constructions. The system operates smoothly, quietly and with a minimum of water wasted.Obviously, many modifications and variations of the present invention are possible in light of the above teach¬ ings. It is therefore to be understood that the full scope of the invention is not limited to the details disclosed herein but may be practiced otherwise than as specifically described. | WHAT IS CLAIMED IS1. A hydraulic flushing device comprising: a tank having a closed upper end; closing means closing the bottom end; connecting means connecting said tank to a domestic water supply; an outlet adjacent to the bottom of said tank; a float normally closing said outlet; a piston mounted below said outlet; a valve connected to the domestic water supply; a conduit from said valve to said piston to supply water under pressure to one side of said piston when said valve is activated;• dislodging means on said piston for dislodging said float when water is supplied to said piston; and said piston adapted to close said outlet before sai float is dislodged whereby water from said tank forces sai piston back to its original position during the flushing operation to open said outlet. 2. The hydraulic flushing device according to Claim 1, including: an upwardly angled nipple connected to said outlet; an upwardly angled tee coupled to said nipple; a ball in the cross-member of said tee- normally resting against the end of said nipple; and said tee having its downward member connecting the cross-member to a toilet bowl, whereby water flowing through the nipple to the bowl pushes the b-all off the seat and the angle of said tee and nipple causes the ball to roll back and seat against the end of the nipple after water stops flowing through the outlet.3. The hydraulic flushing device according to Claim 2 including: grating means in the cross-member of the tee commu¬ nicating with the downward member to prevent restriction of the downward member by the ball. 4. The hydraulic flushing device according to Claim 2 wherein the end of the tee cross-member opposite the end coupled to the nipple includes, vent means venting said nipple to the atmosphere; and sealing means for sealing said vent means when water is flowing through said nipple to said toilet bowl.5. The hydraulic flushing device according to Claim 4 wherein, said vent means comprises a stand pipe connecting the open end of said tee cross-member to the atmosphere; and said sealing means includes a lip on the open end of the cross-member whereby said ball is forced against said lip by the flow of water.6. The hydraulic flushing device according to Claim 5 including: a resilient ring in said cross-member abutting said lip whereby said ball compresses said ring against said lip to seal the open end of the cross-member during flow of water. 7. The hydraulic flushing device according to Claim 1 wherein said dislodging means comprises: an extension out of said piston adapted to engage and push said float off the seat after the piston closes the outlet.8. The hydraulic flushing device according to Claim 7 wherein said dislodging means comprises a rod of predetermined length attached to said piston.9. The hydraulic flushing device according to Claim 1 wherein said valve is an automatic closing flexible disc valve.10. The hydraulic flushing device according to Claim 1 wherein said piston comprises: a cylinder in a sleeve; a flange on the end of said cylinder opposite the dislodging means; and a shoulder in said sleeve for abutment by said flange whereby the length of travel of said piston is limited. 11. The hydraulic flushing device according to Claim 1 wherein: said outlet intercepts said sleeve; and said piston cylinder closes off said outlet when said flange is abutting said shoulder.12. The hydraulic flushing device according to Claim 1 including: a float in said tank for reducing the air-water interface to reduce the absorption of air into the water.13. The hydraulic flushing device according to Claim 12 wherein said float is comprised of a non-water- absorbing plastic.14. The hydraulic flushing device according to Claim 13 wherein the float size is selected to reduce the air-water interface area by at least 95%. 15. A vacuum breaker for attachment to toilet systems comprising: a nipple; attachment means for attaching said nipple at an upward angle to the outlet water of a toilet system; a tee; coupling means coupling said tee to the end of said nipple with the cross-pipe angling upwardly with the nipple; a ball in said cross-pipe normally resting against the end of said nipple; and a down pipe of said tee connecting said cross-pipe to a toilet bowl whereby water may flow through said nipple to said bowl by pushing the ball up the cross-pipe but water flowing in the opposite direction forces the ball against the end of the nipple sealing the tank and supply from any back flow.16. The vacuum breaker according to Claim 15 including: grating means in the cross-member of the tee communicating with the downward member to prevent restric- tion of the downward member by the ball. 17. The vacuum breaker according to Claim 16 including: vent means venting said nipple to the atmosphere; and sealing means for sealing said vent means when water is flowing through said nipple to said toilet bowl.18. The vacuum breaker according to Claim 17 wherein: said vent means comprises a stand pipe connecting the open end of said tee cross-member to the atmosphere; and said sealing means includes a lip on the open end of the cross-member whereby said ball is forced against said lip by the flow of water.19. The vacuum breaker according to Claim 18 including: a resilient ring in said cross-member abutting said lip whereby said ball compresses said ring against said lip to seal the open end of the cross-member during flow of water. U O,-Λ, W | SKOUSGAARD E | SKOUSGAARD E |
WO-1979000784-A1 | 1,979,000,784 | WO | A1 | XX | 19,791,018 | 1,979 | 20,090,507 | new | B63B27 | null | B63B27 | B63B 27/14 | A SHIP'S EMBARKATION DEVICE | A ship's embarkation device and comprises a projecting means, e.g. a ladder (3), which atone end is pivotally connected to a first platform (2), which is pivotally connected to the ship's deck, and at its other end is pivotally connected to a second platform (4). The first and second platforms are unrotatably connected to each other via a connecting bar (5), which is pivotally arranged at both platforms. The connecting bar always keeps the second platform in a horizontal position as well as strengthens the torsional resistance of the device. Moreover the ladder is kept tighter to the ship's deck, which prevents the ladder from swinging as the ship is rolling. | A SHIP'S EMBARKATION DEVICEThe technical field.The present invention refers to a ship's embarkation device comprising of at least one projecting means, e.g. a ladder, to the one end of u/hich there is pivotally attached a first platform, u/hich is connected to the ship's deck, and to the opposite end of u/hich a second platform is pivo¬ tally attached.The background of the inventionWhen installing conventional accomodation ladders (Suedish patent 369.696) uhich also are intended to be used as embarkation devices for pilots etc. a fairly large-scale operation is required on the ship's deck. The platform, uhich is pivotally connected to the ship's deck, is via a torsion axle connected to one or even tiuo folding davits, tuhich are to be u/elded on to the deck. This also applies to the supports for the torsion axle. The davits and the wires running via them shall aliuays keep the second lou/er platform in parallel uiith the ship's deck. The ladder is operated by means of uires, u/hich run from the ladder via the davits to brackets and to a uinch each. The brackets have to be u/elded on to the deck as u/ell, and takes up some spac This type of accomodation ladders fulfils very high demands for safety con¬ sidering embarkation of e.g. pilots and the operation of the ladder and is mainly intended for large ships.According to a previously knou/n accomodation ladder (the Danish patent 5764) the steps are pivotally connected by longitudinal beams uith an upper platform u/ith the purpose of automatically keeping the steps horizon¬ tal at different inclinations of the ladder. The device has no louer plat¬ form and is not arranged or intended as an embarkation device for pilots and similar. Summary of the inventionThe purpose of the present invention is to provide a constructively simple and thereby cheaper embarkation device, by uhich a simplified installation is achieved at the same time as a perfectly satisfac¬ tory function and safety of the accomodation ladder is maintained and the louer platform shall aluays automatically be kept in a horizontal position. The procedure of turning the device to the stou/age position u/ill be simplified as uell. According to the invention this has been solved by pivotally arranging at least one connecting bar betu/een the first and the second platform via first and second pivot axles, thus providing an unrotatable connection betu/een the platforms, u/hich is intended* aluays to keep the second platform in a horizontal positon and also to strengthen the torsional resistance of the device.'The Danish patent specification No. 5764 shou/s an accomodation ladder u/ith' a connecting member, uhose purpose, hou/ever, is only to parallel the steps of the ladder. This device has no second platform.The device according to the invention illustrates several important ad¬ vantages, some of them mentioned belou/.Only a feu details have to be u/elded on to the deck and the stowage spa required is exceedingly small. The connecting bar stabilizes the ladder makes it steadier and safer to ualk on. There is no need of davit arms structing the through-fare on the ladder uhen this is hoisted to its upper position. Furthermore, the ladder is kept against the ship's side more firmly than at devices hanging in vertical uires, and this prevent the ladder from swinging when the ship is rolling. The connecting bar always keeps the lower platform in a horizontal position and also takes up the torsional forces between the platforms when the ladder is turned to and from the stowage position.Further characteristics of the invention will be evident from the sub-c and from the following specification, in which some embodiments are mor closely described in accordance with the enclosed drawings. Description of the drawingsFigure 1 is a schematic side view of an accomodation ladder according to the invention,Figure 2 is a plane view of the accomodation ladder according to figure 1,Figure 3 is a schematic side view of an accomodation ladder according to another embodiment,Figure 4 is a plane view of the accomodation ladder according to figure 3,Figure 5 is a perspective view showing an accomodation ladder according to the invention, provided with a device for swinging the ladder out from the ship's side,Figure 6 is a perspective view showing a modification of the upper platform of the accomodation ladder,Figure 7 is a plane view of a further embodiment,Figure 8 is a side view of the accomodation ladder according to figure 7, andFigure 9 is an end view of the ladder according to figures 7 and 8 in a stowed position.Description of some preferred embodimentsThe ship's deck is denoted with the numeral 1. A first upper platform 2 is pivotally attached to the deck 1 via a pivot axle 24, and the accomoda¬ tion ladder 3 is pivotally mounted to said platform 2 via pivot axles 17. A second platform 4 is pivotally attached to the opposite lower end of the ladder 3 via pivot axles 18. The platforms 2 and 4 are connected by means of a torsion connecting bar 5, which is pivotally mounted via pivot axles 14 and 15 to the two platforms, which thereby are always kept parallel to each other, that is horizontal at every position of the ladder. The connecting bar 5 takes up the torsion forces between the platforms 2 and 4 at the turning of the ladder to and from the stowage position. At the second platform 4 there is attached an arm 6 projecting from said platform, . which arm extends along the ladder 3 on the inside.The accomodation ladder is supported by at least one wire 7 which according to the embodiment in figures 1 and 2 runs from a winch 8.through a block 9 arranged above the deck, e.g. at an upper deck, mast or similar of the ship, and round pulley 10 at the outer corner of the second platform 4 mote from the ladder 3, round a pulley 11 at the inner corner of platfo 4, remote from the ladder 3 along the inside of the arm 6, round a pull 12 at the free end of the arm 6 and to an attachment 13 at the deck 1. hoisting of the accomodation ladder is thus performed with double wire parts, at which the winch 8 is .exposed to less tension. Only one drum i required on the winch 8.In this embodiment the pivot axles 14 and 15, respectively, of the conn ting bar 5 are mounted to the first and second platforms 2 and 4, respe tively, at a support 6 on the inside of the first platform 2 resp. at arm 6; so that the pivot axles 14 and 15 are located in other vertical than the pivot axles 17 and 18, respectively of the ladder 3. By this a effect is achieved, which stabilizes the second platform 4 when the lad lowered. Figure 1 shows with continuous lines the accomodation ladder i hoisted-up position, while a lowered position is shown with dash-dottedAccording to figure 1, plane A, going through the axles 14 and 17, is e tially parallel with the plane going through the axles 15 and 18. This true for any position of the ladder. Furthermore the distance C between axles 14 and 17 is essentially equal to the distance D between the axle 15 and 18.According to figures 3 and 4 of the embodiment there is a possibility t hoist the accomodation ladder also to a position above the deck 1, whic be desired in harbours with great differences in tide and when ships ar so heavily loaded that the deck may be lower than the quay. According t this embodiment the attachment 13 of the wire 7 is therefore arranged a the deck 1 on the same level as the block 9, end the connecting bar 5 i placed at a larger distance from the ladder 3 than according to figures and 2 of the embodiment, at which the wire 7 runs between the ladder 3 the connecting bar 5. The pivot axles 14 and 15 resp., of the connectin bar 5 are located in the vertical plane through the pivot axles 17 and 18, resp., of the ladder 3 in order to make it possible to raise as wel as lower the ladder relative to the deck 1. Figure 3 shows, with contin lines, the ladder 3 in a horizontal position at the deck and, with dash-dotted lines, the ladder when hoisted to a position above the deck and lowered to a position below the deck.BAD ORIGINAL In the embodiment illustrated in figure 5 there is arranged on the deck 1 a swing boom 19, at the free end of which is arranged a block 20. The wire 7 runs from the winch via the block 20 to the second platform 4 and back to a hook 21 hanging down from the boom 19, where it is attached. Said hook 21 is intended to catch the ladder 3, when this has been hoisted up to a hori¬ zontal position. Instead of the hook 21 a disc or a wire-disc can be arranged on the boom 19. When the ladder has been hoisted so that the pulley 12 reache the hook 21 or the disc or the attachment point 13 (fig. 2) the ladder and its platforms is turned up to a vertical position or stoβing position owing to that the pulley 12 of the second-platform 4 at the connecting bar 5 is kept in place while the outer further side of the platform 4 is hoisted farther. The torsional movement of the platform 4, thus arising, is trans¬ ferred tb the first platform 2 via the_ connecting bar 5. By this arrange¬ ment the ladder 3 can be swung out from the ship's side by swinging the boom 19. This can be necessary in case the ship does not lie close to the quay 22, e.g. due to protecting fenders 23 arranged at the quay 22.In the embodiment according to figure 6 the stowage is performed in a some¬ what different way. In this case a parallel movement of the accomodation ladd takes place from a position outside the deck 1 to a position on the deck and vice versa. This can be necessary in those cases where the deck 1 is located below the quay and the ship's side is so close to said quay that it is impossible to place the ladder between the ship and the quay. In such a case the ladder 3 can be hoisted up from its position on the deck. Said parallel movement is done by displacing the first platform 2 on the deck 1 in guides 25.The embodiment according to the figures 7-9 is at first hand intended for small ships and is for this reason further constructively simplified com¬ pared to the above described embodiments. Thus the arm 6 is missing and the device is operated only with one wire part 7. The connecting bar 5 is placed under the ladder 3 and is preferably represented by a tube, which at both ends is provided with perpendicularly arranged tubular pieces 33, which by means of discs 34 are pivotally connected to the respective platform 2, 4 via the pivot axles 14 and 15 resp. By designing- x REAT BAD ORIGINAL OMPI& BI RNAT.OI the connecting bar 5 in this way it can transfer torsion forces, which necessary when the ladder is turned to and from its stowing position on the ship's deck.On the side of the platform 4 facing the ship's side an arm 28 is arran at the free end of which a roller 29 is mounted. When the device is hoi the roller will rest against the ship's side and when the second platfo 4 has reached the level of the ship's deck 1 the roller '29 will roll up a track 30, which at its upper end has a curved portion 31 catching the roller 29, at which when the wire 7 is further pulled the device will b pivoted about the pivot axles 24 and take the vertical position shown i figure 9. In this position the ladder rests on the upper part of a brac 32, at which also said track is arranged. In this position the device i lashed in a suitable way.When the device is to be lowered the lashings are released and the wire is slackened, at which the device is lowered in a very simple way.The invention is not limited to the embodiments shown but can be varied within the scope of the following claims. Thus, instead of the ladder 3, there can be a projecting means comprising of a tube or framework con¬ struction, at which the person or persons, who are to be taken on board, board(s) the second platform, which after this by means of the winch is lifted up on a level with the ship's deck.OMPI^RN!Ύ\ | C L A I M S1. A ship's embarkation device comprising at least one pro¬ jecting means, e.g. a ladder (3), to the one end of which there is pivotally attached a first platform (2) connected to the ship's deck, and to the opposite end of which a second platform (*0 is pivotally attached, c h a r a c t e r i z e d i n, that at least one connecting bar (5) is pivotally arranged between the first (2) and the second platform (<4) via first and second pivot axles (1*1, 15), said bar providing an unrotatable connec¬ tion between the platforms (2, *0, which is intended always to keep the second platform (*0 in a horizontal position as well as to strengthen the torsional resistance of the device.2. A ship's embarkation device according to claim 1, c h ¬ r a c t e r i z e d i n, that the plane (A) going through the first pivot axle (17) of the projecting means (3) and the first pivot axle (1*0 of the connecting bar (5) is essentially parallel with the plane (B) going through the second pivot axle (18) of the projecting means and the second pivot axle (15) of the connec¬ ting bar.3. A ship's embarkation device according to claim 2, c h a ¬ r a c t e r i z e d i n, that the distance (C) between the first pivot axle (17) of the projecting means (3) and the first pivot axle (1*1) of the connecting bar (5) is essentially equal to the distance (D) between the second pivot axle (18) of the projecting means and the second pivot axle (15) of the connecting bar.*1. A ship's embarkation according to claim 3, c h a r a c ¬ t e r i z e d i , that the first and second pivot axle resp. (1*1 and 15 respectively) of the connecting bar (5) is arranged in another vertical plane than the first and second pivot axle resp. (17 and 18 respectively) of the projecting means (3). 5. A ship's embarkation device according to claim 3, c h r a c t e r i z e d i n, that the first and second pivot axl resp. (1*1 and 15, respectively) of the connecting bar (5) is arranged in the same vertical plane as the first and second pi axle resp. (17 and 18 respectively) of the projecting means.6. A ship's embarkation device according to any of the pre vious claims, c h a r a c t e r i z e d i n, that the connec bar (5) is arranged parallel with and along the one side edge the projecting means (3).7. A ship's embarkation device according to any of the pre claims, c h a r a c t e r i z e d i n, that an arm (6), ext towards and parallel with the projecting means (3), is attache to the platform (*0, at the free en of which arm there is mou a first pulley (12) for a wire (7), which is led via a second pulley (10) at the diametrically opposite end of the platform8. A ship's embarkation device according to any of the pre vious claims, c h a r a c t e r i z e d i n, that a swing b (19) is arranged on the deck (1) and at said boom a block (20) for the wire (7) is arranged and also a member (21) to which t wire is attached, said member being arranged to catch the proj ting means (3), when this is hoisted up to a horizontal positi at which a stowage of the device on the deck (1) can be perfor in the usual way.9. A ship's embarkation device according to any of the pre vious claims, c h a r a c t e r i z e d i n, that the devic is vertically adjustable relative to the deck (1) from a middl position on the deck to a position above the deck and to a pos tion below the deck at the ship's side, respectively.10. A ship's embarkation device according to claim 9, c h a r a c t e r i z e d i , that the first platform (2) is dis- placeable in transverse direction of the ship along guides (25 from a position where the device is located on the deck (1) to position outside the ship's side.BAD ORIGINAL ^^UREΛOi PI fa W1PO | NILSSON P; WELIN AB | NILSSON P |
WO-1979000785-A1 | 1,979,000,785 | WO | A1 | EN | 19,791,018 | 1,979 | 20,090,507 | new | G01F1 | null | G01F1 | G01F 1/32A1 | VORTEX SHEDDING FLOWMETER CONSTRUCTION | A vortex flowmeter having a flow obstruction body or vortex forming bar (16, 17, 18) formed in a manner to provide enhanced generation of vortices across a wide range of Reynold numbers of the fluid being measured. The bar includes projections (16A, 17A, 18A) adjacent the lateral edges thereof which tend to cause formation of vortices at the leading lateral edges with respect to the direction of flow and enhance the formation of such vortices along the surfaces extending generally parallel to the flow. Additionally, the flowmeter disclosed provides a mounting (34, 36) for a sensor (37) which makes the device relatively insensitive to acceleration in the mounting structure or supporting pipe of the flowmeter. | VORTEX SHEDDING FLOWMETER CONSTRUCTION BACKGROUND OF THE INVENTION1. Field of the InventionThe present invention relates to vortex shedding flowmeters having flow obstruction bodies to generate vortices and mountings for sensors used with such flow¬ meters.2. Prior ArtIn the prior art various flowmeters have been advanced which use vortex formation for flow sensing. For example, a T shape cross section flow obstruction bar is shown in United States Patent No. 3,972,232, and it has a significantly narrower main body section than the head of the T. Likewise, a flow sensitive body which includes an irregular cross section is shown in Figure 8 of Patent No. 3,116,639, and in other figures of this patent, such as in Figures 11 and 12, bodies having modified cross sections are illustrated. In each of the configurations shown in Patent No. 3,116,639, the leading or upstream facing surface is contoured to provide for laminar flow. By way of contrast, in the present device, the upstream facing surface is provided with small projections which tend to cause the formation of the vortices along the lateral edges of the flow obstruction bars across a wide range of Reynolds numbers and with high response character¬ istics.Additional T shaped flow obstruction bodies, and also bodies which include triangular cross section and other somewhat irregular sections, other than rectilinear or cylindrical are shown in United States Patent No. 3,572,117. Again the particular shapes and operation are different from that shown in the present application. Additional patents which show various flowmeter configurations are cited in my copending application iden¬ tified above. SUMMARY OF THE INVENTION The present invention relates to a vortex shedding flowmeter which has flow obstruction bars con¬ figured with selected cross section features to enhance formation of vortices across a wide range of Reynolds numbers of the flowing fluid. The flowmeter as disclose comprises a flat plate-type device which includes an out rim or ring that holds the bars in place. Preferably th flow obstruction bars are arranged with a plurality of bars side by side spaced across the diameter of a flow pipe or conduit.The cross sectional configurations of the flow obstruction bars or bodies have small protrusions or irregularities (called trips herein) on face portions of the bar facing in the direction of the flow. The pro trusions tend to cause the flow impinging upon a bar to flow laterally, and then abruptly change direction as th diverted fluid turns to flow past the bar. The protru¬ sions, aid in the formation of the vortices along the lateral sides of the flow obstruction bars, (lateral sid means the sides of the bars which generally face lateral or transversely relative to the direction of flow throug the conduit) . Various forms of the invention disclosed all include a type of protrusion which after the flow ha changed direction as it strikes the bar and separates in lateral direction cause an abrupt change of direction of more than 90 as the flow returns to the normal directio of flow through the conduit.Various forms of the invention are disclosed, example a concave recess in the forward facing surface o a generally rectilinear cross section bar causes the flo to change direction in a manner to enhance vortex forma¬ tion.The small.protrusions may extend from the sur- faces of rectangular cylindrical bars.* In such a case, the protrusions will be generally radially extending fin or plates and would extend radially at an angle of about 30° to 45° to the right and to the left of a bisecting plane parallel to the flow axis. This positioning causes the flow impinging on the cylindrical bar to change direction at the fin or protrusion as the flow turns past the bar setting up a tendency to swirl and thus enhance the formation of vortices.While the cross sectional configurations of the bars shown can be used in flowmeters using single bars or multiple bars, the preferred form, as stated previously, is in a multiple bar flowmeter.The sensor that is used to detect vibration of the bars caused by formation of vortices can be any de¬ sired type of sensor such as a semi-conductor strain gauge sensor. The sensor is mounted in the manner to minimize pipe or conduit vibration problems, and also to permit the sensor to be easily inserted and removed from the flowmeter without removing the flowmeter from the conduit with confidence that the sensor itself will not be improperly mounted and will be relatively uninfluenced by vibrations on the supporting pipe or conduit itself. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a vertical sectional view through a typical flow conduit having a flow sensor made according to the present invention installed therein;Figure 2 is a sectional view taken on line 2—2 with parts in section and parts broken away;Figure 3 is a sectional view taken as on line 3—3 in Figure 1; Figure 4 is an enlarged sectional view showing the sensor mounting in a center flow obstruction body modified from the sensor of Figure 1;Figure 5 is a further enlarged fragmentary cζoss sectional view of the sensor and its mounting; Figure 6 is a sectional view taken as on the same line as Figure 3 through a single flow obstructionOMPI/,, WWIIPPOO bar showing a bidirectional flow sensing vortex formin bar made according to the present invention;Figures 7 and 8 are sectional views taken substantially on the same line and in the same position as Figure 6 showing modified forms of the flow obstructi bars made according, to the present invention.DESCRIPTION OF THE PREFERRED EMBODIMENTSFigure 1 shows a fluid carrying conduit or pip 10 which is carrying fluid generally in the direction indicated by arrow 11 and which has a pair of flange typ couplers 12, one on each of two conduit sections, which are spaced apart to receive and sandwich a vortex flow¬ meter plate assembly illustrated generally at 13. The flanges are held together with suitable coupling bolts 1 and they clamp and seal onto the vortex shedding flowmet plate 13.The flowmeter plate 13 in this form of the inv tion is made from a circular plate with orifices or flow apertures cut in the plate to define the cross bars. As can perhaps best be seen in Figure 2, there is a perimet or annular rim 15, and a center flow obstructing bar 16, a flow obstructing bar 17 adjacent a first side thereof, and a flow obstructing bar 18 adjacent a second side thereof. These bars or bodies 16, 17 and 18 are separat by suitable orifices or apertures (or slots) 21 and 22 o opposite sides of the center body 16 which are of equal size and shape, and orifices or apertures (or slots) 23 and 24 to the outside of the bars 17 and 18, which orifi 23 and 24 are also of equal shape and size. The outer edges of each of the orifices or apertures indicated at 21A, 22A, 23A, and 24A are part circular and these edges define the effective flow diameter D of the flowmeter assembly.The flowmeter plate 13 is relatively thin in direction of the fluid stream 11, and the flow obstructi bodies or bars 16, 17 and 18 are formed generally recti- linear but with edge irregularities formed by recesses as shown and explained in connection with Figures 2 and 3. The bars 16, 17 and 18 are made to cause flow separa¬ tion, causing vortices to be formed and shed from the bars along their side surfaces (the surfaces parallel to the flow direction) .A suitable motion sensor 26 is placed into a receptacle 25 and can be held in the receptacle in a suitable manner as will be explained. The sensor 26 is utilized for sensing vibrations of the center bar 16 caused by the formation and shedding of vortices as the fluid in the conduit flows past the bars.When a plurality of spaced obstruction bodies are placed across the conduit and are commonly mounted to a rim as shown, the rim or plate can be slipped into position in place of a common orifice plate without modifying existing mounting members.The center bar 16 is centered on a diametral line of the flow conduit, and the bars 17 and 18 are each spaced an equal distance laterally from the center bar and also an equal distance from the adjacent sides of the conduit.It has been found that when a plurality of the obstruction bars or bodies such as 16, 17 and 18 which are transversely aligned across the conduit are utilized, the formation of vortices will tend to shift across the diameter of the conduit, so that primary or strong vor¬ tices are formed alternately along the sides of the bars. Note that no upstream or downstream bars or obstructions are used, but only the bars centered on a common plane perpendicular to the flow direction.Briefly, the vortices are shown by the curled lines in Figure 3. The vortices will switch back and forth so that vortices are formed between bars 16 and 18, and then between bars 16 and 17 alternately. Such vor¬ tices are shown in a downstream direction from the flow- REOMPI meter of the present invention in Figure 3.Strong vortices are formed along the sides alternately from the switching as disclosed in the previ application mentioned above. This of course causes vibration in the bars as also explained therein.The plate 13 does have a tang portion indicate generally at 15A extending outwardly beyond the peripher rims 15 of the orifice plate. The tang portion 15A is used for mounting the motion sensor assembly 26, which is mounted into receptacle 25 in the center bar or flow obstruction body 16. The receptacle or opening extends downwardly substantially to the midpoint of the bar, or approximately half-way across the conduit.Adjacent the rim portion 15, the opening 25 has a larger bore portion 35 near its outer end. A split chuck member or holder 34 (in two or more sections) having an interior (inwardly facing) frusto conical sur- ' face is positioned against a shoulder formed at the inner end of bore 35 in the rim 15 of the plate. The sensor 26 has a probe portion 37 extending through a collet member 36, which has an exterior (outwardly facin frusto conical surface that mates with and forms an interference or contact fit with the interior surface of chuck 34. The probe portion 37 is preferably made of a ceramic material. The collet 36 may be shrink fitted onto the probe portion 37 or may be slitted so that it will clamp onto the probe as the collet 36 and chuck 34 are forced together in a chucking action.The probe portion 37 of the sensor 26 extends into the opening 25 and as shown a flexible, cantilevere sensing beam 37A is fixed to and projects from the end of the probe 37. The sensing beam carries a small non- conductive ball 37B which bears againstthe interior sur¬ face of opening 25 with a slight resilient force. The beam carries a strain gage 37C (a semiconductor strain gage is preferred) to sense deflection of the beam. The center bar 16 vibrates laterally as the vortexes are shed, in a known manner. The beam 37B will flex, because probe 37 remains stationary, and the strain gage 37C delivers an output signal that indicates flow rate as a function of frequency of flexing. Suitable circuitry may be used for providing a useful output signal as a function of the signal from the strain gage.The sensor 26 has an external fastening flange 38 at the upper end thereof. In the form shown, the flange 38 is attached to the collet 36 which carries the probe portion 37, and flange 38 and collet 36 are urged downwardly through the use of screws 39 threaded into the tang portion 15A of the flowmeter. The screws 39 are tightened to a desired level to exert a force on the collet 36 urging it tightly in position against the sur¬ face of chuck 34 and thus tightening collet 36 onto probe portion 37. Because the chuck 34 and collet 36 can be quite accurately machined in respect to the length of the probe portion 37 of the sensor and of the opening 25, the mating surfaces of chuck 34 and collet 36 serve to position the beam 37A at the end of the probe portion 37 within the opening 25 so that the end of the beam 37A does not engage the- end of the opening 25.The physical support between the flowmeter and the sensor assembly 26 is at the chuck member 34 and collet member 36. The sensor is clamped at the rim 15 rather than held at the vibrating bar or body itself. The use of the tightly engaged tapered surfaces cause the split collet to be forced against the interior surfaces of the bore 35 to properly position the probe portion 37 and beam 37A to sense vibrations of the flow obstruction body, and at the same time isolate the sensor assembly 26 and beam 37A from external shocks or vibrations in the conduit or pipe 10. The rim 15 is clamped tightly to the conduit flanges, and the members 34 and 36 align with the rim at its mounting area. The support for the sensor at members 34 and 36 is rigid and thus the sensing beam 37A will not be flexed substantially by vibration of the flow conduit. The flowmeter is thus relatively insensitive to external shock and vibration but senses the vibrations of the bars caused by the vortices.As a further feature, the threaded members 39 can be removed and the entire sensor assembly 26 can be pulled out easily through the external opening in the tang 15A. When replacing the sensor assembly the surfaces of members 34 and 36 will again mate and position the probe portion 37 of the sensor 26 properly in the aperture or opening 25 of the.center flow obstruction body 16 to sense the vibrations that are set up in the body or bar.The leads from the strain gage 37C may extend through openings in the probe portion 37 and flange 38.A modified form of the sensor is shown in Figure 4. In order to enhance the vibration of the center bar or flow obstruction body particularly at low flows, the bar 42, which corresponds to the bar or body 16 in Figures 1 through 3, has a slit formed by a narrow transverse cut indicated generally at 43 which separates the bar 42 into two sections 42A and 42B. The sections 42A and 42B are each fixed to the support rim 15 as in the previous form of the invention, and cantilever from the rim. The slit 43 is of sufficiently small size so that only a very small proportion of the fluid flows through this slit. Thus, there is no flow between the facing ends of the two bar portions 42A and 42B. However, the vibrations of the bar portions is enhanced and thus the sensor 26 will provide a greater signal and more easily sensed output, particularly at low flows, with the slit in the flow obstruction body. In actual use, the slit has been made very narrow in the range of 10 mils or so, in order to permit enhanced vibration of the flow obstruction body portions without permitting flow through the slit itself.Referring to Figures 2 and 3, in particular, each of the bars or bodies 16, 17 and 18 has a cross section which includes a longitudinally extending recess indicated at 16A, 17A and 18A, respectively, on the side surface thereof facing the flow formed by pairs of small protrusions or protuberances 16B, 17B and 18B which are also called trips or trip members herein. The main portions of the flow obstruction bodies form gener¬ ally evenly contoured and symmetrical bodies. The pro¬ trusions are at each of the forward side edges of each of the bars. The lateral side surfaces which face other bars are planar. The formed protrusions tend to cause the fluid that is flowing axially in the conduit or pipe as shown by arrow 11 to spread or move laterally to this flow direction as the fluid impinges the flow facing sur¬ face of the respective bars, and in so doing the protru¬ sions or trips 16B, 17B and 18B tend to cause a swirling as the separated fluid flows over these protrusions and turns to flow along the transversely facing surface por¬ tion of the bars. The flow past the transversely facing surfaces is parallel to direction of arrow 11. The pro¬ trusions tend to set up a swirling action by causing a partial reversal of the direction of the fluid as the fluid moves past the protrusions and flow obstruction body, and enhance the formation of vortices along the facing lateral surfaces of the bars as shown in Figure 3.The bars 16, 17 and 18 are supported at the top and bottom on rim or ring 15, and will tend to vibrate transversely to the flow direction at a frequency depend¬ ing upon rate of flow as indicated by formation of vor¬ tices. Ignoring the trip members 16B, 17 and 18B the flow obstruction bodies have main portions which have symmetri- cal rectangular cross sections about a bisecting plane parallel to the flow direction. The trips or protrusionsOMP -lo¬ adjacent the forward edges of the side surfaces of the bars (at the corners) are of size and shape sufficient to cause shedding of stronger vortices than a body of th size and shape of the main portion without the trip mem- bers. Also stronger vortices are formed with the trip than with a body of a size equal to the size defined by a body including the trips.In the preferred embodiment shown in Figure 3, assuming that the internal diameter of the flow opening is equal to D , the spacing between the facing surfaces of bars 16 and 18 as shown at 29 is preferably .20D. The trip depth shown in direction transverse to the flow direction as indicated at 30 is .007D. The height of th protrusions in direction parallel to the flow direction be sensed is in the range of .O15D. This dimension is indicated at 31. The width of the bars or bodies in direction transverse to the flow direction is preferably in the range of .085D. This dimension is indicated at 2 As shown dimension 30 is about .085 of the lateral width dimension 28. Related to the lateral width of the bar, the width and height of the protrusions (dimensions 30 a 31) preferably are not substantially greater than .1 tim the transverse width 28 of the bars.The small protrusions are kept narrow and not very high (in direction of flow) to regularly aid in the release or tripping of vortices along the side surface of the flow obstruction bodies. The protrusions project the desired amount from the adjacent surface portions of the flow obstruction bodies. In Figure 6, a typical bidirectional flow sensitive, flow obstruction bar or body is illustrated. In this particular instance, the flow obstruction bodies 50 are mounted on a rim or ring 49 as previously explain and each includes a first pair of surface irregularities or portions 51,51 at the lateral sides of the flow obstr tion body adjacent one face surface. These small protru- υ sions or trips 51,51 are identical to those shown on the bars of Figure 3. Each of the flow obstruction bodies 50 has protrusions 52,52 at the edges of the oppositely facing surfaces. Thus, each body 50 is substantially symmetrical with respect to the plane of the mounting ring 49 and operates identically regardless of the direction of flow relative to the sensor. The protrusions or irregularities 51 and 52 cause enhanced generation of vortices along the side surfaces of the bodies as previously described. In Figure 9, a modified form of the invention is illustrated. In this particular form a flow obstruction bar or body 75 may be mounted in a rim or ring 75A alone or with additional bodies positioned as shown in Figures 2 and 3. The body 75 has a part cylindrical surface recess 76 which forms trips or protrusion edge portions 77,77 adjacent the lateral side edges of the body. The surface 76 is part circular cross section and extends along the longitudinal length of the flow obstruction body 75 a desired amount. Flow in this instance is in direction indicated by the arrow 78. The body 75 may also have a similar recess to that shown at 76 on the oppositely facing surface to provide bidirectional flow capabilities as well. The outer end portion 77 of the flow facing surface provides the protrusions forming trips to enhance vortex formation along the bars.Figure 7 is a modified cross section shape of a flow obstruction bar or body. In Figure 7, a flow ob¬ struction bar or body 60 is mounted in a ring or support 60A at its opposite ends as shown in Figures 2 and 3, and has small, narrow protrusions 61,61 extending laterally out beyond the lateral side surfaces 62,62 of the bar or body and at the flow facing end or surface of the bar. These protrusions 67 are quite narrow and short, and as flow moves in the direction as indicated by 63 it tends to separate, and flow sideways or laterally and then around the trips or protrusions 61,61. Thus the curling or swirling motion at the upstream corners of the latera sides of the flow obstruction body enhances vortex gener tion. The trip members or protrusions are relatively narrow and short in relation to the transverse or upstre and downstream dimensions of the body, as shown. The siz of the protrusions 61 is similar to protrusions 16B, 17B and 18B.Flowing fluid moves laterally along the upstrea backing surface of the bar 60 as it strikes the bar and thus curls back as it goes around the trips or protrusion 61, setting up a pattern that enhances vortex generation.The bar 60 also may be made bidirectional by adding another pair of trips or protrusions at the other corners of the bar 60 to make the bar symmetrical relativ to the plane of the mounting ring 60A, which plane bisect the bar 60 and is perpendicular to the flow direction. In all forms of the invention, the trips or protrusions effectively cause change of direction of flow, which first tends to go toward the lateral sides of the bar or generally perpendicular to the normal direction of flow and then changes direction quickly at the side edges of the flow obstruction body to enhance vortex formation. A flow direction change over 90 is caused by each of the trips as the flow turns down- stream past the bodies or bars. This tends to start early generation of a vortex. r.he trips formed on the flow obstruction bodies extend substantially the entire length of the body itself from adjacent the ends where it is supported with respect to the annular ring or orifice plate. The length of the protuberances or trips described can be varied to suit existing conditions.The mounting members for the sensor assembly are annularly aligned with the flowmeter support rim and thus the clamping of the support rim between the flanges on the conduit sections clamps the region where the senso is supported to provide vibration isolation.The mounting reduces acceleration sensitivity, and the signal from the sensor accurately represents flow conditions.OMPI | WHAT IS CLAIMED IS:1. A vortex flowmeter apparatus comprising a support member, a flow obstruction body mounted on said support member and having a first surface portion which faces toward a normal direction of flow to be measured, said flow obstruction body having second surface portion facing laterally to the direction of flow, means on said flow obstruction body defining at least one trip member projecting from the flow facing first surface in a direction at least partially opposite from the normal fl flow direction, and said trip member being positioned ad cent one of said second laterally facing surface portion said trip member causing fluid which impinges upon said first surface portion of said flow obstruction body to separate as it impinges on the flow facing surface to start and enhance a swirling tendency in the fluid flow as the fluid flows past the one lateral facing surface portion of the flow obstruction body, and sensing means to sense vibrations of said flow obstruction body caused by formation of vortices around said trip member of said body.2. The combination of Claim 1 wherein said fl obstruction body has a generally symmetrical cross secti about a central plane parallel to the direction of norma fluid flow and extending along the longitudinal axis of the flow obstruction body, to thus form a pair of trip members, said trip members each having, a cross sectional width and height projecting from adjacent surfaces of said flow obstruction body not substantially greater tha 0.10 times the maximum dimension of said flow obstructio body in direction perpendicular to said plane.3. A flowmeter assembly comprising a support, a flow obstruction body mounted on said support, said flow obstruction body being adapted to be installed into a 'flow conduit having fluid flowing therethrough, said flow obstruction body having a longitudinal axis and pro jecting into the normal path of fluid flow, said flow obstruction body having a main portion with a generally symmetrical cross section about a plane parallel to the direction of flow through the conduit and lying on the longitudinal axis of said flow obstruction body, said cross section of said flow obstruction body including a first side portion facing in direction toward intended flow and lateral side portions have surfaces generally parallel to the flow direction, a pair of longitudinally extending protuberances forming surface irregularities on opposite side of said plane, said protuberances being posi¬ tioned adjacent the flow facing side portion of the flow obstruction body and having a height and width projecting from adjacent portions of the cross section of the main portion of said flow obstruction body of sufficient magnitude to effectively initiate release of stronger vortices from said flow obstruction body than the vortices released from a flow obstruction body of substantially the same size and shape as the main portion of said flow obstruction body without protuberances. *4. The flowmeter of Claim 3 wherein the pro¬ tuberances are of a size which causes any fluid flow following the surface of the flow obstruction body as it flows past the body to change direction of more than ninety degrees as such fluid flows along the flow obstruc¬ tion body surfaces and around said flow obstruction body.5. The combination as specified in Claim 3 where¬ in the fluid flowing past said flow obstruction body moves generally laterally to the normal direction of flow as it first impinges on said flow obstruction body, said longitudinally extending protuberance causing the flow to at least partially reverse direction from its flow direction immediately prior to flowing past the lateral side surface portions of said flow obstruction body to resume flowing in the normal direction of flow through said conduit. 6. The combination as specified in Claim 3 wherein said protuberances have a dimension protruding from the main portion of said flow obstruction body not greater than 0.10 times the effective maximum lateral dimension of said flow obstruction body.7. The combination as specified in Claim 3 wherein said cross section of the main portion of said flow obstruction body is generally rectilinear, and said protuberances are formed by a concave part cylindrical surface defined on the flow facing surface of said flow obstruction body to form relative sharp edge protuberance projecting toward the direction of flow from the main portions of said flow obstruction body adjacent the later side edges thereof. 8. The combination as specified in Claim 3 wherein said flow obstruction body is ■generally recti¬ linear in cross section, and protuberances comprise raised ribs adjacent the lateral side edges of said flow obstruction body and projecting from the flow facing surface thereof and extending in direction opposite from normal flow direction.9. The combination as specified in Claim 3 wherein the main portion of said flow obstruction body is of a generally rectilinear cross section, and said protuberances comprise projections extending outwardly from the opposite lateral side edges of said flow ob¬ struction body and being positioned with respect to the flow facing side portion of said flow obstruction body so that said flow facing side portion comprises a generally planar surface extending generally perpendicular to the normal direction of flow, and said flow facing side portion defining portions of said protuberances.10. The combination as specified in Claim 3 wherein said flow obstruction body is symmetrical with respect to a second bisecting plane passing longitudinall through said flow obstruction body and positioned generalW perpendicular to the normal flow direction through said conduit, said flow obstruction body thereby having pro¬ tuberances adjacent both the flow facing and downstream portions of said body. 11. The flowmeter of Claim 3 wherein said support comprises a peripheral member, said flow ob¬ struction body being supported at both of its opposite ends on said peripheral member.12. The flowmeter of Claim 11 wherein said flow obstruction body is formed into two sections, said sections being on a common longitudinal axis and supported • at ends adjacent the periphery of the flow conduit, the flow obstruction body sections having facing end surfaces separated by a space sufficiently small to prevent substantial flow between said end surfaces.13. For use in a flow conduit having mating annular flanges for clamping conduit sections together end to end, a vortex flowmeter assembly having a peripheral annular rim clamped between the flanges of a conduit when in working position and at least one flow obstruction bar fixedly mounted to the rim and thereby being supported in the fluid flow conduit with said one flow obstruction bar projecting into a fluid stream, said rim and bar forming plate-like assembly having an outer peripheral edge surface which is accessible from the exterior of a conduit when positioned between adjacent flanges of two lengths of such conduit, said flow obstruction bar forming a body around which vortices are formed as a function of flow past said flow obstruction bar, sensor means for sensing vibrations of said flow obstruction bar caused by said formation of vortices including an elongated probe portion, said bar having an elongated bore extending from the edge surface of said peripheral rim in direction longitudinally of said bar, said probe portion being mounted in said bore, second means forming a first generally frusto conical interior surface portion on the interior of said bore in align ent with said rim so that said first generally frusto conical surface is aligned generally between flanges of adjacent conduit sections when the rim is clamped therebetween, the large end of said first frusto conical surface portion being most closely adjacent the outer edge of said rim, third means on said probe portio forming a generally outwardly facing exterior generally frusto conical chuck member mating with said first frust conical interior surface portion when said elongated pro portion is placed in said bore, and fourth means on the exterior of said rim to hold the mating first and second frusto conical surfaces in contact comprising a threadab adjustable member to permit adjusting the force with whi said mating frusto conical surfaces are engaged, major portions of said probe portion being spaced from the sur faces of said bore except in desired locations.14. A flowmeter assembly comprising a support including an annular rim member, said rim member definin a central interior opening through which flow may pass, a flow obstruction body assembly mounted on said rim member and having a longitudinal axis extending trans¬ versely across said rim member in position so that fluid flowing through the flow opening of said rim member surrounds said flow obstruction body, said flow ob- struction body having a desired cross sectional shape and being mounted to said rim member only at opposite en portions of said flow obstruction body, said flow obstru tion body comprising two independent, cantilevered sec¬ tions formed by a narrow slit in said flow obstruction body, said slit beng sufficiently narrow to prevent sub¬ stantial flow of fluid through said slit.15. The combination as specified in Claim 14 wherein said slit is on the order of 10 mils in width as measured along the longitudinal axis of said flow obstruction body.16. The combination as specified in Claim 14O wherein said flow obstruction body has a cross section shape including a pair of protrusions on the flow facing surface thereof which are small in relation to the cross sectional size of the flow obstruction body and which tend to set up a swirling action of fluid flowing past said flow obstruction body.17. The flowmeter of Claim 14 wherein the longitudinal axis of said flow obstruction body extends along a generally diametral line of said rim. 18. The flowmeter of Claim 17 wherein one of said flow obstruction body sections has an opening defined therein extending along the longitudinal axis, and means mounted in said opening to sense vibra¬ tory movements of said one section.OMPI | ROSEMOUNT INC | FRICK R |
WO-1979000791-A1 | 1,979,000,791 | WO | A1 | EN | 19,791,018 | 1,979 | 20,090,507 | new | C02B3 | null | B01J3, B01J19, C02F1, C02F11 | B01J 3/04B, C02F 11/08, C02F 11/08B | METHOD AND APPARATUS FOR EFFECTING SUBSURFACE,CONTROLLED,ACCELERATED CHEMICAL REACTIONS | The problem of conducting chemical reactions at elevated temperatures and pressures, such as in the wet oxidation of a waste stream, without excessive expenditures of energy is solved by the method and apparatus for effecting accelerated chemical reactions utilizing a reactor (15) extending into a vertical hole (16) in the earth and having an outer flow passage (21) receiving influent fluid from a supply (38) and supply lines (31 and 33) pumped with air by a pressure pump (29). The fluid undergoes an accelerated oxidation in the hole giving off the products of reaction, heat, and an effluent fluid which flows up an inner flow passage (22) to a settling tank (41) and/or other discharge lines (44, 42). Apparatus for control of temperature, pressure and flow rate are also provided to maximize reaction rates and minimize power requirements. | -1-METHOD AND APPARATUS FOR EFFECTING SUBSURFACE, CONTROLLED, ACCELERATED CHEMICAL REACTIONSTechnical Field;This invention generally relates to improvements in effecting chemical reactions and more particularly to a novel and improved method and apparatus for effecting accelerated chemical reactions that is especially effec¬ tive in efficiently carrying out the wet oxidation of sew¬ age sludge and like waste streams, purifying the water content, and also recovering energy in the form of heat. Background Art: There are a variety of chemical reactions that may be accelerated under conditions of a temperature sub¬ stantially above ground surface ambient temperature and a pressure, substantially above atmospheric pressure. A major part of the reactor apparatus heretofore provided for carrying out the various chemical reactions at higher temperatures and pressures typically require high pres¬ sure liquid pumps, high pressure, high temperature heat exchangers and pressure vessels with rotating seals and considerable land surface area. One chemical reaction for which the method and apparatus of the present invention is particularly suit¬ able is for the direct wet oxidation of materials in a waste stream and particularly the direct wet oxidation of sewage sludge. The Zimpro method, Barber-Coleman process and Navy shipboard processors are examples of current methods used to effect direct wet oxidation of sewage sludge and all involve placing the waste in a high temperature, hig pressure reactor at substantially ground surface level.Air is pumped into the reactor vessel and heat is externa applied. Constant mechanical stirring is required to mix oxygen, a reactant, into the liquid and to remove carbon dioxide, a product of the reaction. Some attempt has been made to carry out accelerated chemical reactions below the ground surface level using the increased pressures provided by a hydrostatic column of liquid or fluid. In this connection, particular atten tion is directed to U. S. Patent Nos. 3,449,247 to Bauer, 3,606,999 to Lawless and 3,853,759 to Tit us.DISCLOSURE OF INVENTION A method and apparatus for effecting accelerated chemical reactions utilizes a reactor having a downgoing through-pipe that extends down below the ground surface a substantial distance and back up providing a hydraulic U-tube for a reaction that takes place a substantial distance below the ground surface level. An influent fluid is pumped down the downgoing pipe portion from the ground surface level at a controlled, selected temper ature, pressure and flow rate to a selected depth below the ground surface to form a hydrostatic column sufficien to provide a selected pressure and temperature that causes the reactants to react at an accelerated reaction rate and further down the downgoing pipe portion through reaction zone for a selected retention time whereby heat is released, reaction products are produced, and the flui is heated in the reaction zone. The heated fluid and reaction products are flowed back up the upgoing pipe por tion in heat exchange relation to the downgoing fluid to effect a substantial cooling before exiting the outlet of the upgoing pipe portion. The temperature of the influent fluid in the reaction zone is controlled by adding or removing heat to maximize the reaction rate and to prevent boiling of the fluid in the reaction zone. Once the operation is under way, heat from the exothermic reaction is removed as useful heat energy.If a gas is used in the reaction, the results are enhanced by introducing a stream of gas under low pres- sure in the form of a series of enlarged bubbles, known as Taylor bubbles , formed at the top of the reactor. Preferably the gas is introduced in a plurality of streams at more than one elevation to reduce pumping requirements. These enlarged bubbles cause the least amount of pressure differential in the flow passage and thus minimize pumping pressure to maintain a certain flow rate. These enlarged bubbles also provide intense mixing and contacting to increase the flow of reactants and pro¬ ducts to and from the fluid since the fluid flows over the bubble and there is no boundary layer formed as is found in bubbles of smaller size. The quantity, of gas injected is controlled to provide the proper ratios relative to the influent fluid since insufficient gas pro¬ duces undesirable products and excess gas is wasted and reduces the reactor throughput rate. Fluid flow velocities are maintained at a greater velocity than the bubble rise velocity in order to carry each bubble down to the reaction zone. Pressure and flow rate at the out¬ put of the reactor are controlled to maintain the proper flow rates and pressure in the system.Other objects, advantages and capabilities of the present invention will become more apparent as the descrip¬ tion proceeds, taken in conjunction with the accompanying drawings in which like parts have similar reference numerals and in which:DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic diagram of apparatus embody¬ ing features of the present invention which utilizes a gas as one reactant; Figure 2 is an enlarged schematic diagram of the apparatus of Figure 1 showing in more detail the manner of introducing a gas under pressure into the fluid stream to produce enlarged bubbles which flow down the outer flow passage and up the inner flow passage;-^URE Figure 3 is an enlarged schematic diagram showing the passages and bubbles with the flow in the opposite direction from that of Figure 2;Figure 4 is a schematic diagram of the reactor with designations at various depth locations for reference to the structure shown in more detail in Figures 5-19;Figure 5 is a vertical cross-sectional view of an upper portion of the reactor;Figure 6 is a cross-sectional view taken along lines 6-6 of Figure 5;Figure 7 is a vertical cross-sectional view of an intermediate portion of the reactor;Figure 8 is a vertical cross-sectional view of a lower portion of the reactor; Figure 9 is a vertical sectional view taken along lines 9-9 of Figure 7;Figure 10 is a sectional view taken along lines 10- 10 of Figure 9;Figure 11 is a sectional view taken along lines 11- 11 of Figure 7;Figure 12 is a sectional view taken along lines 12-1 of Figure 7;Figure 13 is a sectional view taken along lines 13- 13 of Figure 8; Figure 14 is a sectional view taken along lines 14-14 of Figure 8;Figure 15 is a sectional view taken along lines 15- 15 of Figure 8;Figure 16 is an enlarged vertical cross-sectional view of Figure 13 showing in more detail the flow of fluid between the jacket and flow line;Figure 17 is a sectional view taken along lines 17-17 of Figure 8;Figure 18 is a sectional view taken along lines 18-18 of Figure 17;Figure 19 is a perspective view of the bottom of the jacket of the reactor;Figure 20 is an enlarged side elevational view of a Taylor bubble; gure s a o om v ew o e n Figure 20; andFigure 22 is a diagrammatic view showing three reactors connected in series and placed in one outer casing.DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring now to Figure 1, the schematic diagram shows a reactor 15 constructed and arranged in accordance with the present invention that extends into a vertical hole 16 in the earth to a substantial extent below the ground surface level designated 17. The reactor 15 shown in general has an outer pipe portion 18 and an inner pipe portion 19 in spaced concentric relation with the outer pipe portion 18 defining an outer flow passage 21 between the outer and inner pipe portions and an inner flow passage 22 through the inner pipe portion 19. The outer pipe portion 18 has a closure cap 24 covering the lower end thereof and the inner pipe portion 19 terminates a selected distance above the closure cap 24 to form a subsurface, hydraulic U-tube structure within hole 16.The reactor 15 shown further has an upper portion projecting above the grovjnd surface level 17 provided with a port 26 in flow communication with the outer flow passage 21 through which an influent fluid is shown as flowing, as indicated by arrows,and a port 27 in flow communication with the inner flow passage 22 through which the effluent fluid is shown as flowing, as indicated by arrows. While the direction of the arrows shows the flow of the influent fluid down the outer flow passage 21 and up the inner flow passage 22, this provides a greater input flow capacity for influent fluids, which usually have a greater viscosity than effluent fluids, but it is understood that the direction of fluid flow can be reversed as illustrated in Figure 3.A low-pressure pump 29 at the ground surface level is provided to pump the influent fluid supplied from a suitable supply indicated at 38 via a supply flow line 31 with a pressure control valve 32 at a selected pressure through port 26 via a flow line 33 coupledO PI age 21, as indicated by arrows. A bypass control valve 34 in a bypass line 35 bypasses the pump 29 for flow directly from flow line 31 to flow line 33 since, after the fluid is flowing through the U-tube structure, in man instances no pumping pressure will be required to sustain a continuous flow therethrough. A back pressure control valve 36 in an outlet flow line 37 from outlet 27 control the flow rate and pressure' of the effluent fluid flowing up through flow passage 22 by virtue of the size of the orifice therethrough. A supply of influent fluid is indicated at 38, and the flow therefrom into flow line 31 is controlled by control valve 32. The pump 29 controls the pressure and flow rate through flow line 33 during start-up and valves 34 and 36 control the pressure and flow rate during operation.The apparatus shown in Figure 1 is suitable for carrying out the direct wet oxidation of a waste stream and particularly aerobic sewage treatment plant sludge waste, although it is understood that the present inventi is capable of carrying out a variety of high-temperature, high-pressure chemical reactions.In the illustrated flow diagram where a sewage slud stream is being processed, the effluent fluid passing through flow line 37 is passed into an ash settling tank41 with clean water being recycled back as a clean or purified diluent to the feed flow line 31 via a flow line42 with a control valve 43 to control the concentration of the influent fluid so that the settings of valves 39 and 43 achieve a blend of influent fluid having a selected C.O.D. The mass of oxygen required to complete the oxidation reaction is termed the chemical oxygen demand (C.O.D) of the sewage sludge. The settling tank 41 has a purified water discharge flow line 44 and an ash flow line 45.Temperature control apparatus is provided for controlling the temperature of the influent fluid in the reaction zone designated R. This temperature control apparatus includes a coolant pump 51 at the ground surfac eve a pumps a coo an u s ore n a groun level coolant tank 52 through a heater 53 at the ground surface level down to the bottom of a heat exchange jacket 55,through a valve-controlled flow line 54, and back up the hole through a valve-controlled flow line 56.The heater 53 may take a variety of forms but, as illustrated schematically, is an electric heater supplied electric power from a power source 53a with a control rheostat 53b for regulating the voltage applied -to a heating element 53c to change the heater temperature setting and thereby the temperature of the coolant fluid flowing in flow line 54. The jacket 55 is of a hollow, annular, tubular construction that is substantially coextensive with the reaction zone R and further is in heat exchange relation with the outer flow passage 21, as is described more fully hereinafter.The other flow line 56 is coupled to and extends from the top of the jacket at the top of the reactor zone up to the ground surface level and is coupled to tank 52 by a return valve-controlled flow line 56a to add heat to a fluid in lines 54 and 56. A heat removal circuit includes a valve-controlled flow line 56b coupled to line 56 down to the top of the jacket 55 and a valve-controlled flow line 54b above the ground surface coupled to a heat exchanger 58 which in turn is coupled to tank 52 to pro¬ vide a closed-loop, fluid flow' temperature control circuit. The flow control valve in flow line 54b controls the rate of flow in this fluid flow circuit.By means of regulating the temperature of the coolant fluid in the jacket 55 and flow lines 54 and 56, the tem¬ perature of the influent fluid in the reaction zone R is controlled. This is accomplished by adding or removing, heat to and from the coolant fluid and is controlled to accomplish substantially a maximum reaction rate with the vapor pressure of the influent fluid at the local tempera¬ ture being maintained always lower than the local pressure to prevent boiling of the influent fluid. The temperature of the influent fluid is increased by adding heat pro¬ vided by the heater 53 that heats the coolant fluid passingOMP throug ow l ne 4 an own nto ac et y t e pres sure supplied by pump 51, with the flow rate of the coo ant fluid controlled by the setting of the control valve in line 54. The upper limit of the temperature of the influent fluid in the reaction zone is controlled by regulating t heat removed from the heat exchanger 58 and the flow rat which is controlled by the setting of the valve in line 54b. The amount of heat removed is directly related to the setting of the valve in line 54b. A turbine 60 is shown coupled to the heat exchanger 58 via a flow line with a control valve 66 as an illustration of the utilization of the energy, and specifically- the heat produced by the reaction,to convert heat energy to mecha iσal energy. Alternatively, a load 67 is shown coupled to the heat exchanger via a flow line with a control valve which couldbe a room heated by the heat produced by the reactor.A pressure sensor for measuring the pressure at the upper limit or beginning of the reaction zone R. includes a small-diameter tube 61, such as a 1/8 inch stainless steel tube, that extends down through the inner pipe portion 19 to the upper limit of the reaction zone R. At the ground surface level a pressurized bottle 62 provides a selected air pressure to flow air down through the tube 61 via a delivery valve 63. Between the bottle 62 and tube 61 there is coupled a delivery air pressure gauge 64 and a pressure regulator 65. To make a pressure read¬ ing, water is flushed out of the tube 61 and the delivery valve 63 is closed. The reading on the pressure gauge 66 is the pressure inside the reactor at the upper limit or top of the reaction zone which is a critical part of the temperature and pressure for the reactor.In chemical reactions where a gas is used as a reactant,and specifically in carrying out the wet oxida¬ tion of sewage sludge where the oxygen content of air is required, it has been found that the operation and results are significantly enhanced by the use of enlarged gas bubbles 78. With specific reference to Figures 20 n , e es c a ac ze y a e a has a generally spherical cap portion 78a, a generally cylindrical main body portion 78b, and a truncated bottom portion 78c. The transverse cross section is circular. In the enlarged view, it is shown that the body portion diverges from the top portion to the base portion along a curve. This bubble is frequently referred to as the Taylor bubble after G. J. Taylor who is credited for accomplishing their original investigation. The Taylor bubbles are compressed as they flow down through the outer flow passage and, upon reaching the reaction zone, the oxygen carried therein is a reactant in a reaction which causes an intense mixing, contacting and a rapid oxidation of the sewage sludge with smaller bubbles returning via the inner passage.The principal advantages of the use of these bubbles as compared to a swarm of very fine bubbles are that the pressure drop per length of pipe for the Taylor bubble is considerably less, thereby reducing the pumping re- quirements to pump the fluid and bubbles down into the earth, and further there is accomplished a greater total mass transfer between the gas and the liquid phase in the reaction zone R. This results in an increased gas- liquid mixing with greater dissolving of the gas in the liquid and a greater.removal of the reaction products from the liquid.The apparatus shown that is utilized for forming these enlarged bubbles is an air compressor 71 at the ground surface which, through one or more flow lines, delivers one or more streams of air at a selected pressure into the upper portion of the outer flow passage to combine with the influent fluid from the input flow line 33. A series or train of enlarged or Taylor bubbles 78 are formed that are carried down with the influent fluid. For this purpose, there is shown a control valve 76 in a flow line 77 that extends into flow line 33 at ground level and a control valve 74 in flow line 75 extending to one depth below the earth's surface, as well as a control valve 72 in line 73 extending yet further into the earth's surface. A terminal pipe section or portion of each of the flow lines 73, 75 and 77 extends in a longitudinal relation to and within the downgoing flow passage with an outlet opening toward the downstream end of the down- going flow passage so that a stream of air is introduced under a selected pressure and flow rate into the influent fluid stream. By the proper selection of pressure, temperature and flow rate in relation to the flow rate and pressure of the influent fluid, bubbles coalesce into a train of Taylor bubbles 78 arranged at spaced intervals along the outer flow passage 21.These enlarged or Taylor bubbles will rise at a uniform rate with respect to water. Their relative veloc with respect to water is given by:where: r = pipe inside radius (ft.)In the apparatus shown the flow velocity of the influent fluid waste stream must be maintained at a great value than the bubble rise velocity in order to carry each of the bubbles down to the reaction zone R. The influent fluid flows over the bubbie and maximizes the mass transfer between the liquid and gas phases in the reaction zone. Since the oxidation reaction is overall first order, the rate of reaction is directly proportiona to the amount of products and reactants in the liquid. The Taylor bubble provides a smaller hydrodynamic pressur loss inside the flow passage as compared to a swarm of smaller bubbles, thereby reducing the amount of energy required to flow the material at a certain rate through the U-tube structure. Smaller size bubbles create a larg hydrodynamic pressure loss throughout the hydraulic colum Also a smaller bubble has a boundary layer of water assoc ted with it which impedes the mass transfer between the two phases. Thus, the Taylor bubble maximizes reaction rates while minimizing horsepower required for pumping th fluid through the pipe system.— /^£\ To minimize the horsepower required by compressor 71, air is introduced at the top of the outer flow passage 21 at more than one elevation, as shown in Figures 1 and 2. Air is introduced at the highest elevation at the lowest pressure in an amount equal to one volume of air per volume of liquid. As the fluid descends, the pres¬ sure increases and the air is compressed. Additional air is injected at a lower elevation and at successively higher pressures, again at an amount equal to one volume of air per volume of liquid. This sequential injection of air at successively greater depths minimizes the com¬ pressor requirements and provides the oxygen necessary to oxidize the reactants in the liquid.The pressure at any point in the reactor depends upon the mass of the fluid above. If only water were used, the pressure gradient would be approximately .43 psi per foot of depth. However, the downgoing flow passage 21 contains a substantial volume of gas which is compressed in volume and heated as it travels downwardly. In summary, by introducing the air at different elevations below the earth's surface, less pumping pres¬ sure is required and,once the process is in operation, the downflowing influent fluid material will draw the liquid in without the necessity of a liquid pump. This Taylor bubble configuration minimizes compressor require¬ ments, creates the least amount of pressure differential and increases the flow of reactants and products to and from the fluid, since the fluid flows over the bubble, and there is no boundary layer formed as found in bubbles of smaller size.The reactor shown in more detail in Figures 5-1 is located inside a well hole, lined with a well casing comprised of an enlarged upper section 81 and a smaller diameter lower section 82 that has grout at 83 outside section 82 throughout the vertical extent of sections 81 and 82, and has a grout plug 84 closing and sealing the bottom of casing section 82. The upper end of well cas¬ ing section 81 is secured as by welding to a circular base plate 86 recessed to be flush with the ground surface 17 .In general, the outer pipe portion 18 and inner pipe portion 19 are supported in a suspended depending manner from the base plate 86 in such a way as to allow for expansion and contraction thereof relative to the wel casing due to temperature changes.The upper end of the top pipe section of the outer pipe portion 18 is secured as by welding to a circular baseplate 87 that rests on base plate 86 to support the outer pipe portion 18 in a suspended depending manner in the casing 82. Two flow'pipes 54 and 56 for conveying fluid to and from the coolant jacket 55 extend down throu a bushing in the base plate between the well casing and the exterior of the outer pipe portion. There is further provided above the ground surface level an extension of the outer pipe portion 18 including a straight coupling 89 threaded on external threads of th top subsurface pipe section of outer pipe portion 18 affixed to plate 87 that rests on plate 86, a pipe nipple 91, a tee coupling 92 and a pipe 93 having a flange plate 94 secured as by welding to the upper end with the lower end threaded into the tee coupling 92. A flange plate 95 rests on flange plate 94 and has the upper end of the inner pipe portion 19 secured thereto as by welding so that the inner pipe portion 19 is supported in a suspende depending manner from the outer pipe portion 18 which in turn is supported on plates 86 and 87.Yet a third top flange plate 96 rests on flange plate 95 and has an upper pipe nipple 97 threaded thereto with a top coupling 98 secured thereto to provide the coupling to the flow line 37 through which the effluent fluid is passed. There is further shown a gasket 101 between plates 94 and 95 and a gasket 102 between plates 95 and 96, together with a bolt fastener 103 to hold the flange plates together in a sealed watertight manner. Th pressure sensing tube 61 is shown as extending down throu the center of flange plate 96 and the inner pipe portion which is shown to extend up above the ground surface leve to connect to flange plate 95. The two flow lines 54 and 56 for conducting the cool¬ ant fluid extend from the ground surface down through support plate 87 and are supported on the outer pipe sec¬ tion, as best seen in Figures 9 and 10. Each coolant fluid flow line has a series of alternating pipe sections shown as a relatively long, rigid pipe section 109 on the order of 100 feet and a flexible pipe section or hose 111 on the order of two feet that are joined end-to-end to one another by a coupling 112. The lower end of the rigid pipe portion 109 rests on a support surface provided by a lower bracket 110 clamped to the outer pipe portion 18. A supporting guide bracket 113 guides the upper end portion of the outer pipe portion 18 in an axial sliding movement and has an annulus 114 which in turn carries a resilient sleeve 115. The rigid pipe section 109 is axially movable in the resilient sleeve to allow for axial movement of these flow lines for contraction and expansion due to temperature changes. Each flexible pipe section 111 is shown in a bowed configuration to allow for expansion and contraction. The coupling 112 on the lower end is slidable with pipe section 109 and the coupling 112 on the upper end is held by bracket 110. The flexible pipe section 111 may be made of a bellows- like conduit covered with a heat-resistant braided cover. As best seen in Figures 7 and 8, the outer pipe portion 18 extending from ground surface into the hole is made up of a plurality of end-to-end pipe sections 118 connected at adjacent ends by API (American Petroleum Institute) couplings 116. These couplings have a sub- stantial taper at each end and are standard well-type pipe couplings. The pipe sections making up the outer pipe portion 18 above the reaction zone as shown are made of black iron with a stainless steel liner 108 shown in Figures 11 and 12 and extend from the reaction zone up to a depth below the surface level of about 500 feet. This construction prevents corrosion.In a like manner, the inner pipe portion 19 is made up of a plurality of end-to-end pipe sections 119 connected at adjacent ends by end welds. As shown in Figure 15, the bottom pipe section of the outer pipe portion 18 has a shaped 180 degree turnaround provided by an end cap 24 to prevent plugging by scouring which directs the flow up through the inner pipe portion 19. Since there is no pressure differential across the wall of the inner flow passage, a thin-walled tube is used. Use of a thin-walled tube decreases cost and allows for better heat exchange between the hot reacted effluent fluid and the cool untreated influent fluid. For reference purposes, the inside diameter of the outer pipe portion 18 above the reaction zone is designat Dl, the inside diameter of the inner pipe portion 19 above the reaction zone is designated D2, the inside diameter of the outer pipe portion in the reaction zone is designated D3 and the inside diameter of the inner pipe portion 19 in the reaction zone is designated D4.The jacket 55 is provided on the outer pipe portion beginning at a selected depth below the ground surface level, which is at the top or beginning of the reaction zone R. At this depth both the outer and inner pipe portions are reduced in size, to provide a substantially constant mass flow rate.As the fluid flows down the outer flow passage, the gas is compressed and as a result the volumetric ratio of gas to liquid decreases with a resulting decreas in the velocity of the liquid. To maintain more nearly constant flow velocity, the outer and inner pipe portions are reduced in size in the area of the reaction zone. Th reduction in size increases the amount of production per capital investment and also maintains at least the flow velocity required to sweep the gas bubbles downward.As shown in Figure 11, an inner pipe section 119a a distance above the reaction zone has a reducing sleeve or coupling 121 along the inside which receives a smaller diameter inner pipe section 119b. In a like manner, .as shown in Figure 12, an outer pipe section 118a below coup ing 121 and above the reaction zone carries a reducing coupling or sleeve 122 which in turn has an inside cut into which a smaller diameter outer pipe section 118b is . iron lined with a stainless steel tubing 108 above fitting 122 extending up to about 500 feet below the ground sur¬ face. The reduction couplings are preferably made of stainless steel and machined to have a smooth, tapered entrance surface to prevent plugging. A larger outer pipe section 123 fits over an annular outer cut on sleeve122 with a space between pipe sections 123 and 118b forming the coolant jacket 55 which extends down to the bottom of the reactor.The heat from the reaction is collected in the jacket 55 and is passed therefrom, or heat may be input, in the form of a heated coolant fluid and/or steam to assist in starting up the reactor. At the upper end of the jacket 55, there is a fitting 120 mounted on pipe section123 coupling flow from line 56 to the interior of the top portion of the jacket. At the lower end of the outer jacket 55, there is an end cap 124 that cups over the lower end of the outer pipe section.123 forming the jacket and is secured thereto as by threads or welding. End cap124 has a vertical aperture 125 in the bottom thereof.A fitting 126 shown in Figures 17, 18 and 19 is secured as by welding to the bottom of the end cap 124 and ex¬ tends laterally out so as to be offset to one side thereof. The fitting 126 has a passage that opens into the bottom of the jacket and has a hole 127 at one end and couples to flow line 54. The jacket with end cap and fitting termin¬ ates a distance above the plug 84 to allow for up-and-down movement thereof relative to plug 84 due to expansion and contraction.To monitor temperature, temperature sensors in the form of thermocouples 131 shown in Figure 4, are placed on the outer pipe portion at approximately 250-foot inter¬ vals and are connected to a temperature indicator T at the surface level.A large heat loss can result from the presence of water inside the well casing 81 and 82. Such water will vaporize and rise to a cooler level, where it condenses and then flows down the external wall surface of the reactor until it is vaporized again. This refluxing action reduc the overall energy efficiency and feasibility of 1he proce To prevent this problem the inside of the casing can be dried by pumping or purging or can be insulated with a layer of insulation indicated at 129, shown in Figures 8, 17 and 18. A plastic-coated fiberglass bat, rock wool or ceramic felt has been found to be effective as an insulation for this purpose which serves as a baffle to prevent conductive and convective heat losses. OPERATIONThe influent fluid which in the specific applica¬ tion described herein is a streamof sewage sludge is pumped from supply 38 via flow lines 31 and 33 into and down the outer flow passage 21. A stream of air under pressure is pumped into the outer flow passage to form a train of spaced Taylor bubbles 78 and the pressure pro¬ vided by pump 29 is sufficient to move both the influent fluid and bubbles down the outer passage 21. As the two proceed down below the ground surface, the temperature and pressure increase and they reach a point at which oxid tion proceeds at an accelerated reaction rate, indicated at line D, and proceeding to the bottom, indicated at line G. The area between lines D and G is designated R.In the reaction zone R the pressures and temperature rapidly mix the oxygen with the water to cause a rapid oxidation of the combustible solids and a generating of heat to heat the fluid. Some of the reaction products resulting from the oxidation are C02, H-O, N + heat. The heated fluid and reaction products, termed the effluent fluid , then flow up the inner flow passage 22 in heat exchange relation to the downflowing influent fluid. Upon exiting the reactor, the effluent fluid is flowed through the ash settling tank and then is either used as a diluent for the influent fluid to maintain the proper influent C.O.D. or is discharged via flow line 44. The blend or concentration of the reactants in « relation to one another in relation to the amount of liqui content (water) of the influent fluid is controlled by the settings of valves 72, 74, 76, 43 and 39 relative to one ano er. s ou e no e a eac o ese con ro s is adjustable or settable at or in the area of the ground surface level.During start-up, heat is usually added to the reac- tion zone to heat the influent fluid by pumping a coolant fluid from tank 52 through heater 53, down flow line 54, through jacket 55, and back up flow line 56. After the temperature rises to about 400°F at the upper level of the reaction zone and heat is produced from the ensuing exothermal reaction, the direction of flow of the coolant fluid in lines 54 and 56 is reversed and pumped from the jacket up through flow lines 54 and 54b into the heat exchange unit 58, from which heat or work via a steam turbine generator 60 may be derived or heat may heat the room 67.Temperature at the start of the reaction is controlled by varying the setting of control 53b and by the flow rate in line 54. Temperature during operation is controlled to maintain the vapor pressure of the influent fluid at the local temperature lower than the local pressure to prevent boiling while maximizing the reaction rate.Referring now to Figure 22, there is shown an arrange¬ ment of the present invention wherein three subsurface reactors 135, 136 and 137 are mounted in one outer well casing 138 for greater treatment capacity in one vertical hole of shorter depth than would be required for one long reactor. Again the casing has grout lining the inside of the hole and has a grout plug seal 139 at the bottom. The void between the reactors and casing is shown filled with an insulation 141.As previously described, each reactor has an outer pipe portion and an inner pipe portion with associated input and output ports above the ground surface. In the arrangement shown there is a tank 142 for reactor 135, a tank 143 for reactor 136 and a tank 144 for reactor 137. A fluid pump 148 and an air compressor 149 are associated with each reactor, as previously described. Influent fluid indicated at line 145 and gas under pressure are pumped into tank 142 and from tank 142 down reactor 135 effluent fluid from reactor 135 to the tank 143. Influe fluid from tank 143 and gas are pumped into reactor 136, with effluent fluid out of reactor 136 pumped into tank 144. Finally, effluent fluid and gas under pressure are pumped from tank 144 into reactor 137 and effluent fluid from reactor 137 is passed to a point of use via line 14This arrangement of three reactors coupled in seri increases the C.O.D. reduction over a single reactor hav the same retention time, apparently due to the fact that the reaction product CO can be removed via the tanks 14Some typical ranges are listed in the following taTABLEExample Range1. ReactorAbove Reaction Zone Diameter Outer Pipe Portion Dl ID 2.465 in. 1 to 24 in Inner Pipe Portion D2 ID 1.560 in. 3/4 to 20Reaction Zone DiameterOuter Pipe Portion D3 ID 1-870 in. 3/4 to 20 Inner Pipe Portion D4 ID .995 in. 0.5 to 18Total Depth 1500 ft. 1000 to 60Depth to Start of Reaction Zone 1000 ft. 500 to 450Length of Reaction Zone R 500 ft. 500 to 300Temperature at Top of Reaction Zone 450°F 300 ° to 55Temperature at Bottom of Reaction Zone 470°F 300 ° to 65Pressure at Top of Reaction Zone 410 psia 200 to 193Pressure at Bottom of Reaction Zone 650 psia 433 to 26002. Influent Fluid with Reactants Sewage Sludge Waste Stream C . O .D . 7600 mg/liter 0 to 20 , 00Pressure ( surface) 0 psia 0 to 200 pTemperature Atrros. Ambient Atrros. AmbieFlow rate About 3 gpm 0 to 500 g TABLE (cont'd.)Example RangeAirPressure 100 psia 0 to 200 psia Temperature Atmos. Ambient Atmos. Ambient Flow Rate 1. 52 cfm 0 to 500 cfm Bubble Velocity . 70 f t/sec 0 . 5 to 2.5 ft/sec3. Effluent Fluid Pressure 80 psia 0 . to 200 psia Temperature Atmos. Ambient Atmos. AmbientFlow Rate About 3 gpm 0 to 500 gpm4. OutputEnergy Btu/Day . 67 x 106 80 to 10 x 10C.O.D. Reduction 70% 0 to 99%Amount Throughput C.O.D./Day 112 lb/day 100 to 100,000 lb/day C.O.D.Flow Rate 3 gpm 0 to 500 gpmRaw Sewage Equivalent* 72,000 gpd 45,000 to 64x10 gpd* = at 1,5600 Ib/C.O.D. per million gallons of raw sewageINDUSTRIAL APPLICABILITY In summary, the method and apparatus of the present invention accomplish a high temperature, high pressure, chemical reaction including the wet oxidation of sewage sludge and other fluid waste but require only low pressure pumping apparatus. Both the initial costs and the operat¬ ing costs are considerably less than other known methods and apparatus achieving similar end results. In addition, the method and apparatus of the present invention require a minimum of low skill maintenance and produce energy in the form of a high quality steam. The invention achieves essentially a 100% destruction of all living organisms and about 98% reduction in the C.O.D., is odorless, and produces a readily dewaterable ash end product. In the present invention all of the control is in the area of the ground surface, there is a minimum power require- ment for pumping relatively large quantities of fluids, and there is a continuous downflowing and upflowing flui flow throughput. The method and apparatus disclosed is suitable for carrying out high-temperature, high-pressur chemical reactions as, for example, in the cracking of petroleum products and for carrying out high-temperature, high-pressure hydrogenation such as in the forming of am in which case the enlarged bubbles would not be necessar | WHAT IS CLAIMED IS:1. In a method for effecting accelerated chemical reactions between at least two reactants, the steps of: flowing an influent fluid with at least two reactants downwardly through a downgoing flow passage at a selected flow rate to a selected depth below the ground surface to form a hydrostatic column of fluid exerting a pressure and provide a temperature sufficient to cause the reactants at said selected depth to react at an accelerated reaction rate and pass further down through a reaction zone extending through said downgoing flow passage a selected distance below said selected depth whereby reaction products are produced and the fluid is heated in said reaction zone, flowing the heated fluid and reaction products from said reaction zone back up to sub¬ stantially ground surface level in an upgoing flow pass¬ age in heat exchange relation to the downflowing fluid as an effluent fluid; and controlling the temperature of the influent fluid in said reaction zone by adding heat to or removing heat from said influent fluid substantially in the -area of said reaction zone to accomplish a maximum reaction rate with the vapor pressure of the influent fluid at the local temperature being maintained always lower than the local pressure to prevent boiling of said influent fluid.2. In a method as set forth in Claim 1 wherein one of said reactants is a stream of gas introduced under a selected pressure into the influent fluid substantially at the ground surface level through an outlet facing the downstream end of said downgoing flow passage to form a series of enlarged gas bubbles that are carried down with the influent fluid to cause intense mixing and con¬ tacting and maximize the reaction in the reaction zone and reduce pumping requirements. 3. In a method as set forth in Claim 1 wherein on of said reactants is a gas that is introduced at a plurality of selected depth intervals below the ground s face level as successive streams at progressively higher pressures.4. In a method as set forth in Claim 1 wherein the pressure of the influent fluid at substantially the ground surface level is in the range of about 0 to 200 psia at substantially atmospheric, ambient temperatures with a continuous downflowing and upflowing fluid flow throughput.5. In a method as set forth in Claim 1 including the step of_ controlling the pressure and flow rate of the influent fluid and effluent fluid at substantially ground surface level.6. In a method as set forth in Claim 1 including the step of controlling the .concentration of said reac¬ tants in relation to one another and in relation to the amount of liquid content of the influent fluid.7.' In a method as set forth in Claim 1 wherein sai effluent fluid is successively recycled back down as influent fluid and up as effluent fluid in a succession of downgoing and upgoing flow passages disposed in a common hole coupled in series for carrying out a succes- sion of chemical reactions on a continuous stream of fluid, the effluent fluid from each successive reactor being passed into a tank open to the atmosphere to remove gaseous reaction products.8. In a method as set forth in Claim 1 wherein sai influent fluid is sewage sludge delivered to the downgoin flow passage at a selected flow rate and selected pressur and one of said reactants is air with oxygen to perform the wet oxidation of sewage sludge. 9. In a method as set forth in Claim 1 including adding heat to said influent fluid substantially in the area of said reaction zone to initiate the reaction.10. In apparatus for effecting accelerated chemical reactions, the combination comprising: a reactor including first and second pipe portions defining a downgoing flow passage and an upgoing flow passage in heat exchange relation to the downgoing flow passage, said downgoing flow passage extending from substantially the ground surface to a depth sufficient to cause a downflowing- fluid therein to form a hydrostatic column of fluid to exert a pressure and provide a tempera¬ ture sufficient to cause two reactants in the fluid at said selected depth to react at an accelerated rate, said down- goingflow passage extending down from said selected depth to form a reaction zone whereby reaction products are produced and said fluid is heated in said reaction zone; means for pumping an influent fluid with at least two reactants from substantially the ground sur- face level through said downgoing and upgoing passages whereby an effluent fluid with reaction products is passed from said reactor; and means for controlling the temperature of the influent fluid in said reaction zone by adding heat to or removing heat from the influent fluid in the area of the _eaction zone to maintain a substantially maximum reaction rate without boiling of the fluid in said reaction zone.11. In apparatus as set forth in Claim 10 wherein said first and second pipe' portions are arranged with one in concentric spaced relation within the other with the outer pipe portion being closed at the bottom forming a hydraulic flow-through ϋ-tube.fr IPO 12. In apparatus as set forth in Claim 10 wherein said reactor-is disposed in a subterranean cased hole providing a subterranean housing for but separate from said reactor.13. In apparatus as set forth in Claim 10 wherein said first and second pipe portions are supported in a depending manner from a common support plate at the grou surface level.14. In apparatus as set forth in Claim 10 wherein said pipe portions are reduced in size at a selected dep below the ground surface substantially at the upper limi of the reaction zone to maintain a substantially constan velocity through said pipe portions.15. In apparatus as set forth in Claim 10 includi pumping means in the area of the ground surface level fo flowing the fluid through said upgoing and downgoing flo passages in a continuous throughput flow.16. In apparatus as set forth in Claim 10 wherein said means .for controlling the temperature of the influe fluid includes a jacket with an inner annular passage surrounding and in heat exchange relation to the outer of said pipe portions through which a coolant fluid is pumped and further includes a pair of flow lines coupled to said jacket and extending up to the ground surface level to circulate a fluid to and from said jacket to th ground surface level.17. In apparatus as set forth in Claim 10 includi a tank, a pump, a heat exchanger, a control valve, and a heat source in the area of the ground surface level coup in a fluid flow circuit with said jacket and flow lines for heating and pumping a heated fluid into said jacket in one mode of operation and for pumping heated fluid fr the jacket through said heat exchanger in another mode o operation to control the temperature of the fluid in said reaction zone.18. In apparatus as set forth in Claim 10 including means for introducing a stream of gas under a selected pressure into the downgoing flow passage in the area of the ground surface level to form enlarged gas bubbles commonly known as Taylor bubbles, characterized by a generally cylindrical main body portion, a generally spherical cap portion, and a truncated portion opposite said cap, that are pumped down with the influent fluid.19. In apparatus as set forth in Claim 18 including a plurality of inlets for said stream of gas located at spaced selected distances below the ground surface level.20. In apparatus as set forth in Claim 18 wherein said means for introducing a stream of gas includes a terminal pipe section in the downgoing flow passage arranged longitudinally of the passage with an outlet opening toward the downstream end of said downgoing flow passage.21. In apparatus as set forth in Claim 10 including a plurality of reactors disposed side-by-side in a single well casing, said reactors being flow-coupled in a series relationship with the influent fluid passed into one of said reactors and the effluent fluid from said one reactor into the next reactor to successively recycle the fluid back down for further reaction for carrying out a succession of chemical reactions on a continuous stream of fluid.- JREOMPI | MCGREW J | MCGREW J |
WO-1979000797-A1 | 1,979,000,797 | WO | A1 | XX | 19,791,018 | 1,979 | 20,090,507 | new | C08G63 | null | C08G63, C09D167, D01F6 | C08G 63/19 | LIQUID CRYSTAL COPOLYESTERS | Liquid crystal copolyesters having melting points low enough to allow the copolyesters to be melted and processed in conventional equipment. The copolyesters are prepared from terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid and a diacyl ester of hydroquinone and contain the following divalent radicals: | -1-LIQUID CRYSTAL COPOLYESTERSThis invention relates to liquid crystal co¬ polyesters having the high mechanical properties of liquid crystal polyesters and melting points low enough to allow the copolyesters to be melt-processed into use¬ ful articles using commercially available equipment. Background of the InventionLiquid crystal polyesters that are all-aro- matic have excellent mechanical properties. Examples of these polyesters are the copolyesters prepared from terephthalic acid, •isophthalic acid, 2,6-naphthaline- dicarboxylic acid and hydroquinone. U.S. Patents 3,160,602 and 3^778,410 describe processes that can be used to prepare these copolyesters. It has been diffi¬ cult to use these copolyesters because the melting points of the polymers have been so high that the polymers can not be melted and formed into useful articles in conven¬ tional processing equipment. We have found that certain all-aromatic copoly- esters prepared from terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid and hydroquinone have melting points that are low enough to permit the copolyesters to be processed into useful articles, such as fibers and molded articles, in conventional equip¬ ment.The copolyesters of our invention are prepared from terephthalic acid, isophthalic acid, 2,β-naphthal- enedicarboxylic acid, and a diacyl ester of hydroquin- one and can be defined as copolyesters having molecular weights suitable for forming fibers and containing the following divalent radicals :OMPl f?NAT\ >yIn our copolyesters the range of terephthali acid is from 20 to 80 mole percent, based on the total moles of terephthalic acid and isophthalic acid combin Since the range of terephthalic acid is based on the s of the moles of terephthalic acid and isophthalic acid at 20 mole percent terephthalic acid our copolyesters have 80 mole percent isophthalic acid and at 80 mole percent terephthalic acid our copolyesters have 20 mol percent isophthalic acid.In preferred copolyesters the range of terep thalic acid is from 30 to 70 mole percent, based on th total moles of terephthalic acid and isophthalic acid combined.Also in our copolyesters the amount of 2,6- naphthalenedicarboxylic acid is from 15 to 60 mole per cent, based on the total moles of terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid In preferred copolyesters the range of 2,6- naphthalene-dicarboxylic acid is from 20 to 50 mole percent.The precise manner in which the melting poin of the polyesters of our invention are unexpectedly lower than the melting points of similar polyesters is illustrated in the accompanying Figure. In the Figure the amount of 2,6-naphthalene- dicarboxylic acid, based on the total moles of tereph¬ thalic acid, isophthalic acid and 2,6-naphthalenedicar- boxylic acid, has been plotted on the abscissa. The temperature in degrees Centigrade has been plotted on the ordinate. Melting points have been plotted for the copolyesters of our invention, containing a quantity of terephthalic acid in the range of 20 to 80 mole percent, based on the total moles of terephthalic acid and isoph- thalic acid. Suitable curves have been drawn through the data points for copolyesters containing the same amount of terephthalic acid and isophthalic acid. For example, the lowermost curve drawn through the solid square data points shows the melting points of copoly- esters containing 40 mole percent terephthalic acid and 60 mole percent isophthalic acid.The data for the copolyesters of our invention were obtained by preparing each of the copolyesters using a process known in the art and then determining the melting points of the copolyesters .The copolyesters of our invention were pre¬ pared by an acidolysis procedure whereby terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid and a diester of hydroquinone are reacted under an increasing temperature ranging up to 3^0-380 C. and a decreasing pressure to form a high molecular weight polymer. As a specific example, the following procedure was used to prepare a copolyester from hydro¬ quinone and 40 mole percent terephthalic acid and 60 mole percent isophthalic acid, based on the moles of terephthalic acid and isophthalic acid combined, and 30 mole percent, 2,6-naphthalenedicarboxylic acid, based on the moles of 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid combined. A mixture of 23-2 g. (0.14 mole) terephthal acid, 34.9 g. (0.21 mole) isophthalic acid, 32.4 g. (0.15 mole) 2.6-naphthalenedicarboxylic acid, and 111 g. (0.500 mole) hydroquinone dipropionate was placed in a 500 ml. flask equipped with a stirrer, short dis tillation column and an inlet for nitrogen. The flas was evacuated and purged three times with nitrogen an dried at 100-110 C. for 30 minutes at 0.3 mm pressur before being immersed in a bath at 275°C. After the mixture was stirred for 30 minutes at 280°C, the tem perature was raised to 300°C. for 30 minutes and then to 325°C. for 30 minutes. Finally the temperature wa raised to 355°C. for 25 minutes and a vacuum of 0.5 m was applied. The polymerization was complete within to 30 minutes. The tough, fibrous, opaque polymer ha a melting point of 334°C.The other copolyesters containing different amounts of 2,6-naphthalenedicarboxylic acid, terephth alic acid and isophthalic acid were prepared by a sim lar procedure but using slightly different reaction temperatures because of differences in melting points Solid-phase polymerization also may be used to increase the molecular weight of the copolyesters of the invention by heating polymer particles in an inert atmosphere or under reduced pressure at a tempe ature below that at which the particles will become tacky and tend to fuse together. Since this thermal treatment may give polymers with increased crystallin and melting points, compared to melt phase polymeriza tion, melt phase polymerization is generally preferre Solid-phase polymerization is preferred, however, if the melting point is above 380 C.The melting points of the copolyesters of t invention were determined with a differential scannin calorimeter. The accompanying Figure shows that the melting points of the polyesters of the invention containing 20 to 80 mole percent terephthalic acid and 15 to 60 per¬ cent 2,6-naphthalenedicarboxylic acid are unexpectedly lower than the melting points of polyesters containing less than 20 or more than 80 mole percent terephthalic acid and less than 15 or more than 60 mole percent 2,6- naphthalenedicarboxylic acid. For example, consider the polyester which contains a constant value of 50 mole per- cent terephthalic acid and is represented by the second curve from the bottom connecting the open square data points. When there is no 2,6-naphthalenedicarboxylic acid present, the melting point is so high the polymer is not useful for melt processing. When even small amounts of 2,6-naphthalenedicarboxylic acid are added the melting point falls rapidly and when 20 mole per¬ cent 2,6-naphthalenedicarboxylic acid is added, the melting point falls to 370 C. As the amount of 2,6- naphthalenedicarboxylic acid is further increased, the melting point continues to fall and reaches a minimum value of 350°C. at approximately 35 mole percent 2,6- naphthalenedicarboxylic acid. As the amount of 2,6- naphthalenedicarboxylic acid is increased, the melting point rises. Although the details of the reduction in melt¬ ing point have been discussed only for the polyester containing 50 mole percent terephthalic acid, the same lowering of the melting point applies to the other poly¬ esters within the scope of this invention. For example, the melting point of the polyester containing 40 mole percent terephthalic acid is also substantially lowered when from 15 to 60 mole percent 2,6-naphthalenedicar- boxylic acid is used. Melting points for the polyesters containing small amounts of 2,6-naphthalenedicarboxylic acid often cannot be obtained because it is not possible -6-to prepare these polyesters. The polyesters melts so high the polymer becomes solid in the reaction flask prior to forming a high molecular weight polyester. A wide variety of diesters of hydroquinone can be used to prepare the copolyesters of this inven¬ tion. Examples of diesters of hydroquinone include the diacetate, dipropionate, dibutyrate and dibenzoate. The diacetate and dipropionate are preferred.The copolyesters of this invention can con- tain minor amounts of other naphthalenedicarboxylic acid isomers in addition to the 2,6- isomer. Also, minor amounts of dicarboxylic acids other than terephthalic acid and diols other than hydroquinone can be used. The copolyesters of this invention can also contain nucleating agents, fillers, pigments, glass fibers, asbestos fibers, antioxidants, stabilizers, plasticizers, lubricants, fire-retardants, and other additives.The inherent viscosity of the copolyesters of this invention cannot be determined because the copoly- esters of this invention are insoluble in typical sol¬ vents used for determining inherent viscosity. Although the inherent viscosity of the copolyesters of the inven¬ tion has not been measured, the molecular weights of the copolyesters of the invention are high enough to be in the fiber forming range. The minimum fiber forming molecular weight of the polymer is about 55000. In most cases copolyesters of the invention have molecular weights above 8,000 and can have molecular weights as high as 20,000 and in some instances the molecular weights can range up to 253000 or even higher.. OM | We Claim :Copolyesters having a fiber forming molecular weight and containing the following divalent radicals:the copolyesters being characterized by the amount of being from 20 to 80 mole percent, based on the total moles of -£→ C- *nd and theamount of being from 15 to 60 mole per- cent, bas dd oonn tthhee ttoottaall mmoolleess 2. The polyester of Claim 1 wherein theamount of is from 30 to 70 mole per- cent and the amount of is from 20 to 50 mole percent.O PI | EASTMAN KODAK CO | JACKSON W; MORRIS J |
WO-1979000799-A1 | 1,979,000,799 | WO | A1 | XX | 19,791,018 | 1,979 | 20,090,507 | new | B32B27 | C08L27, D06M15, A01N9, B32B27, B05D1 | A01K75, D06M15 | A01K 75/00, D06M 15/244 | NET FINISHING COMPOSITION,PROCESS AND PRODUCT | A net finishing composition for treating a net, such as a fish net formed of synthetic material, to form a flexible film thereon, and which is comprised of a low molecular weight, high acetate content vinyl chloride copolymer resin, a monomeric plasticizer and a polymeric plasticizer dissolved or dispersed in a solvent system. A process for treating with the finishing composition and the resultant product is also disclosed. The process comprises immersing a net into a pool of the composition, withdrawing the net from the pool, and curing the coated net. | DESCRIPTIONNet Finishing Composition, Process and ProductTechnical FieldThis invention relates to a compos ition of matter and a process for using same, and more particularly to a net finishing composition for treating nets and the product obtained thereby. Nets, such as fish nets, have from time immemorial been made from natural fibers and have been treated with tar or tar-like materials to protect and enhance the properties thereof. Synthetic materials, such as nylon, polyesters, polypropylene, polyethylene and the like are replacing such natural fibers with nylon presently being in greater demand as a result of the many excellent properties as well as cost considerations.Nylon, i. e. , the monofilament fiber thereof, is woven to form a twine which is subsequently further woven to form the desired mesh size of the net. To protect the thus formed nylon net or the like, such a net is treated with tar and variations of such natural like materials, much as the natural fiber nets have been treated over the centuries, as well as being treated with various synthetic materials. Such treatments have been found to be relatively ineffective with the resulting coatings or films readily washing off or wearing off the manufactured net. With such washing out or wearing out, exposure of the synthetic material to the elements has caused early breakdown of the net resulting in the surveying thereof or at best retreat ment thereof.A s hereinbefore mentioned, nylon has found the greatest use in the fish net industry as compared with other synthetics due to its many excellent properties as well as present cost factors, however, nylon has been found to absorb as much as 20% by weight of its weight in water with concomitant loss in fiber strength. In the manufacture of nets, whether the net is to be used for in sporting events, such as tennis, ping-pong or the like or as fishing nets, the mesh size thereof are set by usage or by governmental regulations. In particularly, the fishing industry, the net mesh size5 is carefully regulated by the Federal Government, i. e. , mesh size is dictated by the type of fish being subjected to trawling. While use of nylon nets have increased the lifetime of net usage as distinguished from natural fiber nets coated with tar or tar-like substances, the usage lifetime is still relatively short.10 Disclosure of InventionThe objects of the present invention are achieved by a net finishing composition which is preferably applied by dipping the net mesh substrate into such composition and which is comprised of a low molecular weight, high acetate content, vinyl chloride copolymer, a15 monomeric plasticizer, a polymeric plasticizer dissolved or dispersed in a solvent system. The plasticizers are present in an amount from 40 to 60 parts, preferably 50 parts per 100 parts of the copolymer with the ratio of monomeric plasticizer to polymeric plasticizer ranging from 1 part to 1 part to 3 parts to 1 part, preferably 2 parts to 1.20 The solvent system includes ketones and aliphatic and/ or aromatic diluents in the range from 75 to 25 to 25 to 75 parts. In one embodiment of the present invention, a net finishing concentrate is provided wherein the copolymer and plasticizers are dissolved in a solvent system comprised of essentially ketones for subsequent dilution in a further• 5 solvent for the treatment of the net.The net finishing composition of the present invention applied to the net substrates exhibits many properties similar to the properties of the tars as well as many properties superior to the properties of tar used to treat natural fiber nets. In this regard, the resulting net'30 exhibits low physical properties, i. e. , low psig with high elongations. Use of a cabon black pigment has significantly aided in psycological acceptance of the resulting net. The essential components of the resin system of the present invention are the low molecular weight, high acetate content, vinyl chloride copolymers and the monomeric and polymeric plasticizers. The amount of plasticizers added to the low molecular weight, high acetate content, vinyl chloride copolymer is from 40 to 60 parts, preferably about 50 parts to 100 parts of the copolymer resin. The ratio of the monomeric plasticizer to polymeric plasticizers is from 1 : 1 to 3 : 1, preferably about 2 : 1.The resin system is dissolved or dispersed in a solvent system such that the solids content of the resulting composition of matter is no less than 20% by weight, and between 20 to 40% solids, with a preferable solids range of 27 to 28% by weight.A solvent system includes ketones and aliphatic aromatic hydrocarbons wherein the ratio of ketones to aliphatic aromatic diluents are from 25 to 75 to 75 parts to 25 parts with a preferred range of 50 parts of ketones to 50 parts of the aliphatic aromatic diluents. It will be understood by one skilled in the art that an increase in the aliphatic aromatic diluents to ketones would be more economically attractive, as well as, result in a product which more closely resembles a tar coating, although higher concentrations of such aliphatic aromatic result in lower solids content in the net finishing composition.While the actual mechanism of the present invention is not clearly understood, it is believed that the net finishing composition of the present invention results from the viscosity and slow drying time of the net finishing compostion which permits penetration and monofilament coating of the individual fibers of the woven net, and that penetration and coating continues during drying for a time period substantially greater than the synthetic net finishing composition here- tofore tried in the art which normally results in casting as herein¬ after more fully discussed.IjUREAlTOMPI Of the low molecular weight, high acetate content, vinyl chloride copolymers, I have found that the acetate content should not be less than about 10% by weight and preferably between 15 to 20% by weight of the copolymer resin. The molecular weight of the copolymer should be in the range from 20, 000 to 65, 000 with lower acetate content being associated with the higher molecular weights.In some formulations, pigments have been added for color effect. I have found that carbon black has demonstrated excellent reinforcing properties as well as to result in a net which is colored similar to the nets used for years in the industry, i. e. psycological acceptance.As her einabove mentioned, due to shipping cost considerations, concentrates of net finishing compositions may be prepared and shipped which only require the addition of diluent solvents at the user site. In this regard, the herein-above discussed resin system is preferable admixed with 100% ketones to form a 45 to 55% by weight solids solution which solids solution is subsequently diluted by adding any conventional aliphatic and /or aromatic hydrocarbon to achieve proper solids content (20% - 40%) prior to net treating. Of the monomeric plasticizers, of which there are many, I have found D. O. D. P. (dioctyl diphthalate) to be particularly usefully advantageous (cost) in the resin system of the present invention. Of the polymeric plasticizers, which there are many in the art, all the primary polymeric plasticizers have been found useful in the net finishing composition of the present invention.The net finishing composition of the present invention has been found to be particularly useful, as hereinabσre discussed, in the treatment of nylon netting for salt water usage, and in this regard, the composition of the present invention permits a one-step treatment of the netting. Net treatment is effected by placing the net finishing composition, (or properly solventized concentrate) at ambient temperatures in a trough and continuously introducing and wi th¬ drawing width- wise the net in total immersion in the net finishing solution for a time from 5 to 10 seconds. The net generally dries to the touch in 1 to 2 hours. It is generally desirable to permit the coated net to cure for at least 72 hours before fishing. It will be appreciated by one skilled in the art that fish nets are of consider- able weight and length an d are not readily handled. Consequently, substantial savings in net handling result through the use of the present invention in that one-step treatment with the composition of the present invention may be effected rather than a double or three-through treatment required when using high molecular co- polymers whereby minimum solids pickup of fro m 20 to 25% is required. It has been additionally found that the use of high molec¬ ular weight, high acetate content resins require weight copolymers which require substantial thinning or dissolution to obtain the required penetration for double or triple dipping. Additionally, double or triple dipping of the net with high molecular weight copolymer essentially results in a casting of the material rather than penetration thereby substantially increasing peeling of the resulting film through handling and abrasion.It has been found that a nylon net treated with the net finish composition of the present invention results in a coated nylon net of significantly increased strength properties, e. g. , up to 25% stronger than a nylon net alone or nylon net treated with tar or tar-like materials. Additionally, it has been found that the resulting coating or film of the present invention substantially reduces water penetration into the nylon filaments and thereby significantly reduces nylon stretching whereby mesh size will remain substantially constant during the fishing season. Thus, the us e of nylon nets treated in accordance with the present invention as com¬ pared with nylon nets tar treated in accordance with the present art practice has resulted in an increase of a fish (menhaden) catch of as great as 50% due to the substantial maintenance of the mesh size.The following example is illustrative of the present invention:EXAMPLEA nylon fish net is introduced into the following net finishing compound having the following components :INGREDIENTSLow molecular weight, high acetate content, vinyl co¬ polymer - *VC113 100 Monomeric plasticizer 33(D. O. D. P. ) Polymeric plasticizer 17**Sanitizer 429 M. I. B. K. ) Solvent - 175 Ketone ) System 175* Registered Trademark of the Borden Company. ** Registered Trademark of Monsanto.The treated net is removed from the net finishing com¬ position and is permitted to dry for a period of about three days. Thereafter the net is onloaded to a fishing trawler of a fleet thereof and is found t o substantially improve daily catch and in some instances by as much as 50% when compared with nylon nets treated with tar-like materials on trawlers in the same fleet.Fouling of nets with organism, such as barnacle-type organism have been an additional problem. I have found that by adding of from 6 - 15 oz. per gallons to the net finishing composition of a series of organo tin esters, e. g. n-tributyl tin succinate, benzoate and linoleate, and quartenary ammonium salts dissolved in a solvent system, that significant anti-fouling effects have re- suited.While the present invention has been used for the treatment of nylon fish nets of a mesh size for menhaden fishing, mesh sizes as well as length sizes are not relevant to the present invention except as to sufficient contact time between the composition and net being treated. Additionally, while the net material has found use in sal t water fishing, nets treated in accordance with the present inventi~VΛ} - f r sporting events and for fresh water fishing would similarly benefit, as well as the fact that any form of nylon netting or like synthetic fiber netting, as well as natural fibers could benefit from the use of the present invention. Additionally, other vinyl chloride copolymers could be used, e. g. , a vinylidine vinyl chloride. | received y t e nternat ona ureau on ugus . .1. A concentrate solution for preparing a net finishing solution for treating a net substrate to improve the physical properties thereof which comprises: a solution of a low molecular weight, high acetate content, vinyl chloride copolymer; a monomeric plasticizer; a polymeric plasticizer and a solvent system, said copolymer having a molecular weight of from 20,000 to 65,000 and having an acetate content of from about 10 to about 20 percent by weight, said monomeric and polymeric plasticizers being present in an amount of from about 40 to 60 parts per 100 parts of said copolymer, the ratio of said monomeric plasticizer to said polymeric plasticizer being in the range of from 1 : 1 to 3 : 1, said solvent system being present in an amount to effect a solids content of said concentrate solution of between about 45 to 55 parts by weight.2. A net finishing solution for treating a net substrate formed of a synthetic material to improve the physical properties thereof which comprises: a low molecular weight, high acetate content, vinyl chloride copolymer; a monomeric plasticizer; a polymeric plasticizer and a solvent system, said copolymer having a molecular weight of from 20,000 to 65,000 and having an acetate content of from about 10 to about 20 percent by weight, said monomeric and polymeric plasticizer being present in an amount of from about 40 to 60 parts per 100 of said copolymer, the ratio of said monomeric plasticizer to said polymeric plas¬ ticizer being in the range of from 1 to 1 to 3 : 1, said solvent system being present in am amount to provide a solids content of from 20 to about 40 parts by weight of the net finishing solution.3. The net finishing solution as defined in Claim 2 wherein said solvent system is comprised of a ketone and an aromatic and/or aliphatic diluent in a ratio of from 25 to 75 to about 75 to 25 parts.4. The concentrate solution as defined in Claim 1 wherein said solvent system is comprised of essentially of ketones and said concentrate has a solids content of about 50 parts by weight.5. The net finishing solution as defined in Claim 2 wherein a vinylidene vinyl chloride copolymer is sub¬ stituted for said low molecular weight, high acetate content vinyl chloride copolymer.6. The net finishing solution as defined in Claim 1 wherein carbon black is added to said net finishing solution.7. The net finishing solution as defined in Claim2 wherein an anti-fouling agent is added to said net fin¬ ishing solution.8. A process for treating a net substrate formed of a snythetic material to improve the physical properties thereof which comprises; a) forming a net finishing soltuion by dissolving a low molecular weight, high acetate content vinyl chloride copolymer, a monomeric plasticizer, a polymeric plasticizer in a solvent system, said copolymer having a molecular weight of from 20,000 to 65,000 and having an acetate content of from about 10 to about 20 percent by weight, said monomeric and polymeric plasticizers being present in an amount of from about 40 to 60 parts per 100 parts of said copolymer, the ratio of said monomeric plasticizer to said polymeric plasticizer being in the range of from 1 : 1 to 3 : 1, said solvent system including ketones and being present in an amount to result in a solids content of from 20 to 40% by weight of said net finishing solution; b) forming a pool of said net finishing solution; c) immersing said net substrate into said pool of said net finishing solution; d) withdrawing said net substrate coated withOMPI wiP said net finishing soltuion from said pool; and e) curing said coated net substrate.9. The process as defined in Claim 8 wherein said net substrate is formed of nylon filaments.10. The process as defined in Claim 9 wherein said solvent system includes aliphatic and/or aromatic dilutents and in a ratio to said ketones from 75 to 25 to 25 parts to 75 parts.11. The process as defined in Claim 10 wherein the ratio of ketones to aliphatic and/or aromatic diluents is 50 parts to 50 parts.12. The process as defined in Claim 9 wherein said solids content of said net finishing solution is about 28 percent by weight.13. The process as defined in Claim 9 wherein said net substrate is cured under ambient conditions prior to fishing.14. The product produced by the process of Claim 8.15. The product produced by the process of Claim 9. | GUGLIELMO R | GUGLIELMO R |
WO-1979000800-A1 | 1,979,000,800 | WO | A1 | XX | 19,791,018 | 1,979 | 20,090,507 | new | A24B3 | A24B3 | A24B3 | A24B 3/04, A24B 3/12 | VAPOR EXCHANGE | A process and apparatus for treating materials such as tobacco or the like by vapor exchange so that the material being treated does not develop partial staining n the material being treated due to condensation. Material to be treated is transported through a treatment zone bounded by a foraminous member that separates the treatment zone from an immediately adjacent zone of high density vapor. The vapor is flowed through the foraminous member and directly into the material at a continuous rate and with a major portion of the vapor flowed from the vapor zone being entrained by the material in the treatment zone. The continuous moderate flow of vapor into the bed of material produces rapid vapor ransfer and with excellent distribution of the vapor within the material being treated. | VAPOR EXCHANGE Background of the Invention This invention relates to material treatment and more particularly to vapor exchange processes and apparatus for treating materials such as tobacco or the like.Tobacco, during processing, is commonly subjected to one or more treatment steps that utilize a gaseous fluid. For example, among the treatment steps to which tobacco may be exposed in a processing sequence to an atomized liquid (casing) which penetrates into the fiber structure of the tobacco; to a heated gas in a roasting process; to a cool gas to cool the roasted tobacco; and to moist sprays to increase the moisture content of the roasted and cooled tobacco as sub¬ stantial moisture content is desirable for suitable suppleness or pliability of the tobacco and to reduce the likelihood of tobacco dust generation and/or ex- cessive fragmentizing of tobacco during processing. Freshly gathered tobacco is normally dried for stor¬ age and it is frequently desirable to increase the moisture content of such dried tobacco prior to processing. It is also desirable that the moisture content of tobacco particles which are to be intro¬ duced into a modern high speed cigarette making machine be maintained within close tolerances. Similar adjustment of desired moisture content of other hygroscopic materials such as cereal flakes and vapor impregnation treatments of solid materials are also frequently desired.Numerous processes and apparatus for adjusting the moisture content of hygroscopic materials have been proposed and used. Perhaps most frequently used is a stream of air into which steam or hot water is sprayed. The air stream in some systems flows in the direction concurrent with the transport direction in other systems flows in a countercurrent direction and in still other systems flows upwardly through a bed of material (such as tobacco) for fluidizing the material. Among the problems encountered is the tendency for the water vapor to condense from the air stream which results in formation of stains on the tobacco and in nonuniform distribution of moisture content through the tobacco. In practice the reorder ing of tobacco with a high degree of uniformity at commercially acceptable rates has been difficult.The present invention provides novel and improved processes and apparatus for providing vapor exchange treatment of tobacco and other materials. In accor¬ dance with an aspect of the invention, the material to be treated is transported through a treatment zone that is bounded by a foraminous member that separates the treatment zone from an immediately adjacent zone of high density vapor. The vapor is flowed through the foraminous member and directly into the material at a continuous rate and with a major portion of the vapor flowed from the vapor zone being entrained by the material in the treatment zone. The continuous moderate flow of vapor into the bed of material pro¬ duces rapid vapor transfer (without such problem as staining due to partial condensation) and with excellent distribution of the vapor within the material being treated.Preferably the treatment zone is immediately above the vapor zone so that vapor rises through the foraminous member for flow into the material in the treatment zone. The vapor flow is preferably main- tained by creating a postive pressure in the range of about 0.1-1.0 inch of water in the vapor zone with a gas flow in a closed circulation path for considera¬ tion such as containment, efficiency and energy con¬ servation. Preferably vapor is derived from warm liquid in a chamber immediately adjacent the treatment zone, the heat and flow conditions being such that the vapor zone is essentially fully saturated at the tem¬ perature of the liquid in the chamber. Various foraminous members may be used including open mesh walls or tube arrays. The vapor exchange may be carried out in a single treatment sequence or series of treatment stages. Either or both the vapor exchange rate and the ultimate vapor content of the material being treated may be controlled by suitable means as by adjusting the transport rate of material or the vapor flow rate or other parameters.In particular embodiments, tobacco reordering apparatus comprises an open top vapor chamber and a porous conveyor of the endless belt type of less than ten percent open area which conveys the tobacco through the treatment zone that is immediately above the vapor chamber. The belt conveyor seats on and encloses the top of the chamber. Water in the chamber is heated to provide an essentially saturated vapor zone immediately below the belt and the chamber is pressurized so that vapor flows upwardly through the pores in the belt in rapid and uniform moisturizing of the tobacco. Supplemental downwardly directed gas flows may be used to provide a stablizing influence on material such as bone dry tobacco and also to provide supplemental transport gas in the zone immediately above the material being processed.Other features and advantages of the invention will be seen as the following description of par- ticular embodiments progresses, in conjunction with the drawings, in which:Figure 1 is a perspective view of tobacco processing apparatus in accordance with the invention; Figure 2 is a cross-sectional view taken along the line 2-2 of Figure 1;Figure 3 is a diagrammatic cross-sectional view of another embodiment of processing apparatus in accordance with the invention; Figure 4 is a diagrammatic cross-sectional view of still another embodiment; andFigure 5 is a cross-sectional view taken along the line 5-5 of Figure 4.Description of Particular Embodiments The apparatus shown in Figure 1 includes stain¬ less steel chamber structure 10 that is about thirty inches wide, about one hundred thirty inches long, and about sixteen inches deep. Chamber 10 is mounted on supports 12. The top wall 14 of chamber 10 de- fines an elongated opening 16 (see Figure 2) that is about twenty inches in width and about one hundred twenty inches in length.Food grade endless belt conveyor 18 has upper run 20 that is seated on chamber top surfaces 14 and extends across opening 16 and a lower run 22. Belt 18 has a matrix of apertures 24 spaced about 1 1/2 inch on center across the width and along the length of belt 18. The size and spacing of apertures 24 determine the percent open area of the belt. The bel is supported by conventional support rolls 26 and driven by conventional means diagrammatically indicat at 28.Disposed above chamber 10 and belt 18 is an insulated housing structure 30 mounted on supports 32. That housing structure includes an elongated plenum 34 (Figure 2) in its upper section from which depends an array of elongated tubes 36 that extend downwardly towards conveyor 20. Apparatus of this general type is shown in U.S. Patents Nos. 3,060,590 and 3,229,377. Extending along either side of the array of tubes 36 is a wall member 40 about one hundred twenty inches in length. Wall members 40 are spaced about eighteen inches apart and define the side boundaries of a treatment zone 42, the base of which is defined by the upper run 20 of foraminous conveyor 18. The cross-sectional area of the passages defined by tubes 36 is about two percent of the cross-sectional area of the treatment zone 42, the tubes being arranged in transverse rows along the length of the treatment zone. Flexible wiping seals 44, carried by each wall 40 at its lower edge, engage the margins of conveyor run 20 and provide seals along the sides of the treatment zone 42. A flexible curtain 46 at each end of housing 30 defines an end boundary of the treatment zone 42.Connected to chamber 10 are five steam lines 50. Each steam line connection is spaced about four inches from the bottom of chamber 10. Water is supplied to the chamber over lines 52 and maintained at a level of about six inches. Lines 50 are connected to a source 54 of steam, and the flow of steam into the water 56 (Figure 2) creates high density vapor in zone 60 within chamber 10 above water 56 and immediately below foraminous conveyor run 20 that forms the upper bounding wall of chamber 10. Alternative or supplemental heating means may be used as desired. For example, it may be advantageous to provide supplemental heating coils within chamber 10 (as diagrammatically indicated in Figure 1) , and to control the density of vapor in zone 60 by controlli the heat input. In the side walls of the chamber 10 are ports 62 which are connected over lines 64 to circulation fan 66. Fan 66 receives air from dis¬ charge port 68 in the upper wall of housing 30 over line 70 and circulates air over lines 64 to ports 62 and over line 72 to plenum inlet port 74.Further aspects of the system may be seen with reference to Figure 2. The upper run 20 of conveyo 18 provides a foraminous member between vapor zone 6 in lower chamber 10 and treatment zone 42 in the upp chamber. Vapor zone 60 is pressurized by air flowin into ports 62 to create a gentle and continuous flow of water vapor up into the tobacco 80 on conveyor run 20. A supplemental air flow from tubes 36 is directed downwardly against the upper surface of the bed of tobacco 80. The gases are exhausted upwardly from the treatment zone through exhaust ports 76 tha extend along the length of a side wall 40 and throug riser 78 to discharge port 68. The air flow passage 62, 64, 72, and 74 are sized so that approximately equal amounts of air are distributed from circulatio fan 66 to the upper plenum 34 and to the vapor zone in chamber 10, fan 66 pressurizing the air to estab¬ lish a positive pressure within vapor zone 60.In operation, the tobacco 80 to be mosturized i continuously fed in conventional manner onto the inp apron 82 of conveyor 18 and formed into a bed of generally uniform depth. Conveyor run 20 transports this bed of tobacco through the conditioning zone 42 at a constant rate where the bed of tobacco is ex¬ posed to upward flow of vapor from chamber 10 and concurrent downward flow of air from passages 36.O The tobacco being processed in the conditioning zone 42 absorbs moisture rapidly and with excellent uni¬ formity. In a typical sequence, both the conditioned tobacco discharged from zone 42 and the belt 18 are at a temperature of about 130°F. The tobacco is then cooled to ambient temperature without extracting significant amounts of moisture.As an example, the moisture content of uncased cut leaf tobacco was increased from 1% to 24% in a single pass of nine minutes duration in apparatus as described above employing a transport belt 18 of about 2% open area. The uniformity of moisture con¬ tent of the reordered tobacco was excellent.In a typical sequence of processing Burley tobacco, the tobacco is dried by heating, which process simultaneoulsy reduces the moisture content of the tobacco. The dried tobacco is cooled and then reordered by raising its moisture content to the desired condition for further processing of the tobacco. In a sequence of processing cased Burley strip, the moisture content of the cased tobacco was •first reduced from about forty percent to about eight percent in a drying sequence and then increased to about eighteen percent in a reordering interval of about 2 1/2 minutes with apparatus as described above. Belt 18 had an open area of about four percent and the water 56 in chamber 10 was heated both by steam injected through conduits 50 and by steam flowing through supplemental coils in the tank. The uniformity of moisture content throughout the re¬ ordered tobacco was excellent.Other examples of processing tobacco with the apparatus shown in Figures 1 and 2 are indicated in the following table: Tobacco Type Cased Cased uncased Uncased Uncased Blended Blended Blended Burley Burley BurleyStrip Strip Strip Depth of Bed 80 (Inches) '4 4 4 4.5 3.5Temp, of Water 56 (°F) 150 150 152 170 150Open Area of Belt 18 (%) 8 8 8 8 8Treatment Time (minutes) 5 7.5 7.5 4.8 5Tobacco Moisture (% wet basis)-IN 0 0 0 0 0 -OUT 12.8 19 18 13 12.7Pressure—Plenum 34 (inches of water) .55 .6 .6 .5* 1.0*Pressure—Chamber 10 (inches of water) .65 .9 .8 .8 .25 *supplemental water vapor introduced into line 72Vapor zone 60 is at approximately the same temperature as water 56 and is essentially saturated, the dry and wet bulb temperatues being substantially equal.In those reordering sequences, both the condi- tioned tobacco and the upper run 20 of belt 18 are at a temperature of about 130°F at the outlet end of the apparatus.In a multiple pass reordering sequence with the apparatus shown in Figures 1 and 2, the moisture content of bone dry (0% moisture) tobacco was in¬ creased to thrity-five percent in four passes. In that sequence a two inch depth of bed 80 was employed, a water temperature of 150°F, a chamber pressure of 1/4 inch of water and no air flow through plenum 34. The moisture content of the tobacco after the first pass was fifteen percent, after the second pass twenty-five percent, after the third pass twenty-nine percent, and after the fourth pass thirty-five percent.Another embodiment is shown in Figure 3. That embodiment includes an insulated housing 130 having a chamber 110 at the base of housing 130 and ah upper plenum 134 with an array of elongated tubes 136 that extend through the lower wall 138 of plenum chamber 134. Endless belt conveyor 118 has an upper run 120 that forms a foraminous boundary wall to chamber 110 and a lower run 122. The treatment zone 142 is defined by upper conveyor run 120 and side walls 140. Flexible wiping seals 144, carried by each wall 140 at its lower edge, engage the margins of conveyor run 120 and provide seals along the sides of treatment zone 142. A body of water 156 is in chamber 110 and a similar body of water 158 is in plenum chamber 134. Heat is supplied to each body of water over steam line-s 150, 152 or by other suitable means so that a zone 160 of high density vapor is created above water 156 immediately adjacent foraminous member 120, and a similar vapor zone 162 is created above water 158 in plenum chamber 1'34.adjacent the upper ends of tubes 136 which provide a foraminous boundary between chamber 134 and treatment zone 142. Fans 166, spaced along the length of side walls of chamber 110 are driven by motors 168 and similar fans 172 driven by motors 174 are provided in the side walls of supply plenum 134. The resulting air flow pressurizes the two vapor zones 160, 162 to create gentle and con- tinuous flows of water vapor through foraminous structures 120, 136 for efficient vapor exchange with tobacco 80 in treatment zone 142, the gases from treatment zone 142 being exhausted through ports 180 at the upper ends of side walls 140 for closed path recirculation within insulated housing 130 to the UREAO PI . WIPO ^ i lower and upper sets of fans 166, 172. Condensate flows to sump 190 and condensate and make up water is circulated (with filtering if appropriated) to main¬ tain proper water levels in chambers 110, 134. Still another embodiment is shown in Figures 4 and 5. In that embodiment, three elongated tanks 210A, 210B, and 210C are provided within insulated housing 230. Associated with each tank is a conveyor 218 which has an upper run 220 that is seated on upper tank walls 214. Supplemental support bars (not shown) extend between tank wall members 214 to provide supplemental belt support Each tank 210 contains a body of water 256 that is heated appropriately as by steam lines 250 to provide a high density vapor zone 260 in the chamber between the water 256 and the foraminous boundary 220. Fans 268 in the tank side walls (driven by motors 270) circulate air within housing 230 into the vapor zones 260. Associated with each tank 210 is a treatment zone 242, the base of which is defined by foraminous upper conveyor run 220 and the sides of which are defined by walls 240 which carry appropriate seals 244 that engage the margins of conveyor run 220.With reference to Figure 4, tobacco 80 to be treated is supplied on the conveyor 270 to conveyor 218A for transport through treatment zone 242A. At the end of transport treatment zone 242A tobacco is transferred via guide plate 272 to transport conveyor 218B for passage through treatment zone 242B and then similarly transferred by means of guide, plate 274 to transport conveyor 218C for passage through treatment zone 242C. Throughout this opera¬ tion, fans 268 pressurize the high density vapor zones 260 to create continuous flows of water vaporO^SN up into the tobacco beds in the treatment zones with gases being exhausted upwardly over the tops of side walls 240 of the treatment zone for recirculation as indicated by the arrows. Condensate flows down the insulated walls of housing 230 to sump 276. The con¬ densate water may be recirculated after filtering if necessary and supplied as makeup water to the bodies of water 256 in chambers 210. Conveyor 218C extends through an evaporative cooler diagrammatically indicated at 280 for cooling the reordered tobacco which is then transferred to output conveyor 282.In a particular embodiment each treatment zone has a width of about four feet and a length of about thirty feet. Belts 218 have four percent open area. Chambers 210 have a width of sixty inches and a height of twenty inches and water 256 is maintained within chambers 210 at a depth of about three inches. The evaporative cooler unit 280 has a length of about ten feet. The invention provides particularly effective tobacco reordering processes and apparatus. The high density vapor zone in close proximity to the bed of tobacco and the gentle continuous flow of vapor into the tobacco bed efficiently, rapidly and economically reorders tobacco to moisture percentages of twenty percent and above without damage to the fragile tobacco leaf material.Various modifications will be apparent. For example, aromatics or flavorings may be included in aqueous solution in the vapor chamber. Liquids other than water may be used for vapor impregnation treat¬ ments or the like. Various material conveying mechanisms, including for example, oscillatory type conveyors, may be employed in other particular embodiments. Specific parameters such as the aperture size and the foraminous structure porosity may be varied depending on the specific material being processed. Therefore, while particular embodiments of the invention have been shown and described, it is not intended that the invention be limited to the disclosed embodiments or to details thereof and de¬ partures may be made therefrom within the spirit and scope of the invention. | Claims1. A vapor exchange process for tobacco and the like comprising the steps of: providing a treatment zone and an adjacent chamber separated from said treatment zone by foraminous structure, providing a body of liquid in said chamber, creating a zone of high vapor density in said chamber above said body of liquid and immediately adjacent said foraminous structure, con¬ veying the material to be processed through said treatment zone past said foraminous structure, and flowing vapor from said chamber through said foraminous structure into said treatment zone during conveyance of material through said treatment zone so that at least a major portion of the vapor flowed from said chamber through said foraminous structure is entrained by said material as it is transported through said treatment zone.2. A process according to claim 1 wherein said treatment zone is immediately above said chamber and material to be processed is conveyed in bed form through said treatment zone.3. A process according to claim 1 wherein a pressure differential across said foraminous structure is created by circulation of gas in a closed path to flow said vapor through said foraminous structure.4. A process according to claim 2 wherein said body of liquid is heated to create said zone of high vapor density and the vapor density in said vapor zone being in excess of eighty percent saturation at the water temperature of said liquid. 5. A process according to claim 4 wherein the pressure differential is in the range of 0.1-1.0 inch of water.6. A process according to claim 1 wherein the material to be treated is tobacco supported on said foraminous structure and further including the steps of moving said foraminous structure relative to said chamber to transport material through said treatment zone.7. A tobacco reordering process according to any preceed- ing claim wherein said liquid is water and is heated to create essentially complete vapor saturation at the water temperature immediately below said forami¬ nous structure.8. Vapor exchange apparatus comprising chamber structure for containing a liquid, means for creating a zone of high vapor density within said chamber structure, a treatment zone immediately adjacent said vapor zone, foraminous structure between said treatment zone and said vapor zone, and means for flowing vapor from said vapor zone through said foraminous structure for vapor exchange with material being transported through said treatment zone.9. Apparatus according to claim 8 wherein said vapor density in said chamber is at least eighty percent saturation at the temperature of the liquid in said chamber structure. 10. Apparatus according to claim 9 wherein said forami¬ nous structure has less than ten percent open area.11. Apparatus according to claim 10 wherein said forami¬ nous structure forms a top wall portion of said chamber structure.12. Apparatus according to claim 8 wherein said forami¬ nous structure forms a top wall portion of said chamber structure.13. Apparatus according to any of claims 8-12 and further including gas circulation means for creating a pressure differential across said foraminous structure to flow vapor through said foraminous structure into said treatment zone.14. Apparatus according to claim 13 wherein said circula- tion means creates a pressure differential in the range of 0.1-1.0 inch of water within said chamber structure.15. Apparatus according to claim 8 and further including a gas flow system for flowing gas downwardly against material in said treatment zone.16. Apparatus according to claim 15 wherein said gas flow system includes a supply plenum above said treatment zone, an array of tubes extending along the length of said treatment zone and across the width of said treatment zone and arranged for flowing gas from said supply plenum downwardly towards said treatment zone, and further including means for exhausting gas from said treatment zone upwardly away from said forami¬ nous structure.17. The apparatus according to claim 16 wherein said supply plenum is arranged for containing a body of water and further including means for creating a zone of high density water vapor within said supply pelnum, so that water vapor is flowed' downwardly against material in said treatment zone.18. Apparatus according to claim 8 and further including an insulated housing in which said chamber structure and said treatment zone are disposed.19. Apparatus according to claim 8 wherein said vapor creating means includes means for heating liquid.20. Tobacco reordering apparatus according to any of claims 8, 9, and 15-19 wherein said foraminous struc¬ ture is a moveable transport member that has a plurality of apertures of predetermined open area, the combined cross-sectional area of said apertures constituting less than about one tenth of the tobacco support area of said conveyor.21. Tobacco reordering apparatus according to claim 20 wherein the liquid in said chamber is water, said vapor creating means includes means for heating said water to create essentially complete vapor saturation at the temperature of the water in said chamber, said transport member is a conveyor of the endless belt type and each said aperture has a predetermined diameter, and further including gas circulation means for creating a pressure differential in the range of' UREOMPI XΉIΎ 0.1-1.0 inch of water within said chamber structure to flow water vapor through said belt conveyor into tobacco in said treatment zone. | WOLVERINE CORP | BUSKE W; HOYT C; THOMPSON A |
WO-1979000806-A1 | 1,979,000,806 | WO | A1 | EN | 19,791,018 | 1,979 | 20,090,507 | new | F24D11 | F24J3, B65D89 | F28D20 | F28D 20/00D | A METHOD OF STORING THERMAL ENERGY IN A GROUND STORAGE DEVICE | In a method of storing thermal energy in aground storage device (1) of large volume, including a ground body for circulating water in a circuit comprising passages (2) in said body, there are used heat-absorbing and heat-emitting means. The heat-absorbing means has the form of a large, natural or artificial watermass, such as a lake, sea-inlet or the like (5), whose water - heated to above a given temperature during warm periods of the year - is charged to the ground storage device (1). The supply of water to said ground storage device (1) is interrupted when there is equilibrium between the temperature of the water supplied (5) and the temperature of the ground storage device (1). | A METHOD OF STORING THERMAL ENERGY IN A GROUND STORAGE DEVICEThe present invention relates to a method of storing thermal energy in a ground storage device of relatively large volume, preferably in a ground storage device which is in direct thermal connection with the surrounding earth and which includes a ground body provided with passages through which water can be circulated in a circuit which includes said passages and external heat-absorbing and heat-emitting devices.An example of such storage of thermal energy is given in Swedish Patent Application No. 7612143-3. The heat- absorbing device primarily considered is a solar energy collector, by means of which thermal energy can be stored during the warmer .periods of the year, to be then taken out during the colder periods. As disclosed in the description of the said Swedish Patent Application, thermal energy must be charged to the device over several years before the storage device can be used to the fullest extent with re¬ spect to its economic yield, despite the fact that the ground storage need only be heated to a temperature mode- rately above the ground temperature, which may be 8°C , for example.Temporary solar energy collectors or special energy sources are required for a number of years to effect this initial heating of the storage device, which must be con- sidered to constitute an additional investment for ensuring that the storage device can be utilized efficiently within a reasonable period of time.The same circumstances prevail in the arrangement of other, similar, large ground storage devices. For reasons of an economic and practical nature, there is a limit to the size and costs that heat-absorbing devices intended for initially heating grund storage devices and maintaining the level of said heat may have, in order to reduce the prepara¬ tory time or to increase the capacity of such devices.OMPI An object of the present invention is to provide a solution to the problem, such as to enable a large quantity of heat of limited temperature to be supplied to a ground storage device of the kind described over short periods during the summertime at relatively low costs.This object is achieved by means of the invention, in accordance with which the heat-absorbing device has the form of large or artificial collections of water, such as lakes, sea-inlets, creaks, rivers, canals etc., having a temperature above a given minimum value, said water being charged to said ground storage device until, at latest, equilibrium is reached between the temperature of said wate and said device. In principle, this type of heat-absorbing device is also a solar energy collector, although it has integrated factor, insomuch as - subsequent to a fair delay during spring - it is active twentyfour hours a day for int the autumn months with a temperature of from 18 to 22°C. By applying different, simple methods, the water of such natural or artificial water masses can be heated to much higher temperatures, e.g. by covering part of the surface of such a water-mass with a layer of heat-insulating materi and supplementing said layer with means for heating the water therebeneath by known solar-energy collecting systems. Thus, by means of the invention, the initial heating of a ground heat-storage device can be accomplished rapidly and cheaply, and the temperature of said device maintained during the warmer periods of the year in a very efficient a economic manner. The only limitation of the initial heatin source used in accordance with the invention vis-a-vis a mo conventional type of solar energy collector is the tempera¬ ture, which is normally limited. This has small importance, however, for initial-heating purposes, and is of no impor¬ tance at all when the ground heat-storage device is to be used in areas where only relatively low temperatures are re quired, i.e. normally water-temperatures of up to 15-20°C i said device. As an example of such areas can be mentioned roads, sidewalks, precincts, football pitches which it is desired to keep dry and free from snow, and the heating of buildings sufficiently to protect against frost. The tempe¬ ratures achieved--.are also sufficient to improve the cultiva¬ tion of crops, algas etc., during the cold periods.In accordance with one embodiment of the invention, the drop of a water-course, for example, incorporated in the water-mass used, or the difference in level to a water-mass situated above the level of the ground. Heat-storage device can be utilized to transport the water from said mass to said device, thereby obviating the need for pumps. So that the invention will be more readily understood and optional features thereof made apparent, an exemplary embodiment of the invention will now be described with refe¬ rence to the accompanying schematic drawing.In the single figure of the drawing there is illu- strated a ground heat-storeage device 1 of the kind described and illustrated in Swedish Patent Application No. 76121H3-3, said device including a plurality of vertically extending mutually parallel pipes 2 which are connected to a common outlet line 3. Each of the pipes 2 has extending coaxially therein a respective inner pipe which is open at the bottom thereof, said inner pipes being connected in parallel to an inlet line H. The inlet line communicates with a lake 5 which is located at a higher level than the device 1, while the outlet line 3 communicates with a lake 6 located at a lower level than said device. The flow of water through the device 1 is regulated by means of valves (not referenced), which may be thermostat controlled, and no pumps are required. If pumps are used, however, it will be possible, of course, to move the water to and from the lakes 5 and 6. It is also possible to connect the lines 3 and 4 to a water-course located between the lakes 5 and 6.If the temperature of the water in lake 5 is too low, part of the surface of the lake can be covered with a buoyant layer 7 of insulating material, such as a plastics material optionally supplemented with auxiliary means for heating the water by -means of solar energy. Such means are well known.The ground heat-storage device may be arranged, for example, beneath the surface of a football pitch, thereby to enable the surface of the pitch to be kept dry from ice by heat derived directly from said device, at least during a greater part of the winter months. The pitch can thus be used much earlier in the spring than is normally the ca As shown in the figure, water may be pumped, by mean of a pump 8, around a circuit which includes the device 1 and a footpath 10.The invention is not restricted to the described and illustrated embodiment, but can be modified within the sco of the claims. | CLAIMS:-1. A method of storing thermal energy in ground storage devices of large volume, preferably in such a device which is in direct thermal contact with surrounding earth and which includes a ground body having passages for circulating water in a circuit which includes said passages and external heat- absorbing and heat-emitting means, characterized in that the heat-absorbing means has the form of a large water-mass, having a surface exposed to the sun, which water-mass may be a natural or artificial water-mass, and that water of a given minimum temperature is charged from said water-mass to said ground storage device until, at latest, equilibrium is reached between the water charged to said ground storage de¬ vice and said heat-absorbing means.2. A method according to Claim 1, characterized in that at least part of the surface of said water-mass is covered by a layer of heat-insulating material, and that measures are taken to heat the water beneath said layer by solar energy.3. A method according to Claim 1 or Claim 2, characterized in that the drop of a water-course forming part of the water-mass, or the difference in level between said water-mass and said device, is used to transport heated water to said ground storage device.O P | LILLIEHOEOEK F; PLATELL O; SUNROC ENERGY AB; WIKSTROEM H | LILLIEHOEOEK F; PLATELL O; WIKSTROEM H |
WO-1979000809-A1 | 1,979,000,809 | WO | A1 | XX | 19,791,018 | 1,979 | 20,090,507 | new | E01F9 | G09F13, E01F15 | E01F9 | E01F 9/015 | A REFLECTION DEVICE FOR ROADSIDE MARKING | A reflective roadside marking post, where the reflector (8) is protected from dirt by a tubular means (4) projecting in front of the reflector. The tubular means is by partition walls (6) divided into a number of axial channels or cells and the reflector (8) is visible through said cells. In order to make the reflector reachable for cleaning purposes it and/or the tubular means (4) is/are movable in relation to the post (1). | 'A REFLECTION DEVICE FOR ROADSIDE MARKINGBackground of the inventionThe present invention refers to a reflection device for roadside marking and of the type comprising at least one tubular means projecting in front of the reflector, said tubular means being intended to provide a stationary air cushion in front of the reflector.Reflection posts are used for improving the visual guiding in darkness on roads where a stationary road lighting is missing and contribute to essentially improve the traffic s fety, l^anv drivers have when driving in the dark felt the unpleasant feeling of' not surely knowing how the road is leading especially when they are dazzled or when the windscreen is spattered. Critical situations caused by this could* be avoided if the road boarders were marked with reflection posts. The reflection posts previously used have been affected by dirt verv soon, whereby the reflection ability is decreased, and the necessary cleaning is time-re¬ quiring and expensive.As examples of reflection posts where the reflective material is unprotected and therefore quickly is soiled can be mentioned the reflection posts .shown in the Swedish patent specifications 317.015 and 366.081.In the Swedish patent specification 378.631 is shown a reflection post, where the reflector is placed in and protected by a tube and where the tube portion projecting in front of the reflector is of a sufficient length for the provision of a protecting air cushion in front of the reflector. The reflector is further- more removable from the tube in order to facilitate the cleaning. Comparative tests initiated by the National Swedish Council for Road Safety Research with other reflection posts have clearly proved the superiority of this reflection post regarding need of cleaning and visibility. The visibility was about 3 times higher than for the next best reflection post while the need of cleaning was only 1/3 than for the other posts.By e.g. the Swedish patent specification 55.2-40'and the US patent specification 1.659.^09 it is previously known to arrange in front of car headlights a device comprising a great number of cells with a relatively high ratio length/diameter. The light beams from the headlights are thereby prevented from diverging to any essential extent and the dazzling effect from the headlight is prevented.Thus these publications describe devices for delive¬ ring light while the present invention refers to a device for reflecting light. These two previously known devices would not be applicable for the pur¬ pose of the present invention, viz. to prevent the reflector from being affected by dirt and retaining a good reflection ability. The device described in the Swedish patent specification 55.2*40 has a far too high ratio between length and dimeter of the cells, for achieving any practically usuable reflection ability. The device described in the US patent speci¬ fication 1. 5 . 09 can on the other hand not act as a soil protection, since there is an opening between the headlights and the device and no air cushion which would prevent soiling can therefore be formed.Summary of the inventionThe purpose of the invention is to provide a reflec¬ tion post of the type described in the introduction, vjthich has the advantages of providing a prevented or delayed soiling and simple cleaning of the reflec¬ tor at the same time as' the length of the tubular means is considerably reduced. This has according to the invention been achieved thereby that the tubu¬ lar means and/or the reflector is/are moveable in relation to a supporting housing and that the tubular means is divided into a number of substantially axial channels by means of partition walls.By dividing the tubular means into several axial channels the length of the tubular means can be considerably reduced retaining the air cushion effect, which prevents or delays soiling of the reflector.Description of the drawingsThe invention will now be further described with refe¬ rence to some embodiments shown in the accompanying drawings.Figure 1 is a perspective exploded view of the upper part of a post with reflection device,Figure 2 is an analogue view of a modified reflection device according to the invention,Figure 3 is a section through a further embodiment of the invention,Figure is a section along line IV - IV in figure3, Figure 5, 6 and 7 are horizontal setions through further embodiments of the reflection device, Figure 8-1-4 are side, front or perspective views of different types of reflection devices according to the invention, Figure 15 is. a vertical section through another embodi¬ ment of the reflection device, Figure 16 is a front view of a further embodiment of the reflection device,Figure 17 is a section on a larger scale along lineX - X in figure 16,Figure 18 is a vertical section through a further embodiment of the reflection device,Figure 19 is a section along line XII - XII in figure18.Description of some embodimentsThe roadside marking post according to the embodiment shown in figure 1 is denoted with the numeral 1 and comprises a tube, which at its upper portion is pro¬ vided with a rectangular opening 2 and on the oppo- site side with two circular openings 3. Through the upper open end of the post 1 a dirt protection means •4 is insertable. Said dirt protection means *4 com¬ prises an outer frame 5, which by means of a number of partition walls 6 forms a tubular means comprising a number of cells, whereby the length of each cell is at least equal to half the inner cross-section of the cell. The end of the frame 5 located in front of the openings 3 has a projecting lip 7, against which a reflection plate 8 is intended to abut. The reflec- tor 8 is visible through the rectangular opening 2 through the cells of the tubular means -4 as well as through the circular openings 3. At one of the short ends of the tubular means 4 is provided a plate 10, which when the tubular means is inserted in the post forms a termination or cover of the post 1.When the reflector 8 is to be cleaned the tubular means -4 is pulled out of the post, so that the reflector can be removed.The embodiment shown in figure 2 differs from the embodiment of figure 1 by the fact that the tubular means -4 is provided with a rear end wall 9> which at its lower end is connected to the tubular means •4. An aperture for the reflector is formed between the end wall 9 and the tubular means 4. In the end wall 9 are provided two circular holes 11 intended to be arranged just opposite the openings 3 in the post 1. The tubular means 4 is pushed down in the post 1 until it abuts a stop 12 in the post. The length of the reflector 8 exceeds the depth of the aperture 11, so that a grip end is provided. When cleaning the reflector 8 the tubular means 4 can be left in the post 1. The tubular means 4 can possibly be fixed to the post 1 in any suitable way, e.g. by screws. A removable cover 13 is provided as an end termination of the post.In the embodiment according to figures 3 and 4 the tubular means 4 can be inserted through side openings 14 and 15 in the post 1. The tubular means has prin- cipally the same design as the one shown in figure 2, but it is furthermore provided with a stop edge l6 limiting the insertion of the tubular means 4 in the post 1. The tubular means is secured against dis¬ placement on one hand thereby that the reflector 8 projects somewhat above the tubular means and on the other hand thereby that the cover 13 for the post is provided with locking pins 17 cooperating with corresponding recesses 18 in the tubular means 4.According to this embodiment it is only required that the cover 13 is removed for making it possible to reach the reflector 8 for cleaning. If also the tubular means 4 has to be cleaned it can easily be removed from the post after removal of the reflector.In the embodiment according to figures 5 and 6 the tubular means is inserted through a side opening in - the post 1. The tubular means 4 has a border 19 gripping round said side opening in the post and thus limiting the insertion of the tubular means in the post. The tubular means 4 is secured to the post 1 e.g. by screws or snap-in members.The reflector 8 is kept in place by a cover 20, which is snapped on the tubular means 4. In the embodiment according to figure 5 the tubular means 4 does not extend right through the tube 1, but only a part into it, whereas in the embodiment according to figure 6 the tubular means 4 extends through the post and out through a side opening in the opposite side of the post. A second reflector 21 is placed in a recess on the outside of the cover 20.In order to reach the reflectior 8 for cleaning pur¬ poses it is in the embodiment according to figure 5 necessary to remove the tubular means 4 through the side opening and the cover 20 from the tubular means. In the embodiment according to figure 6 is it . sufficient to remove the cover 20 from the tubular means 4, whereby the reflector 8 can be reached.In the embodiment according to figure 7 an insert22 is placed in the side opening in the post 1, said insert 22 having a border 23 gripping round the side opening. The insert 22 is fixed to the post 1. The tubular means 4 can be detachably secured to the in- sert 22, e.g. by means of beads 23 which are pressed into openings or cavities in the insert. The reflec¬ tor 8 is secured between the insert 22 and the tubu¬ lar means 4 and can be reached for cleaning by removin the tubular means from the insert.In the embodiment according to figures 8-15 the reflec¬ tor 8 is fixed to the post 1 close to the upper end thereof. Such reflection posts are common .in many countries, but have as previously suffered from the drawback of being dirty very quickly, whereby the reflection ability is considerably decreased. In order to avoid this a dirt protection comprising a tubular means 4 of the above mentioned type is placed in front of the reflector 8.In order to facilitate cleaning of the reflector 8 the tubular means 4 must be removed, which can be made in many different ways. In figures 8 and 9 the tubular means 4 is pivotally mounted to a bracket 24, which is placed above the reflector 8. The tubular means 4 can easily be pivoted upwards as shown in figure 9» thus leaving the reflector 8 free for cleaning. The tubular means 4 is preferably detachably secured at its lower edge to the reflector 8 or the post 1 e.g. by snap action.In the embodiment according to figure 10 the tubular means can be snap-locked round beads 25 at the upper and lower edges of the reflector 8.In the embodiment according to figure 11 the tubular means 4 is pivoted about hinges at one of its long sides and in figure 12 the tubular means is pivoted about a hinge 26 at its upper edge.In the embodiment of figure 13 the tubular means 4 can be pushed down in front of the reflector 8 in guides and be removed by pulling it upwards. The same applies for the embodiment according to figure 14, but here the tubular means 4 is connected with a cover 27 forming an end termination of the post 1. In the embodiment according to figure 15 the cover 27 is pivotallv connected to the tubular means -4. The embodiment according to figures 16 and 17 differs from the above described embodiments by the fact that the reflector or reflectors 8 are secured to a member 28 projecting from the post 1, which in this case has a triangular cross-section, said member 28 having shoulders 29 on opposite sides behind which shoulders a pair of partition walls 6 of the tubular means 4 grip. The tubular means -4 comprises two halves, arranged on opposite sides of the member 28 in front of the reflectors 8 and which can he turned about beads 30 and mke the reflectors 8 free for cleaning. The reflec¬ tion device can be manufactured as a separate unit, which can be attached to an ordinary post.In the embodiment according to figures 18 and 19 the reflector or reflectors 8 are in the same way as in figures 16 and 17 fixed to the member 28 projecting from the post 1, which in this case has a circular cross-section, said member 28 being screwed 31 to the post 1. The tubular means 4 is integrally connected with a portion 32 projecting down into the post 1, said portion 32 having an attachment 33 for a spring 34. The spring 3 is at its opposite end connected to an attachment 35 in said member 28. The tubular means 4 and the connected portion 32 can be pushed downwards in the post 1 against the action of the spring 34, whereby the reflectors 8 are free for cleaning.An automatic cleaning would in this case be possible, where a device with rotating brushes is placed on the tubular means 4 pressing this downwards and simul¬ taneously cleaning the reflectors 8. The tubular means 4 automatically returns to its initial position when ' the pressure from the device with the rotating brushes is interrupted. Th >e invention is not limited to the embodiments de- scribed above but can be varied within the scope of the claims. | . .1. A reflection device for roadside marking and of the kind comprising at least one tubular means projecting in front of the reflector and being supported by a post, said tubular means being intended to provide a stationary air cushion in front of the reflector and being removeable from the reflector for making this accessible for cleaning purposes, c h a r a c t e r i z e d i n, that the tubular means (h) is divided into a plurality of substantially axial channels by means of partition walls (6), whe in each channel the ratio between the axial length of the channel and the inner transverse dimension of the channel is at least 1:2 and does not exceed a limit determined by road safety demands concerning the largest angle of incidence at which the light towa the device is re lected and that the post ( 1 ) is provided with guide means for the tubular means (4), which is insertable or fittable into the post, so that it at least substantially is rece within the limiting surfaces of the post or its imaginary extensi2. A reflection device according to claim 1, c h a r a c t e r z e d i n, that the tubular means (h) is insertable into the post(l) through an open upper end thereof to a position where it at least substantially is received within the post and that the reflector (8) is held behind the tubular means within the post an is removeable from the post.3. A reflection device accordning to claim 2, c h a r a c t e z e d i n, that means (7;9) for detachably holding the reflector(8)' are arranged at one end or side of the tubular means (4).k . A reflection device according to claim 1, c h a r a c t e z e d i n, that the tubular means (k) is insertable through a sid opening in the post (l) to a position where it at least substa ially is received within the post and that the reflector (8) is behind the tubular means within the post and. is removeable from t post . 5. A reflection device according to claim 1 , c h a r a c t e r ! - z e d i .n, that the re lector .or reflectors (8) is/are attached to a member (28) projecting upwards from and being fixed to the post (l), that the tubular means (k) in one position is arranged in front of the reflector or reflectors and in this position together with said member (28) projecting from the post form an extension of the post with substantially the same cross-sec¬ tional shape as this and in another position is arranged to expose the reflector or reflectors for cleaning purposes.6. A reflection device according to claim 5> c h a r a c t e r i ¬ z e d i n, that the tubular means (4) is hingedly mounted at the post (1) and can be swung from a position in' front of the reflector or reflectors (8) to a position where the reflector or reflectors is/are exposed and vice versa.7- A reflection device according to claim 5. c h a r a c t e r i ¬ z e d i n, that the tubular means ( -4 ) against the actions o±* a spring (13) -- displaceable downwards in \.hθ post (l) to a. position where the reflector or reflectors (8) is/are exposed. | BJOERLUND J | BJOERLUND J |
WO-1979000810-A1 | 1,979,000,810 | WO | A1 | XX | 19,791,018 | 1,979 | 20,090,507 | new | A01G25 | null | A01G25, B05B17 | A01G 25/09C | A SELF-PROPELLED IRRIGATOR | A self-propelled irrigator comprising a reel on which a hose is wound up. The water supplied through the hose is fed into chambers (p) in a driving wheel (a) from a water outlet (i) located in front of the vertical, diametral plane of the driving wheel when seen in the moving direction. The chambers are defined by side walls in the driving wheel (a) and partitions connecting said walls. hese partitions are curved backwards in the direction of rotation relative to the wheel radii and form guiding plates guiding overflowing water from a filled upper chamber into the preceding chamber for accumulation of the driving power. The chambers comprise narrow inlet slots forming flow restrictors for water flowing out of the chambers carried over the rear alf of the wheel. As a result these chambers not yet emptied provide a braking effect necessary on hilly grounds. | Technical FieldThe present invention relates to a self-propelled irrigator for irrigation of row crops, lawns, and the like areas, and comprising a hose wound up on a reel, water from a statio- nary tap flowing through said hose to a nozzle unit such as a sprinkler and to an outlet through a driving wheel com¬ prising containers along its periphery, said containers be¬ ing supplied with water when they are in an uppermost posi¬ tion in front of the vertical, diametral plane of the wheel and releasing water during the movement past their lowest position.Background ArtGerman patent specification No. 215,616 discloses an irri¬ gator comprising a water distributing pipe situated between two driving wheels. Along the periphery these driving.wheels comprise tiltable cups, which are supplied with water when they are in their uppermost position and emptied when they hit a stop in their lowest position and thereby tilt. These known cups are therefore only filled with water when they are in a particular uppermost position, which, especially when the apparatus is being started, involves an insuffi¬ cient or no propellant moment. Furthermore, the mechanical tilting of the cups in their lowest position involves a sud¬ den emptying which does not provide a necessary braking ef- feet when the apparatus moves downhill. Consequently, the apparatus moves forwards at an uncontrollable speed, to which must be added that these tiltable cups are expensive to ma¬ nufacture and to keep in repair.Disclosure of InventionThe object of the invention is to provide an inexpensive apparatus of the above type, which ensures a more regular and a more powerful propulsion compared to these known appa- ratuses in such a manner that the apparatus according to t invention - in spite of the considerable and varying load from a hose wound up on the reel - can move forwards at a uniform speed even on a slightly hilly ground, and which furthermore permit a uniform irrigation with, controllable amounts of water.The self-propelled irrigator according to the invention is. characterised in that the containers are chambers separate by partitions curved backwards in the direction of rotatio relative to the wheel radii, said partitions connecting tw side walls perpendicular to the wheel axis, and whereby th outer portions of said partitions form guiding plates in¬ clining towards the wheel axis in such a manner that they can guide the trickling or overflowing water into a narrow slot at the trailing edge of the partition ahead of the di rection of rotation when the chambers are in their uppermo positions in front of the vertical, diametral plane of the wheel when seen in the driving direction, and furthermore such a manner that the inlet slots turning downwards on th rear half of the wheel form flow restrictors for the outfl wing water.The driving wheel can be inexpensively manufactured, e.g. plastics, and requires no maintenance. In addition, a unif irrigation of the area is obtained since the apparatus mov forwards by a considerably power and at a uniform speed, a so when moving on hilly grounds. The constant, controllabl jet of liquid through theOutlet fills the chambers on the front of t wheel, since the water — when the uppermost chamber at the start is filled - flows into the preceding chamber and - w this chamber has been filled - forwards to the next chambe situated therebelow etc. , unti 1 the torque is sufficient f driving the wheel forwards. Subsequently, the chambers are slowly emptied at the back of the wheel,which provides a necessary braking effect and consequently a uniform, stepwi operation. The wheel is influenced by imbalance implyingO that the wheel moves forwards at regular intervals each time a plurality of chambers have been filled. Then the water flows out, and the wheel stops until a corresponding plura¬ lity of new chambers has* been filled. The slow emptying of the chambers implies that the tendency of the wheel to roll faster when driving downhill is counteracted because a higher number of not yet emptied chambers are carried to the rear half of the wheel. By regulating the water flow through the outlet to the chambers, the driving speed of the apparatus and consequently the amount of water supplied to the ground can be regulated.In order to guide the water safely downwards to the prece¬ ding chamber and in order to avoid waste of water, it is according to the invention preferred that the side walls.of the driving wheel extend radially past the free trailing edges of the partitions.For smaller lawns it is completely sufficient that the appa¬ ratus comprises only one driving wheel at one end of the wheel axis and a general supporting wheel of the same diame- ter at the opposite end of the axis. However,- for irrigation of row crops and larger grass areas in parks and sports grounds, a driving wheel can be provided at both ends of the wheel axis. The wheels may furthermore be displaceably arranged on the wheel axis whereby their mutual distance can be changed.In an embodiment of the irrigator according to the inven¬ tion a predetermined wheel diameter provides an increase of the tractive capacity for propelling the apparatus, and this embodiment is according to the invention characterised in that the driving wheel forms part of the reel, on which the hose is wound, and the width of which corresponds substan¬ tially to the width of the reel. Since the driving wheel is built into the reel, it may have a considerable width where¬ by the chambers may contain a correspondingly high amount of water providing a heavy torque.In a simple and inexpensive embodiment of the apparatus ac¬ cording to the invention, the reel itself forms the driving wheel and comprises closed end bottoms provided with, edge portions projecting radially outwards from the reel cylinde and forming road wheels, and whereby at least one of said edge portions together with- an additional jradial flange de¬ fine a groove located under the water outlet, said groove communicating freely with the chambers of the driving wheel the partitions of said chambers forming paddle blades ex¬ tending from end bottom to end bottom within the reel. Reel bearings and particular road wheels are not necessary in such a construction, and since the diameter of the reel nee not be smaller than the diameter of the road wheels it is possible to wind up a relatively long hose on the reel, sai reel thereby driving directly on the hose or on the edge portions of the end bottoms projecting outwards.When the hose reel itself forms the driving wheel, it is according to the invention preferred that the portion of the reel on which, the hose is wound up is surrounded by a cylindrical jacket protecting the chambers between the paddle blades against fouling.This cylindrical jacket may according to the invention be radially spaced from the ends of the paddle blades forming the partitions of the chambers. As a result, the water can flow quickly through the chambers as well as said chambers can be easily cleaned by rinsing with water.Brief Description of DrawingsThe invention will be described below with reference to the accompanying drawings, in whichFig- 1 is a front view of an embodiment of the irrigator according to the invention.Fig. 2 is a side view of the driving wheel of the apparatus, whereby a side plate is removed.Fig. 3 is a front view of a second embodiment of the appa- ratus according to the invention.Fig. 4 is a perspective view of a third embodiment of the irrigator according to. the invention.Fig. 5 is a sectional view through the reel taken along the arrows II-II of Fig. 4,Fig. 6 is an axial, sectional view through a fourth embodi¬ ment of the irrigator, whereby the reel is not provided with a cylindrical jacket, andFig. 7 is an axial, sectional view through a fifth embodi¬ ment of the irrigator according to the invention.Best Mode for Carrying Out the InventionThe irrigator illustrated in Fig. 1 comprises a driving wheel a formed by two side plates. A plurality of chambers £ regu¬ larly distributed about the axis, cf. Fig. 2, is situated between these two side plates. Each of these chambers is closed towards the centre of the wheel by an end wall ex¬ tending into a partition curved radially backwards in the direction of rotation. This partition ends up in a wall por¬ tion inclining backwards, an inlet slot for water being shaped at the free trailing edge of said wall portion. The substantially radial walls may also be formed as continuous paddle blades curved backwards.The driving wheel a is unpivotably mounted at the end of a pipe b forming a wheel axle, at the opposite end of which aMPI 'IPO fixedly mounted supporting wheel c is provided, the diamete of which corresponds to the diameter of the driving wheel A reel d is rotatably mounted on the pipe b, and a water hose s_ is wound up on the reel. This hose is connected to tap at the end of the area to be irrigated. Such taps may for instance be situated on a pipe at regular intervals of about 20 m, said pipe being located at the end of the law or field with crops to be irrigated. The end of the hose wound up on the reel is connected to a branch f_ turning fo wards in the direction of travel in such a manner that th reel unwinds the hose from under the apparatus, so that s hose does not impede forward movement. The branch f_ is mou ted on a swivel ~^_ located above an aperture in the pipe thus permitting inflow of water from the hose to the inte rior of the pipe. The pipe b_ also comprises a swivel e opp site a second aperture in the pipe wall, and through this aperture water is carried through a pipe to a sprinkler irrigating the area. The pipe £ furthermore comprises a branch pipe having an outlet, through which water is made to flow downwards into the front and uppermost chambers' p_. First this uppermost chamber is filled, whereafter the wa ter flows on the outside of the chamber wall downwards int the preceding chamber etc. until the driving wheel a has such an imbalance that it turns forwards, and the water in the lowest chamber starts to flow out, whereafter the whee stops until the imbalance is sufficiently great to drive t wheel forwards. The pipe i. may optionally be provided with a valve or a cock regulating the outflow of water to the chambers and consequently the speed of the apparatus acros the ground. The swivel e comprising the outlet i and the sprinkler k is at its lowest end provided with a rod h. A moving wheel is mounted on this rod in such a manner tha it is always ahead of the apparatus and maintains the pipe in a vertical position.The rod h and the wheel may advantageously be replaced b a U-shaped yoke trailing backwards and simultaneously servOMP as a handle. During the forward movement, this yoke slides on the rod, which provides a minimum friction and prevents the apparatus from being stopped by holes in the ground.This embodiment as well as other embodiments of the appara- tus according to the invention have the advantage that the water supply to the sprinkler and to the propellant means can easily be regulated independent of each, other. This means that the apparatus can also be used as a stationary irriga¬ tor. Furthermore, the irrigation is independent of th-e water pressure since a rise in the pressure involving a faster propellant speed implies that a correspondingly higher amount of water is irrigated from the sprinkler.The embodiment of the apparatus illustrated in Fig. 3 is particularly intended for large parks, sports grounds, and for irrigation of row crops in market gardens. In this em¬ bodiment, driving wheels a and sprinklers k are provided on both sides of the apparatus. Furthermore, the driving wheels are adjustably mounted in axial direction on axial extensions n, which also applies to the front wheels r displaceably mounted on axles o_. The pipe comprising the outlet i for supply of water to the chambers in the driving wheels may be correspondingly extended.In the embodiment illustrated in Fig. 7 the reel d is rotat- ably mounted on an axle b unpivotably connected to the road wheels and the driving wheel a_, the diameter of which is slightly smaller than the inside diameter of the reel. The width of the driving wheel a is only slightly smaller than the inside width of the reel, and the long water chambers provide a considerable torque on the road wheels when filled with water. The water supplied through the hose to the con¬ necting branch f_ flows through a conduit u via a swivel e and a vertical conduit to a sprinkler k and an outlet i.. Subsequently, the water flows down into a groove outside the reel d and through apertures in the bottom of the groove down into the chambers of the driving wheel. In the embodiment illustrated in Figs. 4 to 6, the water also flows from the connecting branch f_, cf. Fig. 6, thro the conduit u via the swivel e_ and the conduit £ to the sprinkler k and the outlet _i. Subsequently, the water flo down into the groove defined by an edge portion £ project outwards from the closed end bottom of the reel and a rad edge flange v situated inside said end bottom. The groove open towards the chambers £ of the driving wheel a, said chambers being defined by the end bottoms of the reel and substantially radial, however curved, paddle blades x as well as an inner cylindrical pipe b_. Here the reel is ut lized as driving wheels in its entire width out to the ed portions £ forming road wheels. These paddle blades may, course, also be assembled in another manner at their inne edges, a transverse pipe or an axle at the centre of the reel not necessarily being provided.In the embodiment illustrated in Fig. 6 the chambers £ ar open outwards along their entire length., and the paddle blades x are secured to the end bottoms, the edge portion £ of which projecting outwards forming road wheels. The e bottom illustrated left in Fig. 6 co-operate with the edg flange v in preventing the hose from rolling out over the reel ends. If desired, an edge flange v may also be provi ded at the end bottom illustrated left in the Figure, whe by a groove is formed, which is supplied with water from additional outlet JL.In the embodiment illustrated in Figs. 4 and 5, the porti of the reel on which the hose is wound up is surrounded b a cylindrical jacket y protecting the chambers against fouling. | AMENDED CLAIMS(received by the International Bureau on 20 August 1979 (20.08.79))1. A self-propelled irrigator for irrigation of row. crops, lawns, and the like areas, and comprising a hose (s) wound up on a reel, water from a stationary tap flowing through 5 said hose to a nozzle unit (k) such as a sprinkler and to an outlet (jL) through a driving wheel (a) drivingly connec¬ ted to ground wheels and comprising containers along its periphery, said containers being supplied with water when they are in an uppermost position in front of the vertical, 0 diametral plane of the wheel and releasing water during the movement past their lowest position, characteri zed in that the containers are chambers (£) separated by parti¬ tions curved backwards in the direction of rotation relative to the wheel radii, said partitions connecting two side walls 5 perpendicular to the wheel axis, and whereby the outer por¬ tions of said partitions form guiding plates inclining to¬ wards the wheel axis in such a manner that they can guide the trickling or overflowing water into a narrow slotat the trailing edge of the partition ahead of the direction of 0 rotation when the chambers are in their uppermost positions in front of the vertical, diametral plane of the wheel when seen in the driving direction, and furthermore in such a manner that the inlet slots turning downwards on the rear half of the wheel form flow restrictors for the outflowing 5 water.2. An irrigator as claimed in claim .1, character i z ed in that the side walls of the driving wheel (a) extend radi¬ ally past the free trailing edges of the partitions.3. An irrigator as claimed in claims 1 and 2, charac- 30 t eri z ed in that the driving wheel (a) forms part of the reel (d) , on which the hose (s) is wound, and the width of which corresponds substantially to the width of the reel.4. An irrigator as claimed in claim 3, c h a r a c t e - r i s e d in that the reel itself forms the driving whee (a.) and comprises closed end bottoms (c) provided with, ed portions (£) projecting radially outwards from the reel c linder and forming wheels, and whereby at least one of sa edge portions together with an additional radial flange ( define a groove located under the water outlet (_i) , said groove communicating freely with the chambers (£} of the driving wheel [a] , the partitions of said chambers formin paddle blades (x) extending from end bottom to end bottom in the reel.5. An irrigator as claimed in claims 3 and 4, c h a r a t e r i _s e d in that the paddle blades (x) are surround by a cylindrical jacket (y) forming the hose-receiving sur face of the reel adjacent the water-receiving groove.6. An irrigator as claimed in claim 5, c h a r a c t e r i s e d in that the cylindrical jacket (y) is radially spaced from the ends of the paddle blades (x) .ξϋROM Π - STATEMENTUNDERARTICLE19In view of US, A 1507506 cited in the international novelty re¬ port, claim 1 should be amended as follows:In line 6: before comprising should be inserted: drivingly connected to ground wheels and .OM.PI | GROENNELYKKE SVEN; GRONLYKKE S | GRONLYKKE S |
WO-1979000813-A1 | 1,979,000,813 | WO | A1 | EN | 19,791,018 | 1,979 | 20,090,507 | new | H01L31 | H01L31, C25D11, C25D5 | H01L31 | H01L 31/068 | SHALLOW-HOMOJUNCTION SOLAR CELLS | Improvements in shallow-homojunction solar cells based upon a plurality of layers of a direct gap semi conductor material such as GaAs, as well as their fabrication, are disclosed. The shallow-homojunction solar cells have a n+/p/p+ structure (26, 24, 22) in which the n+ top layer (26) is limited to a thickness which permits significant carrier generation to occur in a lower semiconductor layer (24). An antireflection coating (28) is applied over the n+ top layer (26), and a particularly preferred method for applying the antireflection coating is by anodization. These solar cells can be grown on relatively inexpensive substrates, if desired, such as silicon or germanium. | DESCRIPTIONSHALLOW-HOMOJUNCTION SOLAR CELLSGovernment SupportWork relating to this invention was supported by the United States Air ForceRelated Application This is a continuation-in-part of Serial No. 889,078, filed March 22, 1978.Technical Field This invention is in the field of homoiunction photovoltaic devices, including solar cells.Background ArtSolar cells have been developed for generating electrical energy directly from sunlight. In general, these cells can be classified as either heterojunction devices, which depend upon junctions such as those formed between two different semi¬ conductor materials or between a metal and a semi¬ conductor or from a metal/insulator/semiconductor sandwich, and homojunction devices which depend only upon junctions formed between layers of the same semiconductor material doped to different impurity levels to provide different electrical properties. - 2 -Heretofore, homojunction cells using direct-gap semiconductor materials have generally exhibited dis¬ appointing efficiencies. One reason for the relativel low efficiencies in homojunction solar cells is be- lieved to be the high absorption coefficient which is inherent in direct gap semiconductor materials such as gallium arsenide. For example, approximately half of the carriers due to AM 1 radiation are gen¬ erated within 0.2 um of the surface of gallium ar- senide. Therefore, for materials such as GaAs, which also has a high surface recombination velocity, most of the carriers generated by solar radiation recombine before they reach the junction causing a significant decrease in conversion efficiency. One approach which has been used to overcome this problem has been the use of a thin window layer of gallium aluminum arsenide (Ga-^_.χAlχAs) grown over the G-aAs wafer by liquid phase epitaxy. Such cells may be referred to as heteroface cells. Because the recombination velocity is much less at a Ga^-jAl^s/GaAs interface than at a GaAs sur¬ face, higher conversion efficiencies have been achieved. Thus, Hovel and Woodall report conversion efficiencies of up to 22% for hetero- face solar cells but only up to 14% for GaAs homojunction solar cells for air mass 1 (AM 1) radiation. See Hovel and Woodall, J. M. , 12th IEEE Photovoltaic Specialists Conf., 1976 (Institute of Electrical and Electronic Engineers, New York, 1976), p. 945. Nevertheless, aluminum is so reactive in the vapor phase that it is difficult to prepare high quality Ga,_ Al As layers by conventional chemi¬ cal vapor deposition, which is a highly preferred fabrication method. Because of this, it has been necessary to grow Gaι_χAlxAsx layers by metal- organic chemical vapor deposition. See Dupuis, R. D., Dapkus, P. D., Yingling, R. D. and Moody, L. A., Appl. Phys. Lett., 31, 201 (1977). This method can be both more expensive and more time consuming than conventional chemical vapor depo¬ sition. Disclosure of the Invention This invention relates to improved shallow- homojunction photovoltaic devices and methods for their fabrication. These shallow-homojunction de¬ vices are based upon a plurality of layers of direct gap semiconductor materials suitably doped to pro- vide an n +/p/p+ structure. An antireflection coat¬ ing is applied over the n top layer and the n top semiconductor layer is also limited to a thick¬ ness within the range which permits, upon light irradiation, significant carrier generation to 4- occur in the p layer below the n top layer.Thus, the top junction is referred to as a shallow- junction.In a particularly perferred fabrication method, the antireflection layer deposited on the n+ top semiconductor layer is formed by anodization. The anodic layer forms an excellent antireflection coating and requires no vacuum processing. Addi¬ tionally, the anodization process serves to reduce the thickness of the top semiconductor layer without resulting in significant surface degradation.Thus, homojunction solar cells can be provided which have conversion efficiencies approaching those obtainable with heteroface cells. Fur- ther ore, the use of a Gaι_xAlxAs layer is avoided which eliminates a relatively complicated and ex¬ pensive step in the overall fabrication of a solar cell. Still another significant advantage of the photovoltaic devices described herein is the ease with which ohmic contacts can be applied to them since they have high concentrations of dopants in their outer layers. This is particularly important because shallow homojunctions can have their junction qualities destroyed by attempts to form ohmic con¬ tacts at elevated temperatures. With this device, ohmic contacts can be applied by directly plating a metal layer on the semiconductor surfaces without elevated temperatures so that the junction quality is preserved.These shallow homojunction solar cells addi¬ tionally possess vastly superior resistance to degradation by electron bombardment than either Ga1_χAl As heterojunction cells or shallow homojunc¬ tion GaAs cells having a p top layer. Because of this, the shallow homojunction cells described herein have great potential for use in space applications. The heavily doped p+ layer additionally enables excellent solar cells to be grown on substrate mat¬ erials other than the host semiconductor materials, i.e., the semiconductor material which absorbs sun¬ light and generates electrical current.Gallium arsenide solar cells, according to this invention, have been grown on gallium arsenide and germanium substrates with equally outstanding effi¬ ciencies of over 20% at AM 1. Brief Description of the DrawingsFIG. 1 is a cross-sectional elevational view of a typical prior art solar cell employing a thin Ga-^xAlxAs window; FIG. 2 is a cross-sectional elevation view il¬ lustrating one embodiment of a solar cell according to this invention;FIG. 3 is a cross-sectional elevation view of another embodiment of a solar cell according to this invention;FIGS. 4(a) and 4(b) are schematic illustrations of the application of gold contacts to a solar cell of this invention;FIGS. 5(a) and 5(b) are schematic illustrations of the application of tin contacts to a solar cell of this invention;FIG. 6 is an exploded cross-sectional view illustrating the area around one contact finger of a solar cell fabricated according to this invention; FIG. 7 is a plot of data illustrating the quantum efficiency at varying wavelengths for a solar cell fabricated according to this invention;FIG. 8 is a plot comparing measured reflectivity to theoretical reflectivity for an anodic anti- reflection layer applied to a GaAs shallow-homojunc¬ tion device according to this invention;FIG. 9 is a plot of data illustrating the quantum efficiency at varying wavelengths for a solar cell of this invention having an anodic anti- reflection coating;FIG. 10 is a graphical presentation of the impurity profile for a GaAs shallow-homojunction photovoltaic device of this invention grown on a germanium substrate; FIG. 11 is a plot of data illustrating the__ O PI spectral response of a GaAs solar cell of this invention having an n+ layer thinned by an anodi- zation-strip cycle;FIG. 12 is a plot of data for the spectral response of a GaAs solar cell of this invention and comparing internal and external quantum efficiency;FIG. 13 is a plot of data illustrating the power conversion efficiency as a function of n+ layer thickness for four GaAs solar cells of this invention;FIG. 14 is a plot of data illustrating the decrease in Isc with increasing electron irradi¬ ation fluences for a GaAs shallow-homojunction solar cell of this invention; FIG. 15 is a plot of data illustrating the decrease in Isc, Voc, fill factor and power conversion efficiency with increasing electron irradiation fluences for another GaAs shallow- homojunction solar cell of this invention.Best Mode of Carrying Out the InventionThe invention will now be further described with particular reference to the Figures.A prior art homojunction photovoltaic device 10 is illustrated in FIG. 1. The substrate 12 is formed from an n GaAs wafer. Typically, substrate 12 might be doped to a carrier concentration of 10-***-■■-•■-10-**-7 carriers/cm-**-*. Layer 14 is formed over layer 12 and comprises p GaAs. Layer 16 is formed from p+ Gaι_χAlχAs and might have a carrier con- centration of 10----8 carriers/cm3. typical thickness for layer 16 is less than one micrometer. This Gaι_xAlxAs window has been used because the re¬ combination velocity for carriers generated upon solar illumination is much less at the Gaι_xAlxAs/ GaAs interface than it is within GaAs itself. In practice, a device of FIG. 1 can be formed by depositing a thin layer 16 of p+ Ga _χAlχAs over an n GaAs substrate and subsequently diffusing some of the p-dopants from the Ga^.j^Al^s layer into the GaAs substrate to form layer 14.Unfortunately, Gaι_χAlχAs coatings are difficult to apply using chemical vapor deposi¬ tion and are relatively difficult to use in the formation of an ohmic contact. Because of this, ohmic contacts are typically applied to devices such as that shown in FIG. 1 by employing vacuum coating techniques followed by alloying. These techniques are relatively expensive and detrimental to shallow-homojunctions.FIG. 2 illustrates one embodiment of an im¬ proved photovoltaic device of this invention. Therein, substrate 22 is formed from a wafer of p+ GaAs. Substrate 22 might be formed, for example, from GaAs suitably doped with p-dopants such as zinc, cadmium, berylium or magnesium to a carrier concentration of at least about 10 18 carriers/ cm . The thickness is not critical for substrate 22, but might be between about 1 and about 500 urn. Layer 24 is formed on the upper surface of layer 22 and is a layer of GaAs suitably doped with p-dopants to a carrier concentration of about 10 -10 carriers/3 cm . The thickness of layer 24 depends upon the minority carrier diffusion length and absorption coefficient, with a typical range for GaAs of from about 1 to about 5 um.Layer 26, formed from n+ GaAs, is epitaxially deposited upon layer 24. Layer 26 may be formed fromGaAs suitably doped with n-dopants, such as sulphur, selenium or silicon to a carrier concentration of atOMPI least about 1017 carriers/cm3. It is critical to limit the thickness of layer 26 to one which allows sig¬ nificant carrier generation within layer 24. Thus, layer 26 would typically be limited to a maximum thickness of 1500 A, and preferably less. Great care is necessary to assure that such thin layers are uniform, and not all deposition techniques are suitable. The techniques believed to be suitable include chemical vapor deposition, molecular beam epitaxy, liquid phase epitaxy and ion beam implantation. In addition, if care is taken to dope the top layer 26 to a sufficiently high concentration, an ohmic contact can be formed on the surface without degrading junction character- istics.It has been found that the n /p/p structure has significant advantages over previously employed structures. The p+ layer, for example, forms a back surface field junction with the p layer to provide high efficiency current collection. The high doping level in the p+ layer also simplifies the application of an ohmic contact thereto and this high doping level also allows the shallow- homojunction cell to be formed on a different sub- strate material which reduces the cost or provides other advantages. In this regard , the heavily doped p layer allows tunneling between any heterojunction formed between dissimilar materials thereby making ohmic contact feasible. The n+ top layer reduces the series resistance of solar cells having this structure. It also sim¬ plifies the formation of an ohmic contact to the cell because of its high doping level.The p layer also provides a major advantage in the n+//p/.p+ structure. Gr ea9te r cell efficiencies are possible with this structure compared to other shallow homojunction structures, such as p /n, because of the greatly increased diffusion length of minority carriers, i.e., electrons, in a p layer compared to the diffusion length of minority carriers in an n layer, i.e., holes.The overall cell structure of n /p/p thus provides a shallow-homojunction device which can be manufactureed inexpensively, is capable of pro¬ viding high efficiencies, can be deposited on sub- ' strates formed from different materials, and has outstanding resistance to degradation by electron bombardment which is a severe problem encountered in space applications.Top layer 28 is an antireflection coating which reduces the reflection of GaAs and thus increases absorption of solar energy. The antireflection coating might be, for example, successive layers of transparent materials having relatively high and relatively low indices of refraction, respectively. For example, an antireflection coating might be prepared by electron-beam evaporation of titanium dioxide and magnesium fluoride. It is particularly preferred to apply the anti- reflection coating by anodization. Application of anodic coatings can be done without any vacuum processing and is an inexpensive way of producing excellent antireflection coatings. In addition, the application of an anodic layer necessarily reduces the thickness of the top GaAs layer. For example, it has been found that application of an anodic layer typically reduces the thickness of the GaAs layer at the rate of about 2/3 part of the 5 volume of GaAs to one part by volume of anodic layer. Typically, the thickness of the antireflection layer would be based upon quarterwave theory.Anodic coatings can be formed by employing the device as the anode in an electrolytic cell. By proper selection and control over the cell parameters,' including the electrolyte and voltage applied, thin uniform anodic coatings can be formed. Suitable electrolytes are well known and a specific one found to be suitable is a solution formed by mixing 3 grams of tartaric acid into 100 ml of water, adding sufficient NH4OH to adjust the pH to about 6.2, and then adding 250 ml of propylene glycol. The voltage applied should be sufficient to produce the anodic coating in the thickness desired.Although the description above has. been limited to GaAs cells, other direct bandgap semiconductors such as InP and CdTe are also suitable. Addition¬ ally, the direct bandgap semiconductor layers can be deposited on substrates formed from different materials.FIG. 3 illustrates a shallow-homojunction de¬ vice 30 formed on p+ germanium substrate 32, The thickness of substrate 32 might be from 0.1 Jim to 500 urn and it might be formed from single crystal Ge *■18 doped with p-dopants to a carrier level of 10 car¬ riers/cm or greater. GaAs layers are then applied to Ge substrate 32, by chemical vapor deposition or other techniques, to form the desired shallow-homo- junction device from p GaAs layer 22, p GaAs layer 24 and thin n GaAs layer 26, which are similar to layers 22, 24 and 26, respectively, in FIG. 2. Antireflec¬ tion coating 28 is subsequently applied over thin n GaAs layer 26 to complete this embodiment.O There is a major cost advantage possible in the manufacture of GaAs shallow-homojunction solar cells when the actual gallium arsenide employed can be minimized by depositing the cell on a substrate of less costly material, such as germanium or silicon. Gallium arsenide solar cells theoretically have higher conversion efficiencies than cells formed from indirect bandgap materials, such as silicon and germanium. In addition, gallium arsenide cells poten- tially should be more radiation resistant in space en¬ vironments. By growing gallium arsenide cells on materials such as silicon or germanium, which have lower costs, the advantagesof both types of materials can be achieved. Substrates formed from materials different from the host semiconductor can offer other advantages in addition to cost advantages. Germanium, for ex¬ ample, has higher thermal conductivity than GaAs which is an advantage in heat dissipation. Germanium also has a lower melting point and lower vapor pressure than GaAs, which might allow easier laser crystallization on a substrate such as graphite. Laser crystallized germanium having large grains would provide a good substrate for chemical vapor deposition of GaAs.The use of substrates which are different from the host semiconductor is possible because of the heavy doping of the substrate and the p layer of the device. This permits tunneling to occur around the heterojunction between the substrate and p layer so that it does not act as a barrier. Thus, a good ohmic contact can be formed. - 12 - It should be understood that the embodiment shown in FIG. 3 is still considered to be a homo¬ junction cell, even though it technically contains a boundary between dissimilar materials, namely the boundary between p Ge substrate 32 and p GaAs layer 22. Although this boundary might techni¬ cally be referred to as a heterojunction, the heavy doping allows ohmic contact. This should be con¬ trasted with the heteroface between p GaAs layer 14 and thin p. Ga1-χAlχAs layer 16 in FIG. 1, which serves the function of reducing surface recombina¬ tion velocity of carriers generated in laye 14 upon solar irradiation. It should also be con¬ trasted with a typical heterojunction between dis- similar materials which is used to create a barrier to current flow in heterojunction devices. Because of these differences in purpose, solar cell 30 il¬ lustrated in FIG. 3, and other similar cells', will be referred to herein as shallow-homojunction solar cells formed from direct gap semiconductors deposited on different substrate materials.Although substrate 32 has been illustrated to be single crystal Ge, other substrates could be employed. Single crystal silicon, for example, could also be employed. In fact, substrate 32 might also be formed from polycrystalline or amorphous materials, including silicon and germanium.Electrical contact to the thin n+ layer can be easily made because of the high doping level therein. Contacts can be formed by electroplating metals. such as gold, tin,1 etc. Specific procedures for the electroplating of these metals differ, however, and are respectively illustrated in FIGS. 4 and 5. In both of these figures, the shallow-homojunction solar cell has the structure illustrated in FIG. 3.In FIGS. 4(a) and 4(b), a typical application of gold contacts is illustrated. In this technique, the thin n+ layer 26 is first anodized to form anodic coating 28 while simultaneously thinning n+ layer 26.The anodization potential can be set to achieve the appropriate thickness for the antireflee4-ion coating and n layer. A photoresist mask 30 is then placed over anodic coating 28 and finger openings 32 (FIG. 4 [a]) are etched through anodic coating 28 employ¬ ing an etch such as dilute hydrochloric acid. Gold contacts 34 are then electroplated onto n layer 26 through photoresist mask 30. Photoresist mask 30 is then removed by dissolving it in acetone to produce the device of FIG. 4 (b) .The application of tin contacts is illustrated in FIGS. 5(a) and 5(b). Photoresist mask 30 is directly applied to thin n+ layer 26 and tin con¬ tacts 36 are electroplated onto layer 26 through mask 30 (FIG. 5[a] ) . Photoresist mask 30 is then removed and the thin n layer 26 is anodized (FIG. 5 [b]) . When this procedure is employed, the thin n layer 26 remains thicker under tin contacts 36 than under the remainder of anodic coating 28. Thus, layer 26 has raised shoulders 38 directly beneath tin contacts 36 as can be seen in FIG. 5(b) . Thus, there is a larger separation between the metal contacts and the p-n junction for tin contacts than for gold contacts. Because the n+ layer is extremely thin after anodization, this in¬ creased separation should improve device yield and reliability.- tJREX^ _ OMPI The use of tin contacts is also advantageous for optimizing the n+ layer thickness since the anodic oxide formed on gallium arsenide can be stripped with dilue HC1 and the cell reanodized without removing the contacts. Because the thickness of the oxide layer is very uniform and easily controlled by adjusting the anodizing voltage, a series of alternating anodization and stripping steps can therefore be used for con- trolled reduction of n+ layer thickness. The thickness of the gallium arsenide removed during each anodization can be accurately determined by using elliposometry to measure the anodic oxide thickness and multiplying this value by an appro- priate factor.Some anodic antireflection coatings may be somewhat unstable in harsh environments. If this is a problem, it can be overcome by application of a thin (e.g., 100 A), transparent, protective coating of a material such as Si0_ or phosphosilicate glass. Such protective coatings can be applied by pyrolytic deposition techniques.FIG. 6 is a cross-sectional view illustrating one finger of a solar cell having such a protective SiU2 coating 40. Device fabrication is similar to that described above for FIGS. 4(a) and 4(b), except that a hydrofluoric acid etch is employed prior to the hydrochloric acid etch. Contact finger 34 can be formed from gold plated to a thickness of about 4 p . The back contact 42 can also be formed from plated gold. Although the Si0_ protective, layer was described as being applied prior to contact formation, it could also be applied after the con¬ tacts have been formed.^ ^O PI Λ. WIPO As those skilled in the art will recognize, other metals could be used in place of gold and tin for purposes of establishing electrical contact with the photovoltaic device which is described herein. In devices fabricated as illustrated in FIG. 4, any metal could be employed including gold, silver, platinum, tin, aluminum, copper, etc. ■ In devices fabricated as illustrated in FIG. 5, those metals can be used which form a sufficiently thick oxide layer during anodization such that current leakage through metal contacts is reduced enough to allow the semiconductor surface to be anodized. Tin, aluminum and copper are examples.Devices of this invention have at least one n-p homojunction and at least one other junction sufficient to increase current collection. This other junction requires an impurity profile where¬ in the majority carriers all have the same charge and wherein an electrical field is created by the impurity profile which aids in collecting minority carriers. The p layer also allows the use of substrate materials other than the host semi¬ conductor material. Specific examples of suitable junctions include high/low homojunctions and graded profile junctions where the impurity doping level increases with distance from the n-p junction.This invention can be further specifically illustrated by the following Examples. EXAMPLE 1GALLIUM ARSENIDE SHALLOW-HOMOJUNCTION PHOTOVOLTAIC ' DEVICEGaAs layers were grown in an sCl3-Ga-H2 system. The reactor tube had an inner diameter of 55 mm, and the H2 flow through the AsCl^ evaporator andOMPI over the Ga boat was in the range 300-500 cm /min. The p and n dopants were introduced in the vapor phase by using (C2H5)2Zn and H^S, respectively. The reactor tube was vertical, allowing rotation of the substrate, which resulted in greater doping uniformity in the layers. Use of high purge flows allowed the reactor tube to be opened at the bottom to load and unload substrates without losing the H2 atmosphere inside the tube. Thus, the furnace could remain at growth temperature during the loading procedure, decreasing the cycle time between runs. Once inside the reactor tube, the substrate could be preheated in pure H2 just before being introduced into the reactant gas flow at the growth position. For a more detailed description, see Bozler, C. O., Solid State Research Report, 7_, 52, Lincoln Laboratories, M.I.T. (1975).A p layer, 1.7 um thick, was first grown on a p , Zn-doped (100)-oriented GaAs substrate with a18 3 carrier concentration of 10 carriers/cm ,followed by a thin n+ layer. The p layer (p-— cm ) and n layer (n-»« x 10 18cm—3) were doped with Zn and S, respectively, by using (C2H5)2Z and H2S sources. The sheet resistance of the n+ layer was 70 . To determine the thickness of this layer, the I-V characteristic between two ohmic contacts to the layer was measured while a channel was being etched between the contacts. When the I-V char¬ acteristic for back-to-back diodes was observed, etching was immediatedly stopped, and the channel depth was measured with a profilometer. The n+ layer thickness measured by this technique was 1300A!The initial fabrication step following layer growth was the pyrolytic deposition of Si02 glassO PI (1000 A) on the GaAs wafer at -400°C, in order to protect the n+ layer during the succeeding steps. Openings for ohmic contact fingers were etched in the glass coating using photolitho- graphic techniques. There were 10 openings, 0.5 cm long and 12 um wide, spaced 1 mm apart. The wafer was sputter-etched to remove GaAs to a depth of 40 A in the finger openings, then sputter-coated with successive layers of Au- 12% Ge (300 A) and Au (2000 A). The Au/AuGe film was defined photolithographically into 25-um-wide fingers, interconnected at one end, that overlaid the openings in the glass. All of the photolitho¬ graphic steps were carried out with standard equip- ment used for silicon wafer processing. The wafer was then annealed under flowing 2 for one second at 300°C on a graphite heater strip to establish ohmic contact between the AuGe fingers and the n+ layer, as verified by measurements of test con- tacts on the wafer. The conventional technique of alloying at 450°C was not used because it was found to cause penetration of the n layer, and subsequent destruction of the homojunction.The contact fingers to the n+ layer were electroplated with Au to a thickness of 4 um.The back contact to the ρ+ substrate was made with sputtered Au. The active area of the cell was de¬ fined by etching a 1 cm x 0.5 cm rectangular mesa in the GaAs, and the glass layer was removed with buffered HF. The fingers of the cell at this stage had a cross sectional configuration similar to that illustrated in FIG. 6, except that there was no anodic layer 28. Finally, the cell was antireflec- o tion-coated with successive layers of SiO (700 A)O PI and gF2 (1200 A) formed by electron beam evapora¬ tion. For GaAs with this two-layer coating, the average reflectivity measured over the 0.5-0.9 um wavelength band was less than 5%. An efficiency measurement of the cell was made by using a high-pressure Xe lamp with a water filter as a simulated AM 1 solar source. The incident intensity was adjusted to 100mW/cm-2, using a, NASA standard Si solar cell, calibrated for AM 1, as a reference. The open-circuit voltage was 0.91 V, the short-circuit current 10.3 mA, and the fill factor 0.82, giving a measured conversion effi¬ ciency of 15.3%. When the contact area is subtracted, the corrected efficiency is 17%. The n factor at 100 mA/cm^ is 1.25, as obtained from the dark I-V characteristic, indicating good material quality with long carrier diffusion lengths. The series resistance is 0.5Λ.The quantum efficiency of this cell as a func- tion of wavelength is shown in FIG. 7, and, as can be seen, quantum efficiency is highest at the longer wavelengths, with a gradual decrease at shorter wavelengths.This cell was fabricated by sputtering and alloying techniques, which although possible because of the relatively thick n layer, are not preferred.EXAMPLE 2 GALLIUM ARSENIDE SHALLOW-HOMOJUNCTION PHOTOVOLTAIC DEVICE HAVING ANODIC ANTIREFLECTION COATING A photovoltaic device was prepared as in Example 1 except that the antireflection coating was an anodic coating, and all ohmic contacts were electro- - plated.OMP The GaAs layer used was grown in an AsCl3-Ga-H2 CVD system on p+ Zn-doped (100)-oriented substrate, with a carrier concentration of 1018cm 3. A p layer about 2 jam thick was first grown on the substrate followed by an n+ layer (n-'S x lO^cm 3) were doped with Zn and S, respectively, by using (C2H5)2 Zn and H2S sources. Following GaAs growth, the n+ layer was anodically oxidized as follows. The electrolyte solution used for anodization was prepared by mixing 3 g of tartaric acid with 100 ml of H^O, adding sufficient NH4OH to adjust the pH to about 6.2, and then adding 250 ml of propylene glycol. The final pH was 4.6-5.8. Anodization of the GaAs was performed at room temperature, using a platinum wire as cathode. A smooth anodic layer of uniform thickness was obtained by using a constant current source with a voltage limiter. The source was set at a current corresponding to a current density of about 750 for the GaAs anode, and the maximum output voltage was set at about 43 V. The current initially remained con¬ stant until the voltage increased to its limiting value, after which the voltage remained constant and the current decreased. Anodization was termin¬ ated when the current fell to one-tenth of its ini¬ tial value. The thickness (measured by ellipsometry using a He-Ne laser) of the anodic layer was about 20 A/V and did not depend strongly on current density. The layer produced took less than 5 minutes, was about o o850 A thick, and consumed about 550 A of the GaAs layer. The anodic layer was stable up to at least 250°C in air. The optical constants were mea- o sured by ellipsomtery at 4358 and 5461 A using a Hg o lamp and at 6328 A using a He-Ne laser. The values of the refractive index n at these wavelengths are 1.91, 1.85 and 1.83 respectively, as shown in the inset of FIG. 8. The values of extinction coefficient k are very low, and for the thickness of anodic layers used, absorption of the optical constants (and the effectiveness of the antireflection coating) is illustrated in FIG. 8 by the close agreement between the measured reflectivity spectrum of an 800 A thick anodic layer on GaAs and the value for this struc¬ ture calculated using values of n obtained from the curve shown in the inset of FIG. 8, k = 0 for the anodic layer, and bulk optical constants for GaAs.A layer of Au about 3 um thick was then electro¬ plated on the p+ substrate as the back contact. Photoresist AZ 1350J was spun on the anodic layer, and photolithographic techniques were used to etch openings for ohmic contact fingers in the anodic layer. (The anodic layer dissolves readily in AZ photoresist developer, as well as in HC1.) There were 10 openings, 0.5 cm long and 12 um wide, spaced 1 mm apart and interconnected with a bar at one end. A layer of Au about 3 um thick was then electroplated into the openings, and the wafer was annealed in N2 for 1 sec at 300°C on a graphite heater strip to produce ohmic contact between the Au fingers and the n+ layers. Finally, the active area of the cell was defined by etching the GaAs to form a 1-cm x 0.5 cm rectangular mesa.OMPI Efficiency measurements, using a high-pressure Xe lamp with a water filter as a simulated AM 1 . source, were made. The incident intensity was ad¬ justed to 100 mW/cm2, using a NASA-measured GaAs solar cell as a reference. The cell was also measured on the roof of the laboratory at an ambient temperature of about 20°C. The solar flux density measured with a pyranometer was 98 mW/cm2, close to AM 1 conditions. The open-circuit voltage was found to be 0.97 V, the short-circuit current 25.6 mA/cm2, and the fill factor 0.81, giving a measured conversion efficiency of 20.5 per cent, without correcting for the area of the contact fingers. The quantum efficiency of this cell as a function of wavelength is shown in FIG. 9. The quantum efficiency exceeds 90 percent at the maximum, but it decreases quite strongly at shorter wavelengths.EXAMPLE 3 GALLIUM ARSENIDE SHALLOW-HOMOJUNCTION PHOTOVOLTAIC DEVICES ON GERMANIUM SUBSTRATESThe growth procedures and apparatus of Example 1 were used, except as noted. The Ge substrates were oriented (100) 2° off toward (110) and were prepared by coating them with Si02 on the backside to reduce Ge autodoping of the GaAs layers during growth. The electron concentration in nominally undoped layers deposited on these coated substrates was 5 x 1015cιtf . The lattice constants and expansion coefficients ofGe and GaAs are well matched, a favorable condition for obtaining good quality epitaxial layers. The doping profile used for the solar cells is shown in FIG. 10. The p+ Ge substrate was highly doped with Ga (8 x 10-■■-■■■■cm ) in order to overdope any As that might diffuse into the Ge during the deposition of the GaAs and to assure tunneling through any thin barriers which could arise at the heterojunction interface. The p+ GaAs buffer layer was highly doped with Zn, again to assure tunneling and also to overdope Ge diffusing into the GaAs during growth. The change in hole con¬ centration from 5 x 1018cm~3 in the buffer layer to 1 x 10 cm in the active layer provided a backsurface field to increase the collection effi¬ ciency. The n+ layers were doped to a carrier con- centration of 5 x lO^cm 3 with sulfur, had a sheet resistivity in the range 45-100 tyO, and their electron mobility was'-'lOOO cm /V-sec.An AR coating was produced on the n+ layer by anodic oxidation, which consumed a thickness of GaAs equal to 0.66 times the thickness of oxide produced. The anodizing solution was prepared by adding 3 g tartaric acid to 100 ml H20, adjust¬ ing the pH to 6.2 with NH40H, and adding 250 ml propylene glycol. The thickness of the oxide layer was proportional to the limiting voltage used for anodization. The thickness required o for an optimum AR coating was 850 A, which was obtained for a limiting voltage of 43V.Contact to the very thin n+ layer was made easily because of its high doping level. Elec¬ troplated Au formed ohmic contacts with a spec¬ ific resistance of 8 x 10~5 A-cm2. Electroplated Sn also formed ohmic contacts, although their resistance was not measured. Sn had the advan-.TϋREA OMPI i IPO tage that in the solution used for GaAs anodi¬ zation, Sn was also anodized, forming an oxide resistive enough to allow the GaAs to be anodized in the presence of Sn contacts. Two different fabrication procedures were used for cells with Au and *Sn contact fingers, as illustrated in FIGS. 4 and 5. For devices with Au contacts, the n+ layer was anodized first, finger openings were etched through the oxide using a photoresist mask, and Au was plated using the same mask. For cells with Sn contacts the Sn fingers were plated first, using a photo¬ resist mask, the photoresist was then removed, and the n+ layer was anodized. With this pro- cedure the n+ layer was thicker under the Sn contacts than under the anodic oxide, so that there was a larger separation of the metal from the p-n junction than with Au contacts. Because the n+ layer is so thin, the increased separation was believed to be better. for device yield and reli¬ ability.A mesa etch of the GaAs was used to define the active area of the cells, and the back contact to the Ge substrate was made by Au plating. No alloy- ing or vacuum processing was used in cell fabrica¬ tion.Measurements of spectral response as a function of n+ layer thickness were made on small cells, 0.05 cm2 in area, having two Sn contact fingers 0.5 mm apart connected to a Sn bar at one end. The n+ layer, which was initially 2000A thick with a sheet resistance of 45 St/U, was thinned by alter¬ nate anodization and stripping. The external quantum efficiency, which is the ratio of the number of carriers collected (I /q) to the number of incident photons, was measured after each of three anodizations at 43 V, so that the cells were antireflection-coated during each measure¬ ment. The values of Isc and incident photon flux were measured as a function of wavelength in a spectrometer which was arranged so that all tHe light fell between the two contact fingers. The results for cell 1 are given in FIG. 11, which shows that thinning the n+ layer results in a marked improvement in quantum efficiency, espec¬ ially at shorter wavelengths. This is expected because of the high absorption coefficients for GaAs (104-105cm-1) , which increase with decreas¬ ing wavelength, and the high surface recombina- tion velocity, which is believed to be around 10 cm/sec. The power conversion efficiency for each n+ layer thickness is also given in FIG. 11. These values were measured with the cell fully illuminated by a simulated AMI source, with no correction made for the finger area.FIG. 12 shows the final spectral response of cell 2, which was fabricated next to cell 1. The n+ layer was slightly thinner than that of cell 1, and the response was therefore slightly improved at the short wavelengths. The curve for internal quantum efficiency, which is the ratio of Ic./q to the rate at which photoms enter the semiconductor, was obtained from the measured external efficiency by correcting for the spectral reflectivity of the AR-coated cell. This curve indicates that the cell design is very near the optimum.The AMI power efficiencies of cells 1 and 2 and two other small cells fabricated side by side on the same wafer are plotted in FIG. 13 as a function of n+ layer thickness. In order to ob¬ tain additional thickness values, cells 2, 3 and 4 were first anodized to 10, 20 and 30 V, respect¬ ively, after which the oxide was stripped. All 4 cells were then anodized together to 43V to pro¬ vide an AR coating, stripped, anodized to 43 V, stripped again and once more anodized to 43 V. Efficiency measurements were made after each 43 V anodization. After the third such anodization, the efficient of cell 3 had dropped to 10% while cell 4 had essentially no sensitivity to light.Assuming that the cell output drops to zero when removal of the n+ layer is completed, for cells 1-4 complete removal would occur at a total anodization voltage between 149 and 159 V, the final values for cells 3 and 4, respectively. It was assumed for the purposed of plotting the data that complete removal would occur at 154 V. Using the removal rate of 13.3 A/V, the initial n 1 layer o thickness was found to be 2050 A.- To obtain the thickness of the n+ layer remaining after each successive anodization the total thickness removed was calculated from the sum of the voltages used to that point and subtracted from the initial thickness.The thickness values given in FIGS. 11 and 12, as well as those of FIG. 13, were obtained in this manner. For all the points in FIG. 13 the fill factor was 0.82 and Vr_r- was 0.97 V. As the thick-+ ° ness of the n layer is reduced below 200 A thick, the efficiency drops precipitously from the maximum value of 21.2% . Seven larger cells, 1cm x 0.49 cm, were made from three different wafers. Either Au or Sn was used for the contact finger pattern, which consisted of 20 fingers 0.5 cm apart with a connecting bar at one end. The fingers covered 4% of the total , area. One cell with Au contacts was partially shorted and one with Sn contacts was thinned too much. Power efficiency measurements, using a high pressure Xe lamp with a wafer filter as a simulated AMI source, were made on the other five cells. The incident intensity was adjusted to lOOmW/cπr' using a NASA-measured GaAs solar cell as a reference.. Table 1 lists the measured values of V , Isc, fill factor and efficiency, as well as the initial sheet resistance and the total anodization voltage.Independent measurements as NASA Lewis Research Cen¬ ter have confirmed these results. The sheet Re¬ sistance value gives some indication of the initial thickness of the n+ layer; a value of 100 Sϊ O corres- o ponds to approximately 1200 A. The total anodization voltage is the sum of the limiting voltages used in a series of anodization-strip steps where the thin- t¬ ing ratio . is 20 A/V. For each cell the final ano¬ dization was carried out at 43 V to provide the AR coating. The conversion efficiency values, not corrected for contact areas, are all in the 17-20% range. TABLE 1EXAMPLE 4 ELECTRON BOMBARDMENT OF GaAs SHALLOW-HOMOJUNCTION SOLAR CELLSIt has been reported that irradiation of Gaι_χA1xAs/ GaAs heteroface solar cells with electrons, causes the conversion efficiencies of these cells to be dramatically decreased. This is believed to be partly because of the difusion lengths of minority carriers in p and n layers decrease with increasing electron irradiation, and partly because the sur¬ face recombination velocity at the Ga, Al As/GaAs interface increases with increasing electron irrad¬ iation. It was hypothesized that the n /p/p structure of the cells described herein would dramatically increase the resistance to cell degradation under electron irradiation. If so, the n /p/p GaAs shallow-homojunction solar cells would be outstanding candidates for space appli¬ cations, involving space vehicles, solar powered satellites, etc.To test the hypothesis, a series of experi¬ ments was run in which shallow-homojunction GaAs solar cells, as described herein, were irradiated with 1 MeV electrons from electron fluences rang- ing from 1014 to 1016 electrons/cm2. The 1016 2 electron/cm fluence is equivalent to dosages which electronic devices would be subjected to over 50 years in synchronous orbit.In one experiment, a GaAs shallow-homojunction solar cell prepared according to Example 1 and having a thin τ layer of about 1000A without an antireflection coating thereon was subjected to electron fluences of 0, 8 x 10 , 3.2 x 1015 and 1.0 x 10 o electron/cm . The change in the short circuit current, I caused by these electron fluences was determined by integrating the quantum efficiencies with the solar spectrum at air mass 0 (AM 0), which is representative of space conditions. FIG. 14 is a plot of I /(Isc) 0 here sc)o is the original short circuit current before electron bom¬ bardment. As can be seen, at a fluence of 1 x 10 electron/cm , the decrease in I was only about 7%. The corresponding Ga,-'aXAlXAs/GaAs cell is reported in the literature to undergo a 99% decrease in I under a corresponding electron fluence. See Walker, C.E., By ik, C.E., Conway, E.J., Heinbockel, J.H., and Doviak, M. J., Analytical and Experimental Study of 1 MeV Electron Irradiated GaAlAs/GaAs Heteroface Solar Cells, J. Electrochem. Soc. : Solid-State Science and Technology, 2034-36 (1978) .FIG. 15 illustrates corresponding data for a GaAs shallow-homojunction solar cell having a o thin n+ layer of about 1400 A with an anodic AR- coating under electron fluences ranging from 5 x 10 to 7 x 10 electron/cm . This cell was also measured under simulated AM 0 conditions at the above range of dosages. As can be seen from FIG. 15 where items having the subscript c in¬ dicate values prior to electron bombardment, short circuit current (I ) decreased by about 20% at 7 x 1015 electron/cm2, the open circuit voltage,V , also decreased gradually. The fill factor, oc ff, actually increased slightly before it began to decrease with increasing fluences. The conversion efficiency *h of the cell, which was about 14% at AM 0 before electron irradiation, still had over 60%. of its original efficiency after being bombarded with7 x 10 15 electrons/cm2. $fREA»OMPI Industrial ApplicabilityThis invention has industrial applicability in the fabrication of solar cells, particularly solar cells for use in space applications.EquivalentsThose skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the following claims. | CLAIMS1. A shallow-homojunction photovoltaic device . formed from a direct bandgap semiconductor+ x , + material doped to provide a /p/p layered structure, said n layer being sufficiently thin to allow significant carrier generation to occur in the p layer upon irradiation of said device with light.2. A shallow-homojunction photovoltaic device of Claim 1 wherein said n layer has a thickness o 0 below about 1500 A.A shallow-homojunction photovoltaic device of Claim 2 wherein said device has an antireflection coating over said n layer.4. A shallow-homojunction photovoltaic device of 5 Claim 3 wherein said direct bandgap semi¬ conductor material comprises GaAs.5. A shallow-homojunction photovoltaic device of Claim 4 wherein said device has a substrate formed from a different material than GaAs.206. A shallow-homojunction photovoltaic device of Claim 5 wherein said substrate is formed from silicon or germanium.A shallow-homojunction photovoltaic device of Claims 3, 4, 5 or 6 wherein said antireflection25 coating comprises an anodic coating. 8. A method of applying an electrical contact and an anodic antireflection coating to an n layer of a direct gap semiconductor device, comprising: a. applying a metal contact to-j- said n layer, said metal being anodizable; and, there¬ after4. b. anodizing said n layer whereby its thickness is reduced and an antireflection layer is formed thereover.9. A method of Claim 8 wherein said anodizable metal comprises tin.OMP | MASSACHUSETTS INST TECHNOLOGY; MASSACHUSETTS INST TECHN | BOZLER C; CHAPMAN R; FAN J; MCCLELLAND R |
WO-1979000829-A1 | 1,979,000,829 | WO | A1 | XX | 19,791,018 | 1,979 | 20,090,507 | new | C07D285 | A01N9 | A01N43, A01N57, C07D285, C07F9 | A01N 43/88, A01N 57/16, C07D 285/16, C07D 285/16E, C07D 285/18, C07F 9/6544, M07D 285/16E, M07D 285/18 | INSECTICIDAL 2-SUBSTITUTED-IMINO-3-ALKYL-5-DIALKOXYPHOSPHINOTHIOLOXY-6H-1,3,4-THIADIAZINE,INTERMEDIATES THEREFOR AND PREPARATION THEREFOR | Thiadiazine compounds of the formula (I) (FORMULA) wherein R<s1>s is alkyl, R<s2>s is alkyl, cycloalkyl, alkenyl or aryl, R<s3>s is alkyl and R<s4>s is alkyl, are useful as insecticides. The thiadiazine compounds are prepared by the addition of a dialkylhalothiophosphate to a tetrahydro-6H-1,3,4-thiadiazin-5-one. The thiodiazin-5-one precursor is prepared by reacting a thiosemicarbizide with an alkyl alpha-halothio acetate or with a haloacetic anhydride. | INSECTICIDAL 2-SUBSTITUTED-IMINO-3-ALKYL-5- DIALKOXYPHOSPHINOTHIOLOXY-6H-1,3,4-THIADIAZINE, INTERMEDIATES THEREFOR AND PREPARATION THEREFORThe present invention relates to thiadiazine com¬ pounds useful as insecticides, and preparation of the thia¬ diazine compounds. It also relates to intermediates for preparation of such compounds and preparation of the inter¬ mediates.Chem. Abstr., Vol. 80, 82906p (1974), discloses thiadiazinones and their mono- and dithiophosphates.The insecticidal compounds of the invention are 2-substituted-imino-3-alkyl-5-dialkoxy-phosphinothioloxy- 6H-l,3,4-thiadiazines represented by the formula1 wherein R1 is alkyl of 1 to 6 carbon atoms, R2 is alkyl of 1 to 6 carbon atoms, alkenyl of 3 to 6 carbon atoms, cyclo¬ alkyl of 5 to 6 carbon atoms, phenyl, or phenyl substi¬ tuted with 1 to 2 substituents selected from the group con¬ sisting of alkyl of 1 to 6 carbon atoms, fluoro, chloro, bromo, iodo, nitro, trifluoromethyl, trichloromethyl, tri- bromomethyl and alkoxy of 1 to 4 carbon atoms, R3 is alkyl of 1 to 6 carbon atoms and R4 is alkyl of 1 to 6 carbon atoms.Representative alkyl R1, R2-, R3, and R^ groups include methyl, ethyl, isopropyl, n-butyl, isohexyl, n- hexyl, etc.Representative substituted phenyl R2 groups in¬ clude 4-methylphenyl, 2,4-dimethylphenyl, 2-fluorophenyl, 3,5-dichlorophenyl, 3-bromophenyl, 4-iodophenyl, 2-methyl- 4-chlorophenyl, 4-nitrophenyl 3-trichloromethylphenyl, 2- methoxyphenyl and 2-chloro-4-nitrophenyl. Representative alkenyl R2 groups are allyl, 2-butenyl and 3-hexenyl. Preferably Rl is lower alkyl of 1 to 3 carbon atoms, especially methyl.Preferred alkyl R2 groups are alkyl of 1 to 4 carbon atoms and preferred aryl R2 groups are phenyl and phenyl substituted with 1 to 2 substituents selected from alkyl of 1 to 4 carbon atoms, fluoro, chloro, bromo, tri- fluoro ethyl and trichloromethyl. Preferably, R2 is alkyl of 1 to 4 carbon atoms.Preferably R3 and R4 are alkyl of 2 to 4 carbon atoms, especially ethyl.A preferred class of thiadiazines of formula I is that wherein R^ is lower alkyl of 1 to 3 carbon atoms, especially methyl, R2 is alkyl of 1 to 6 carbon atoms, R3 is alkyl of 2 to 4 carbon atoms and R4 is alkyl of 2 to 4 carbons.The compounds of the invention can be prepared by the addition of a dialkoxyhalothiophosphate (III) to a 2-(substituted-imino)-3-alkyl-tetrahydro-6H-l,3,4-thiadia- zin-5-one (II), as depicted in the following reaction (1)R1N SR2-N=C Nil + X-P-OR3 - (D {1) S C=0 « ORMCH2(II) (III) wherein Rl, R2, R3 and R4 have the same meaning as stated before, and X is chloro or bromo, preferably chloro.Reaction (1) can generally be conducted by react ing substantially equimolar amounts of the thiadiazinone (II) and the thiophosphate (III), i.e., the molar ratios of thiadiazinone (II) to thiophosphate (III) generally vary from about 1:1.2 to 1.2:1, although molar ratios from about 1:1.1 to 1.1:1 are preferred. A substantially equivalent amount of a base can be used to scavenge the hydrogen halide by-product. Such bases are preferably inorganic bases, e.g., alkali metal carbonates such asOMPI sodium carbonate and potassium carbonate, and alkali metal bicarbonates such as sodium bicarbonate. The molar ratio of base to the thiadiazinone (II) is generally about 1.1:1 to 1:1. The reaction can be conducted in an inert liquid organic diluent. Suitable inert organic diluents include alkanones such as acetone, methyl ethyl ketone; acyclic alkyl ethers such as dimethoxyethane and dibutylether; cyclic ethers such as dioxane or tetrahydrofuran; halo- alkanes such as dichloromethane and aromatic compounds such as benzene, toluene, and chlorobenzene. Generally, the amount of diluent employed ranges from 1 to 50 mols per mol thiophosphate (II).Reaction (1) is suitably conducted at a tempera¬ ture of from about 15°C to the boiling point of the dilu¬ ent, although temperatures of from about 20°C to 100°C are preferred. The reaction is generally conducted at or above atmospheric pressure. The reaction time will, of course, vary depending on the reaction temperature and the particular reactants employed. Generally, however, the reaction time varies from several minutes to 24 hours. The thiadiazine product (I) can be isolated from the reaction mixture by conventional procedures, e.g., extraction, chromatography, crystallization, etc.Reaction (1) can also be conducted with the hydrogen halide salts of the thiadiazinone (II). In this modification of reaction (1), two equivalents of the base material are generally used, i.e. , the molar ratio of base to thiadiazinone is generally about 2.2:1 to 2:1. It is generally preferred to use the hydrogen halide salt when the imino substituent (R2) of the thiadiazinone (II) is aliphatic.The thiadiazin-5-one reactants (II) used in reaction (1) are novel compounds and can be prepared by the cyclization of a semithiocarbazide (IV) with a halo¬ acetic anhydride (V) , as depicted in the following reaction (2) :OMPIA R2-NH-C-NII-NH2 (X CH2CO) 20 ( ID (2) R 1(IV) (V)wherein R1, R2 and X have the same meaning as previously stated.Reaction (2) is generally conducted by reacting substantially equi olar amounts of the semithiocarbazide (IV) and the haloacetic anhydride (V) in the liquid phase. The molar ratios of semithiocarbazide to anhydride (V) generally vary from about 1:1.2 to 1.2:1, although molar ratios of from about 1:1.1 to 1.1:1 are preferred. The reaction is normally conducted in an inert liquid diluent, e.g., organic solvents such as chlorinated hydrocarbons. The reaction is conducted at a temperature of from about 0° to the boiling point of the diluent, although tempera¬ tures from about 25°C to 100°C are preferred. The reac¬ tion is generally conducted at or above atmospheric pres¬ sure. Generally, the reaction is completed within one- half to 24 hours. The product (II) can be isolated and purified by conventional procedures such as extraction, filtration, crystallization and chromatography. Gener¬ ally, when the thiadiazinone product (II) has an aliphatic i ino substituent (R2) , the product is most conveniently isolated as a hydrogen halide salt.The thiadiazin-5-one reactants (II) can also be prepared by reacting the semithiocarbazide (IV) with an alkyl halothioacetate (VI) as depicted in the following reaction (3) : s o R2-NH-C-NH-NH2 + XCH2CSR -► (II) (3) (IV) (VI) wherein R1, R2 and X have the same meaning as previously stated and R is alkyl of 1 to 6 carbon atoms, preferably of 1 to 3 carbon atoms.Reaction (3) is generally conducted by reacting substantially equimolar amounts of the semithiocarbazide (IV) and the halothioacetate (VI) in the liquid phase. The molar ratios of semithiocarbazide to halothioacetate (VI) generally vary from about 1:1.2 to 1.2:1, although molar ratios of from about 1:1.1 to 1.1:1 are preferred. The reaction is normally conducted in an inert liquid ' diluent. Suitable inert organic diluents include alkan- ones such as acetone, methyl ethyl ketone; acyclic alkyl ethers such as dimethoxyethane and dibutylether; cyclic ethers such as dixoane or tetrahydrofuran; haloalkanes such as dichloromethane; and aromatic compounds such as benzene, toluene, and chlorobenzene. Generally, the amount of diluent employed ranges from 1 to 50 mols per mol of semithiocarbazide (IV). The reaction can be con¬ ducted at a temperature of from about 0°C to the boiling point of the diluent, although temperatures from about 25°C to 100°C are preferred. The reaction is conducted at or above atmospheric pressure. Generally, the reaction is completed within one-half to 24 hours. The product (II) can be isolated and purified by conventional procedures such as extraction, filtration, crystallization and chroma- tography. Generally, when the thiadiazinone product (II) has an aliphatic imino substituent (R2), the product is most conveniently isolated as a hydrogen halide salt.Example 1 — Preparation of 2-(3,4-dichlorophenyl- imino)-3-methyl-tetrahydro-6H-l,3,4-thiadiazin-5-oneTo a stirred solution of 37.5 g (0.15 mol) 2- methyl-4-(3,4-dichlorophenyl)semithiocarbazide in 200 ml dichloromethane was added 25.5 g (0.015 mol) chloroacetic anhydride. The resulting reaction mixture was heated under reflux for 16 hours, cooled, neutralized with sodium bicarbonate, washed with water, dried over magnesium sul- fate and evaporated under reduced pressure to give an oily solid. The solid was slurried with ether, filtered and dried to give 12 g of the product, as a grey solid, m.p.118°-120°C. This product is tabulated in Table A as compound No. A-6.Example 2 — Preparation of 2-(3,4-dichloro- phenylimino)-3-methyl-5-diethoxyphosphino- thioyloxy)-2,3-dihydro-6H-l,3,4-thiadiazineA slurry of 14 g (0.048 mol) 2-(3,4-dichloro- phenylimino)-3-methyl-tetrahydro-6H-l,3,4-thiadiazin-5- one, 7 g (0.048 mol) potassium bicarbonate, and 9.1 g (0.048 mol) diethylchlorothiophosphate in 200 ml acetone was heated under reflux for 8 hours, cooled and stirred at about 25°C for overnight. The reaction mixture was fil¬ tered and evaporated under reduced pressure to give an oil. The oil was chromato raphed on silica gel using 50/50 petroleum ethyl/diethyl ether as the eluant to give 11 g of the product, as a yellow oil. This product is tabulated in Table B, as compound B-7.Example 3 — Preparation of2-(t-butylimino)-3-methyl-tetrahydro-6H-1,3,4-thiadiazin-5-one hydrochlorideTo a stirred solution of 16.1 g (0.1 mol) 2- methyl-4-t-butylsemithiocarbazide in 200 ml dichloro¬ methane was added slowly 17.1 g (0.1 mol) chloroacetic anhydride. The resulting solution was stirred at about 25°C for about 8 hours. The reaction mixture was filtered to give 14 g of the product, as a white solid, m.p. , 224°- 225°C. The infrared spectrum of the product showed car- bonyl absorption at 5.95 micron. Elemental analysis for c8H16clN30S showed:Calc. Found%S 13.5 13.3%C1 14.9 * 15.5Example 4 — Preparation of 2-(t-butyl- imino)-3-methyl-5-diethoxyphosphino- thioyloxy-2,3-dihydro-6H-l,3,4-thiadiazineA slurry of 10.0 g (0.0421 mol) 2-(t-butylimino)3-methyl-6H-l,3,4-thiadiazin-5-one, 11.6 g (0.0842 mol) *.: potassium carbonate and 8. 2 g ( 0.0421 mol) diethylchloro- thiophosphate in 200 ml acetone was heated under reflux for 8 hours. The reaction mixture cooled, stirred over¬ night, filtered and evaporated under reduced pressure to give an oil residue. The residue was dissolved in di¬ chloromethane, washed with water, dried over magnesium sulfate and evaporated under reduced pressure. The crude product was then chromatographed on silica gel using diethyl ether as the eluant. The purified product (6 g) was an amber oil. The product is tabulated in Table B as Compound No. B-l.Example 5 — Preparation of 2-(t-butylimino)-3- methyl-6H-l,3,4-thiadiazin-5-one hydrobromideTo a stirred solution of 5.75 g (0.05 mol) 2- methyl-4-t-butylsemithiocarbazide in 50 ml dichloromethane was added dropwise 9.15 g (0.05 mol) ethyl alpha-bromothio- acetate at 25°C. The reaction mixture was stirred at 25°C for 20 minutes (slightly exothermic reaction) and then heated under reflux for 4 hours. After cooling, the pre¬ cipitated solid was filtered, washed with hexane and dried to give 7.3 g of product, m.p. 215-216°C.The compounds tabulated in Tables A and B were prepared by procedures similar to those of Examples 1-5. The structure of each compound tabulated in Tables A and B was confirmed by nuclear magnetic resonance and/or infra¬ red spectroscopy. TABLE ACompounds of the formulaCH3Elemental AnalysisC H NNo. R2 m.p. ,°C Calc. Found Calc. Found Calc. Found A-l 4-Cl-jz. 143-145 12.5l 13.21A-2 i-C3H7 122-124 14.ll 13.81A-3 n-C3H7 126-130 37.6 35.6 6.3 5.9 18.2 17.2A-4 t-C H9 127-129 40.4 39.3 6.8 6.6 17.7 17.1A-5 3-CF3-J-- 83-84 45.7 44.4 3.5 4.1 14.5 15.0A-6 3,4-Cl2-jrf 118-120 41.4 40.7 3.1 3.1 14.5 14.1A-7 ≠ 140-144 46.6 43.4 4.7 4.8 16.3 15.5A-8 cyclohexyl 133-135 45.6 47.1 6.9 7.8 15.9 16.8A-9 CH2=CHCH2 68-70 37.9 35.1 5.5 5.6 19.0 17.9TABLE BCompounds of the formulaI CH3Elemental Analysis C H NNo. R2 R3 R4 m.p. ,°C Calc. Found Calc. Found Calc. FoundB-l t-C4H9 C2H5 C2H5 Oil 18.ll 17.9lB-2 n-C3H7 C2H5 C2H5 Oil 18.9l 19.4lB-3 CH3 C2H5 C2H5 Oil 20.61 20.61B-4 cyclohexyl C2H5 C2H5 Oil 44.3 43.6 6.9 6.9 11.1 10.8B-5 2-F-jz, C2H5 C2H5 oil 43.0 40.9 4.9 4.8 10.7 10.6B-6 i-CβHy C2H5 C2H5 oil 39.9 38.4 6.5 6.4 12.4 11.4B-7 3,4-Cl2-^ C2H5 C2H5 oil 38.0 37.4 4.1 4.3 9.5 9.7B-8 CH3 CH3 CH3 oil 29.7 30.2 5.0 5.0 14.8 14.6B-9 CH2=CHCH2 C H5 C2H5 oil 39.2 37.1 6.0 5.7 12.5 11.5B-10 φ C H5 C2H5 oil 45.0 41.4 5.4 5.4 11.3 10.0UTILITYThe thiadiazine compounds of this invention we tested as follows to illustrate their insecticidal activ ty. Test results are reported in Table C.Test ProceduresAphid (Aphis gossypii Glover): An acetone sol tion of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 40 ppm. Cucumber leaves infested with the cotton aphids were dipped in the toxicant solution. Mortality readings wer then taken after 24 hours.Two-spotted Mite (Tetramuchus urticae) : An ac tone solution of the candidate toxicant containing a sma amount of nonionic emulsifier was diluted with water to ppm. Lima bean leaves which were infested with mites we dipped in the toxicant solution. Mortality readings wer taken after 24 hours.Housefly (Musca domestica I . ) : A 500 ppm ace¬ tone solution of the candidate toxicant was placed in a microsprayer (atomizer). A random mixture of anesthetiz male and female flies was placed in a container and 55 m of the above-described acetone solution was sprayed on them. A lid was placed on the container. A mortality reading was made after 24 hours.American Cockroach (Periplaneta americana ^. ): A 500 ppm acetone solution of the candidate toxicant was placed in a microsprayer (atomizer). A random mixture o anesthetized male and femal roaches was placed in a con¬ tainer and 55 mg of the above-described acetone solution was sprayed on them. A lid was placed on the container. A mortality reading was made after 24 hours.Alfalfa Weevil (H. brunneipennis Boheman): A 500 ppm acetone solution of the candidate toxicant was placed in a microsprayer (atomizer). A random mixture o anesthetized male and female flies was placed in a con¬ tainer and 55 mg of the above-described acetone solution was sprayed on them. A lid was placed on the container. A mortality reading was made after 24 hours.BUR_ O Rootworm (Diabrotica u . undecimpunctate Mannerheim) : A batch of 20-30 two-day-old Diabrotica eggs was placed on the bottom edge of a 236-ml plastic cup. The cup then received the following materials:(1) 66 g soil treated with 15 ppm of the test compound; (2) 15 ml water; (3) 10 presoaked (in water for 2 hours) corn seeds evenly distributed on the soil sur¬ face; (4) 66 g soil treated with 15 ppm of test compounds; and (5) 15 ml water. The cup was placed in an incubation chamber and lightly watered as needed to keep the soil damp. After 14-16 days the test cup was examined under a dissecting microscope by observing the corn roots and soil through the clear plastic walls of the cup. Control of newly hatched larvae was rated by visually evaluating the degree of corn root damage by feeding larvae in conjunc¬ tion with visible presence of live and/or dead larvae. TABLE C — Insect Control, %No. Aphid Mite Housefly Roach Weevil Rootworm LooperB-l 70 0 60 100 100 75 100B-2 100 99 90 0 100 80 20B-3 100 99 100 100 100 0 100B-4 85 0 0 0 0 0 0B-5 94 0 0 . 0 0 0 0B-6 99 94 100 - 100 78 50B-7 0 70 22 - 0 98 100B-8 99 98 99 . - 100 0 80B-9 100 50 22 0 100 100 80B-10 98 0 0 0 0 100 80The thiadiazine compounds of the invention are toxic to a variety of crop and household pests, in addi¬ tion to the typical pests exemplified above. Like most agricultural chemicals, they are not usually applied full strength, but are generally incorporated with conventional biologically inert extenders or carriers normally employed for facilitating dispersion of active ingredients for agri¬ cultural chemical applications, recognizing the accepted fact that the formulation and mode of application may affect the activity of a material. The toxicants of this invention may be applied as sprays, dusts, or granules to the insects, their environment or hosts susceptible to insect attack. They may be formulated as granules of large particle size, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, or a any of several other known types of formulations, depending on the desired mode of application.Wettable powders are in the form of finely divided particles which disperse readily in water or othe dispersant. These compositions normally contain from 5-80% toxicant and the rest inert material which includes dispersing agents, emulsifying agents, and wetting agents. The powder may be applied to the soil as a dry dust or preferably as a suspension in water. Typical carriers include fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wet, inorganic diluents. Typi¬ cal wetting, dispersing, or emulsifying agents used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfonates and their sodium salts; alkylamide sulfonates, including fatty methyl taur- ides; alkylaryl polyether alcohols, sulfated higher alco¬ hols, and polyvinyl alcohols; polyethylene oxides; sul- fonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition products of long chain mercaptans and ethylene oxide. Many other types of useful surface-active agents are available in commerce. The surface-active agent, when used, normally comprises from 1% to 15% by weight of the pesticidal composition.Dusts are freely flowing admixtures of the active ingredient with finely divided solids such as talc, natural clays, kieselguhr, pyrophyllite, chalk, diatom- aceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours, and other organic andOM. A inorganic solids which act as dispersants and carriers for the toxicant. These finely divided solids have an average particle size of less than about fifty microns. A typical dust formulation useful herein contains 75% silica and 25% of the toxicant. <-Useful liquid concentrates include the emulsifi¬ able concentrates, which are homogeneous liquid or paste compositions which are readily dispersed in water or other dispersant, and may consist entirely of the toxicant with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone, and other non-volatile organic solvents. For application, these concentrates are dispersed in water or other liquid carrier, and normally applied as a spray to the area to be treated.Other useful formulations for insecticidal appli¬ cations include simple solutions of the active ingredient in a dispersant in which it is completely soluble at the desired concentration, such as acetone, alkylated naphtha¬ lenes, xylene, or other organic solvents. Granular for¬ mulations, wherein the toxicant is carried on relatively coarse particles, are of particular utility for aerial distribution or for penetr *ation of cover crop canopy.Baits, prepared by mixing solid or liquid concentrates of the toxicant with a suitable food, such as a mixture of cornmeal and sugar, are useful formulations for control of insect pests. Pressurized sprays, typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low-boiling dispersant solvent carrier, such as the Freons, may also be used. All of these techniques for formulating and applying the active ingredient are well known in the art.The percentages by weight of the toxicant may vary according to the manner in which the composition is to be applied and the particular type of formulation, but in general comprises 0.1 to 95% of the toxicant by weight of the pesticidal composition. The pesticidal compositions may be formulated and applied with other active ingredients, including othe nematocides, insecticides, fungicides, bactericides, plan growth regulators, fertilizers, etc. In applying the chemical an effective amount -and concentration of the tox cants of this invention is, of course, employed.The terms insecticide and insect as used herein refer to their broad and commonly understood usage rather than to those creatures which in the strict bio¬ logical sense are classified as insects. Thus, the term insect is used not only to include small invertebrate animals belonging to the class Insecta , but also to other related classes of arthropods, whose members are seg mented invertebrates having more or fewer than six legs, such as spiders, mites, ticks, centipedes, worms and the like. | CLAIMS :1 . A compound of the formul awherein Rl is alkyl of 1 to 6 carbon atoms, R2 is alkyl of 1 to 6 carbon atoms, alkenyl of 3 to 6 carbon atoms, cyclo¬ alkyl of 5 to 6 carbon atoms, phenyl or phenyl substituted with 1 to 2 substituents selected from the group consist¬ ing of alkyl of 1 to 4 carbon atoms, fluoro, chloro, bromo, iodo, nitro, t ifluoromethyl, trichloromethyl, tri- bromomethyl, and alkoxy of 1 to 4 carbon atoms, R is alkyl of 1 to 6 carbon atoms and R4 is alkyl of 1 to 6 carbon atoms.2. A compound according to Claim 1, in which R is alkyl of 1 to 3 carbon atoms.3. A compound according to Claim 1 or 2, in which R3 and R4 are alkyls of 2 to 4 carbon atoms.4. A compound according to Claim 1, in which l is alkyl of 1 to 3 carbon atoms, R2 is alkyl of 1 to 6 carbon atoms and R and R4 are alkyls of 2 to 4 carbon atoms.5. A compound according to any preceding claim, in which R and R4 are ethyl.6. A compound according to Claim 5, in which R is methyl and R2 is t-butyl. 7. An insecticidal composition which comprises a biologically inert carrier and an insecticidally effecti amount of a compound according to any preceding claim.8. A method of killing insects which comprises c tacting said insects or their habitats with an insectici dally effective amount of a compound according to any on of Claims 1 to 6 or a composition according to Claim 7.9. A compound of the formulaR1R 22N=C^ NH i iS C=0NCH2wherein l and R2 are as defined in Claim 1.10. A method of preparing a compound according t Claim 9 which comprises reacting a thiosemicarbazide of the formulaS n R2-NHC-NH-NH2Rl wherein Rl and R2 are as defined in Claim 1, with chloro acetic or bromoacetic anhydride in the liquid phase.11. A method of preparing a compound according to Claim 9, which comprises reacting a thiose icarbizide of the formulaSIIR2-NHCNHNHIRlO wherein R! and R2 are as defined in Claim 1, with an alkyl alphahalothioacetate wherein said alkyl has 1 to 6 carbon atoms and the halo is chloro or bromo in the liquid phase.12. A method according ,to Claim 11, wherein said alkyl has 1 to 3 carbon atoms.13. A method according to Claim 11 or 12, wherein R2 is alkyl and said compound is isolated as a hydrogen halide salt.14. A method according to any one of Claims 11 to13, wherein the reaction temperature is from about 25°C to 100°C.15. A method according to any one of Claims 11 to14, wherein the molar ratio of thiosemicarbazide to thio- acetate is about 1:1.2 to 1.2:1.16. A method of preparing a compound according to Claim 1, in which a compound according to Claim 9 or a hydrogen halide salt thereof is reacted with a dialkyloxy- halothiophosphate of the formulaISX-P-OR3I• OR4 wherein R and R4 are alkyls of 1 to 6 carbon atoms and X is chloro or bromo. | CHEVRON RES; CHEVRON RES CO | CLEVELAND J; EDWARDS L |
WO-1979000833-A1 | 1,979,000,833 | WO | A1 | XX | 19,791,018 | 1,979 | 20,090,507 | new | B22F3 | C21D1, B22F3, C22F1 | B22F3, C22F1 | B22F 3/14 | METHOD OF AND APPARATUS FOR HOT PRESSING PARTICULATES | Articles (11) are formed by hot pressing metal or metallic particulates (12) at temperatures between about the recrystallization temperature and about the solidus temperature for the metal or alloy after first preheating the particulates and the die (14). The particulates are hot pressed for a very short period of time, usually less than five seconds at about 12 tons per square inch or greater to compact and weld the particles together into a wrought metal article (11) having substantially greater tensile strength and a better isotropic strength than a conventional cast or powder metallurgy article of the same metal or alloy. Additionally, the articles (11) can be made with 99+ percent of theoretical density and with substantially no gas porosity. The article's surfaces may be smooth and held to relatively close tolerances with a good uniformity of surface hardness. Articles can be formed using conventional die presses to press articles repetitively without welding of the articles to die walls even when using aluminum particulates. The preferred particulates are substantially larger in size than the conventional powder materials used in powder metallurgy nd appear to be strain hardened during the hot pressing thereof. | METHOD OF AND APPARATUS FOR HOT PRESSING PARTICULATESThis invention relates to the formation of precision metal articles from metal or metallic particles and to a method of and apparatus for compacting and -consolidating such particles at elevated pressures and -temperatures.From a commercially significant standpoint, -the use of particulate metals to form articles has been limited principally to aluminum powder or other powder__etallurgy materials and products therefrom. The present invention is directed to expanding the horizons for the ■use of particulate materials beyond the powder metallurgy technology and beyond the metals commonly used therein to encompass iron, lead, magnesium, copper, molybdenum, •and other materials as well as aluminum. Also, with the present invention, hot pressed particulates are formed into articles with such superior properties that -enable the use of such articles in applications heretQ- fore not thought possible. As will be explained in-greater detail, it is possible to manufacture directly by a hot pressing technique precision parts with sufficient strength, dimensional precision, and surface characteristics that the parts may be used directly or with a minimum of machining operations. The most common and hence proper reference for -the state of the art of forming articles from particu¬ late metal is the art of aluminum powder metallurgy. Typically, the aluminum powder metallurgy process requires the use of pure aluminum metal powder which may be coated with a lubricant and cold pressed in a die to form a green product. Then the green product is sintered for 20 minutes in a protective atmosphere. The sintered ■ product, somewhat distorted, is later repressed or coined in a press to the finished article. The aluminum powder metallurgy article made with such a process is generally brittle and has some porosity and lacks the high tensile -strength of products machined from annealed and forged aluminum bars. On the other hand,, the hot pressing method of the present invention allows the use of either pure metal aluminum or alloy aluminum materials and the use of ■aluminum alloy scrap commonly called swarf . The use of scrap as a raw material provides a major reduction in the -cost of raw materials for the product. With the hot pressing method of the present invention, aluminum or -aluminum alloy particles may be hot pressed directly and -quickly into a desired shape with precision dimensional -surfaces in contrast to the cold pressing, sintering, and -coining operations used for powdered aluminum metallurgy, as above described.Additionally, it has been found possible to strain harden the particles as they are being hot pressed into' precision dimensioned products to provide increased .mechanical properties more akin to cast-wrought annealed products but without the expense of an annealing process. Some work has heretofore been done with hot pressing of aluminum particles into sheets, as disclosed in U.S. Patent No. 3,076,706. The hot pressing method disclosed therein is substantially different in that different pressure and temperature relationships were used and further in that the sheet.was formed betweenOM xolls having an opening pass at the ends thereof. More •specifically, the sheet was formed between water-cooled rolls with the temperature of the rolls at the nip being -about one-half the temperature to which the aluminum particles were preheated. Further, the calculated pres¬ sure was about 12,000 psi and the resulting sheet had a generally fibrous character. Typically, the sheet was' reduced in thickness by cold rolling subsequent to for¬ mation and then annealed and crystallized at about 600°F to obtain the desired physical characteristics for the .sheet. In the present invention, however, the pressures are significantly higher, for example, 12,000 to 100,000 psi and the temperatures employed are higher and result in a non-fibrous product. Grain growth is avoided and the metal article has properties more akin to a wrought- annealed aluminum- article than a cold-worked fibrous -metal article as made in U.S. Patent 3,076,706. Further, products made with the hot pressing technique of the pressing invention may give the appearance of- being annealed although they have not been annealed.The present invention also has a preferred apparatus which has the capability of forming articles with relatively thick cross sections, e.g., 1/2 inch or greater, at elevated temperatures and pressures without the articles welding or otherwise sticking to the die. With the present invention, aluminum particles may be hotpressed in dies made of ordinary tool steel which can withstand the relatively low temperatures of 400° to 600βC employed in the hot pressing process. The material sticking to the die problem is further alleviated by the use of die lubricants such as graphite or other materials. For the thicker cross-sectional articles, the hot pressing process may employ a two-step or phase compaction in a single die with an initial compaction of the particles to remove substantially the main voids therebetween within a first portion of the die. Preferably, the apparatus vill have an automatic die lubrication system. Further, it has been found that the large particles are preferably agitated or otherwise kept moving while they are being preheated so that they do not agglomerate and will freely mix and pour to fill the cavities in the hot pressing die. If desired, the heated aluminum particles may be kept in a protective atmosphere within a feed box for the die but the actual pressing may be done in an ambient atmosphere because of the relatively short pressing times used in the compacting operation.Accordingly, the general object of the invention • is to provide a new and improved hot pressed particulate article and to provide a method of and an apparatus fcr manufacturing such an article. A more specific object of the invention is to provide a new and improved wrought article made from -compacted particles of aluminum or aluminum alloys hot pressed at elevated temperatures and pressures to provide a strain hardened product. A further object of the invention is to provide•a method and apparatus which can mold precision products with good mechanical properties from low-cost particulate xaw materials and in time periods of 30 seconds or. less. These and other objects of the invention will become apparent from the following detailed description -taken in connection with the accompanying drawings in -which:FIGURE 1 is a diagrammatic view of an apparatus for practicing the method of hot pressing metal or etal- lie particles into articles in accordance with'thepresent invention;FIGUEE 2 is a graph illustrating the effect of temperature changes on the thickness differential articles made with the invention? FIGURE 3 is a graph illustrating the effect of a change of temperature on the surface finish of hot pressed articles made in accordance with the invention;FIGURE 4 is a graph illustrating the effect of pressure on the surface finish of the articles made in accordance with the invention; 5 - FIGURE 5 is a graph illustrating the effect of pressure on a Rockwell Hardness differential between different portions of an article made in accordance with . the inventionsFIGURE 6 is a graph illustrating the effect of 10 a change in temperature on the Rockwell Hardness for the articles made in accordance with the invention*FIGURE 7 is a graph illustrating the effect of the change of temperature on the ultimate tensile strength of articles made in accordance with the 15. invention?•FIGURE 8 is a graph illustrating the effect of citanges in pressure on flash thickness for articles made in accordance with the invention;- FIGURE 9 is a graph illustrating the effect on 20 Rockwell Hardness of articles hot pressed at temperatures -below and substantially above the solidus temperature;FIGURE 10 is a graph illustrating the effect on ultimate tensile strength of hot pressing at temperatures below and above the solidus temperature; ■25 FIGURES 11, 12, 13 and 14 are magnified photo¬ micrographs of etched sections of hot pressed articles formed by hot pressing particulates in accordance with the invention; —FIGURE 15 is a magnified photomicrograph of an -30 etched section of a hot pressed article formed by hot pressing magnesium particulates as described in Example5 hereinafter;FIGURE 16 is a magnified photomicrograph of an etched section of a hot pressed article formed by hot 35 pressing magnesium particulates as described in Example6 hereinafter; and FIGURE 17 is amagnified pho_cιrdc_-θgraph of an etched section of a hot pressed article formed by hot pressing particulates of copper as described in Example 7 hereinafter. 5 As shown in the drawings for purposes of illustration, articles 11 may be formed by hot pressing heated particles 12 in a hot pressing apparatus having a heated die 14. The illustrated die comprises a heated die body 16 having an internal cavity 18 which -is filled10 with preheated particulates from a heated feed means or box 22 in which are stored the preheated particulates. The die may take various shapes and forms but herein is illustrated as having an upper top punch 24 connected to a conventional press for downward movement into_ the die15 cavity to compress a charge of particulates at a desired pressure and for a given amount of time. A bottom punch .26 is movable upwardly in the die cavity to eject the compacted article 11 from the die cavity. The ejected article may be shifted transversely from the die by a -20 transfer means 28 which may shift the article into a quenching tank 32, if a quenching is desired.In accordance with the present invention, articles 11 formed of hot pressed metal or metallic particulates may be made by a unique hot pressing process25 with strength and other properties superior to properties obtained from directly cast metals and with properties ■such as tensile strength greater than those of cast articles and approaching those of wrought articles formed Jby working the cast article. Moreover, the articles30 appear to have more isotropic tensile strengths than do cast articles of the same metal. The articles appear to be cold worked and annealed to provide a wrought article even though the articles have not been given a conven¬ tional annealing or heat treatment subsequent to the35 formation thereof. The particulates used in the pre¬ ferred hot pressing process are relatively large asO -compared to powder particles and it is thought that these larger particulates afford sufficient volume of metal to be worked when being consolidated under elevated tempera¬ tures and pressures within a die. It appears although it 5 is not certain that particles are strain hardened when • -deformed and compressed to eliminate the voids there¬ between. The preferred articles are formed with high densities approaching substantially theoretical density. Further, the exterior surfaces of the articles may be10 smoother and held to closer tolerances than exterior surfaces of cast articles.In accordance with the present invention, •articles 11 can be produced economically and repetitively from the die 14 when using current die presses to hot i5 press articles 11 at relatively high speeds and with materials, such as aluminum or aluminum alloys, which are normally thought to weld themselves to dies or to pre¬ clude the formation of relatively thick cross-sectional articles.•20 __ore specifically and in accordance with the present invention, the preferred method comprises the . -steps of: providing particulates 12 of metal or metal¬ lic alloy (preferably having a surface area to volume xelationship in the range of 3 to 1,000) and being free25 flowing to fill the die cavity 18, preheating the parti¬ culates (as within the preheat box 22) to a temperature within the range of between about the recrystallization temperature for the metal or alloy and about the solidus temperature for the alloy (i.e., the melting point of30 the metal) , heating the die cavity 18 to a temperature sufficient to maintain the particulates within said temperature range during a subsequent hot pressing, hot pressing the preheated particulates by the application of sufficient pressure (e.g., 12,000 to 100,000 psi) to35 consolidate the particulates into a high density article for a. time period of less than 30 seconds while main-'BUR_46r_.OMPI^ - taining the particulates within said temperature range, removing the article 11 from the heated die cavity 18. -The preferred process and articles formed therefrom are made with particulates in the form of particles larger in size than conventional powder particles because such larger' size particles do not tend to sinter weld to each other when preheated and because it is thought that the larger size particles are able to cold work and/or strain harden whereas the very fine powder particles may not. As used herein, the term particulates is generic to the preferred larger size particles having (SA V) surface -area to volume relationships in the range of about 3 to 1000 and to the powders, such as aluminum powders, which typically have SA/V relationships of 1500 or larger. Thus, as used herein, the term particulates is used in a generic sense to refer to both larger size particles .and the smaller size powders and the term particles is used to indicate metal pieces having an SA/V relationship of about 3 to 1000. Metal pieces with SA/V relationships substantially above 1000 will be termed powders hereinafter.As used herein, the surface area to volume re¬ lationship is defined by dividing the surface area in square inches by the volume in cubic inches. The rela- tionship will thus be expressed in terms of inches to the 10 1 power. Of course, a similar division may be •performed for a metric area in square millimeters divid¬ ed by a volume in cubic millimeters. In the preferred method, the products may be compressed with sufficient pressure to obtain a density of about 99% of theoretical density. Further, particles may be heated and hot pressed at about the solution annealing temperature for the metal or alloy and then subsequently age hardened to pro¬ vide a further strengthening of the article. * It is an important aspect of the process that the particles are hot pressed while at a temperature -above their recrystallization temperature and below their melting or solidus temperature for a short period of time (30 seconds or less) and then cooled below the recrystal¬ lization temperature before the grains in the particles 5 can recrystallize and grow or anneal. For example, for aluminum alloy particles, the article may be hot pressed for less than 4 seconds at a temperature above the re¬ crystallization temperature but below the solidus tem¬ perature and removed and cooled quickly below the re- 10 crystallization temperature so as to prevent substantial -grain growth or any substantial annealing. Surprisingly, it has been found that the hot pressed article is hard rather than soft. If one allows the hot pressing tem¬ perature to go above about the solidus temperature or 15 above the melting temperature to the extent that a sig¬ nificant portion of the particles attain a liquid state before or during hot pressing, the hardness and tensile strength will be significantly diminished. As used here¬ in, the term about the solidus temperature is intended 20 to include temperatures which may be as much as 10% or - -even 20% higher than the theoretical solidus temperature for a given alloy for the reason that at these tempera- rtures slightly above the theoretical or exact solidus•temperature for the alloy there is insufficient liquid -25 from the particles present to substantially adversely .-affect the results.__dditionally, articles made with generally ^uniformly shaped and sized particles and hot pressed in accordance with this invention may provide more uniform 30 isotropic properties such as transverse and longitudinal tensile strength than is the case with cast or wrought • -articles of the same metal or alloy. By preheating and then hot pressing uniform particles such as needles or spheres of substantially uniform size, the particles de- 35 form and join to form a uniformly appearing matrix or a lamellar cross section which provides better isotropicOMPI fa -qualities for the article.In contrast to usual porosity found in powder metallurgy articles, the articles 11 may be made with substantially zero porosity and full density, that is, a density equal to about 100% of the theoretical density. These high density articles are also found to be signif¬ icantly more leak-proof to oil or gas than the more po- xous sintered powdered aluminum metallurgy articles or die cast aluminum articles. The microstructure of the article is similar to that of an article that is fully annealed even though no annealing has taken place. The surface characteristics of the articles are very good, being very uniform and highly reproducible as to hardness -and dimensional tolerances. Referring now in greater detail to the pre¬ ferred process, one form of particle which has been -successfully used is a needle-shaped aluminum particle formed by pouring molten aluminum into a perforated'spin¬ ning cup and using centrifugal- force to snap off particu- late needles emerging from the apertures. A general description of one process for forming aluminum particles is disclosed in U.S. Patent No. 3,241,948. The preferred particles are fairly uniform in size and have a minimum -of oxidation. Aluminum needles having'lengths ranging from 0.1 to 0.250 inch and a maximum diameter of about 0.015 inch have been used. Apparent densities for the .aluminum needles range from about 1.3 gram/cc for the •coarser needles to 1.1 gram/cc for the finer needles, the latter being close to the apparent density for con- ventional aluminum powder of 1.1 grams per cc.The raw material used to form the aluminum needles may be scrap aluminum which will usually have some alloying metal therein. The scrap (commonly called swarf ) can be cleaned and degreased prior to being melted within a furnace and poured into the perforated rotating cup to be spun out as needles. By spinning at -a constant speed and temperature, the aluminum particles-obtained may be uniform in size and possess a high degree of luster with nearly 100% utilization of the molten aluminum being poured into the cup. Aluminum particles of about 1/4 inch in length have been used successfully. Other much larger aluminum particles , such as3/16 inch cubes , also have been hot pressed in accordance. with the method described herein. It is considered that spherical particles may be even more advantageous because of their lower surface area to volume relationship and their good packing and filling characteristics within the ie. The uniformity of particles as to both size and ■shape is preferred to obtain more isotropic qualities for the hot pressed article. . Rather than melting the scrap and reforming the same into acicularly or spherically shaped particles , scrap machine shop drillings or cuttings may be broken up _Ln a hammer mill to the desired size and then hot pressed in the die. That is , the swarf , if small enough in size, may be used directly for the hot pressing process .The particles are preheated to about their hot pressing temperature prior to being inserted into the die cavity 18. Preferably, the particles are preheated . within a means such as a feed box 22 by resistance heaters (rot shown) and an inert hot gas flows through the feed box to prevent substantial oxidation of the particles while in residence in the feed box. Also, the particles may be agitated while in the feed box by sliaking them with a v___ ating means (not shown) to prevent their sticking to one another while in the feed box. Preferably, the particles will be at or slightly warmer than the temperature at which the .subsequent hot pressing occurs to account for any tetrjpeiaturε loss during transfer frαn the feed box into the heated die 14.The very short periods of time to compact the particles and to remove the article from the die and to cool the same below the recrystallization temperature is a key factor not only to the properties obtained for the-BU REA UOMPI >fa WIPO Λ> ,^ - -article itself but also is a key factor in the economics of producing parts cheaper than heretofore. In contrast, the typical time period for sintering powder compact in powder metallurgy is 20 minutes or more and later heat 5 treating operations require hours or fractions of hours. Quenching in water or other liquid will obtain a supersaturated solution and then the article may be allowed to naturally age at room temperature. For example, aluminum alloy particles may be hot pressed10 quickly and then immediately ejected and quenched. The hot pressed aluminum article may then be allowed to naturally age for four days at room temperature to pro-. vide a T-4 heat treated aluminum article. The aluminum-article may, if desired, be further heat treated to T-615 condition by placing the article in a temperature of about 250?F for a period of about 18 hours. For most metals, the number and kinds of alloying agents used for pre¬ cipitation hardening are well known. Although only aluminum has been mentioned specifically as being hardened-20 by precipitation, it is to be understood that other alloyed metals, such as magnesium or steel, may be precipitation hardened.Consideration now will be given in greater detail to the various parameters of temperature, pressure25 and time for one specific example, namely, aluminum alloys, and other parameters for other metals may be obtained and ascertained. For ~ _uτ.emetal aluminum parti¬ cles, the temperature will not exceed the melting temper¬ ature of 660°C at which some melting of aluminum will30 occur. Likewise, the temperature will be above the re¬ crystallization temperature for aluminum. For aluminum alloys, the temperature of recrystallization and the solidus temperature will vary with the amount of alloying material. Generally speaking, the temperatures used in35 the process will be from about a recrystallization temper¬ ature of about 400°C for aluminum alloys to the solidusBUREA0MP1 , IPO -cαrve temperature of about 600°C. The solution anneal¬ ing temperature will be closer to the solidus curve than the recrystallization temperature for aluminum alloys.Better mechanical properties are obtained when hot pressing aluminum alloy particles at higher tempera¬ tures closer to the solidus temperature because the particles will be more plastic and will consolidate and fill any crevices or fine details in the mold, as will be explained for aluminum alloys being hot pressed at tem- peratures of about 800°F to 900°F, in connection with the graphs of FIGURES 2 to 10, than when hot pressing at lower temperatures, such as 600° to 800°F. That is, it appears that the particles are more plastic and flow and - weld easier when at the higher temperatures than at lower temperatures near the recrystallization temperature. However, it will be recognized that a temperature of about 900°F is still below the solidus temperature and that there is a marked fall-off of properties if the particles are hot pressed at temperatures above the solidus and at which a significant amount of the parti¬ cles have become molten.The ability to hot press the aluminum particles at temperatures of 900βF or lower for a time period of only several seconds permits the use of dies constructed from ordinary tool steel. This is in contrast to higher cost superalloy metals that must be used for processes in which higher temperatures and longer pressing time -periods at higher temperatures are required. Likewise, because of these low temperatures and because of the relatively short time in the die, the metal particles are not highly oxidized. It is to be understood that particles may be heated in other and various ways from that disclosed herein. Preferably, the heated metallic alloy particles are heated in the box to a temperature and for a sufficient time for the alloy constituents to go into solid solution for a later precipitation hardening.The preferred hot pressing operation is accom¬ plished in ambient atmosphere, but if a reduction in the -oxidation is desired, particularly for ferrous particles heated to higher temperatures, such as 1800βF, a pro¬ tective atmosphere may be used about the heated particles when being transferred into and while being hot pressed in the die 14. Usually, a vacuum need not be employed at the die, as this adds to the expense of the process, although some conventional hot pressing techniques use a vacuum. When hot pressing ferrous particles at tempera¬ tures of 1800°F or higher, the heated die 14 should be made of more expensive superalloy materials to provide the requisite strength and longevity for the die at these higher pressing temperatures.The temperature ranges for hot pressing other particles may be varied but it is preferred to hot press copper or copper alloy particles at about 600°-800°C. The magnesium particles can be hot pressed at about the same temperatures used for aluminum or aluminum alloy particles.-Generally speaking, the process is preferably isothermal with the die 14 and the particles being pre¬ heated to the hot pressing temperature. This preheating is necessary because the time of hot pressing is usually so short that the articles could not be heated uniformly throughout in the very short period of the pressing time. Herein, the upper and lower pressing rams were not heated with only the mold walls defining the cavity being pre- heated. Of course, it is possible to heat the rams as well as the mold walls.The hot pressing pressures may be varied depending upon the particles being used and the density desired' for the product. For aluminum alloy particles, pressures in the range of 12,000 psi to 100,000 psi are sufficient to press the aluminum particles into articlesOMP WIP having substantially 100 percent full theoretical den¬ sity. For lower densities, the pressures may be on the lower side. Once full density has been achieved for the -article by application of a given pressure, the applica- tion of additional higher pressures merely serves to cause the article to tend to bind or weld to the side walls of the die. Also, the higher and excessive pres¬ sures force the hot pressed metal further into the die clearance openings and result in greater thicknesses of flash or burrs which will usually be removed. The increase in flash or burr thickness with increases in hot pressing pressure is illustrated in FIGURE 8. The pres¬ sures used for aluminum of about 12,000 to 50,000 psi at temperatures of 950°F or less do not readily damage tool steel dies and the die may be used repetitively for the. production-like manufacture of particles.Aluminum and aluminum alloys have an affinity for welding or alloying themselves to the die walls at elevated temperatures and pressures used in hot pressing or powder metallurgy processing. The walls of the die cavity 18 are lubricated.with a conventional graphite or lubricant to reduce the likelihood of the article adher¬ ing to the die walls. The movement of the particles in the die during hot pressing is considerable as the height of the hot pressed article is about one-half the height of the particles filling the die prior to compaction. A significant movement of the particles along the die wall -during hot pressing has been found to wipe the die lubri¬ cant from the die wall- leaving the die walls generally unprotected during the final pressing portion of the cycle.In accordance with the present invention, the problem of welding or adhering of the hot pressed parti¬ cles to the die wall has been overcome by a multi-step hot pressing method in which an initial and major com¬ paction is made in a first portion of the die and a final higher density consolidation is made in another_tnd second portion of the die. The initial compaction of the particles reduces the fill volume in the die to about the final size for the article with the particles under- going more gross movements and hence- to scraping some of the die lubricant from the die walls. The welding of the article to the non-lubricated areas of the die walls is avoided by shifting the initially and partially consoli¬ dated article in the die to a portion which was not filled with particles and hence not scraped of the die lubricant thereon. Then the final and usually higher pressure is applied in this second portion of the die. The final pressure consolidates the article to its full and final density usually at r- close to theoretical density and the final pressure is usually significantly higher. By way of example only, scrap metal aluminum particles were compacted at 950°F by .very low pressure of 4,000 psi to about 85 percent of. theoretical density and then shifted upwardly into the die cavity where lu— bricant was still present. At this time, the upper die further compacted the particles to 99 percent plus of theoretical density with the particles undergoing rela¬ tively small movement along the die walls during this final 15 percent compaction which takes up most of the internal voids and may be made at about 24,000 psi. The entire process may still be made in under ten seconds with the initial pressure taking only one second or two and the final pressure application likewise taking only one or two seconds. The difference between the one and two-step process of hot pressing is noticeable in that articles made with a one-step process tend to be scored on the outer surface thereof when contrasted with arti¬ cles made with the two-step process.Typical lubricants are graphite or boron nitride. The residue of the lubricant on the outer surface of the articles made by the two-step process may even be advantageous with the lubricant again being used during a subsequent forging in a forging press.By way of example, the following examples will be given for illustrative purposes: Example 1EC aluminum scrap containing 2 to 3% copper as an impurity was converted into needle-like particles by melting the scrap and pouring it into a spinning cup of3 inch diameter having holes of 0.052 inch diameter. EC aluminum refers to aluminum typically found in elec¬ trical cables as a current-carrying conductor. The mol¬ ten metal was at 1300°F and the cup was spun at 1500 rpm. The needles were cooled and collected. The needles had a good luster. A charge of needles about 0.5 inch in depth was inserted into a split die formed of tool steel con¬ taining a tool body having a cavity opening measuring 1-7/8 inch by 3/8 inch. The die was placed in a stain¬ less steel closed chamber evacuated to 28 inches σf .mer¬ cury and heated to 950°F. At this temperature, the ram was actuated to apply 30,000 psi pressure to the needles for about two seconds. The die was then taken from the chamber and split open and the resulting compacted article having a thickness of abou 0.25 inch was readily removed. The article quickly air cooled at ambient room temperatures to a temperature below the recrystallization temperature. The needles were found to be thoroughly compacted, welded and intermeshed into a unitary article having a density equal to almost 100% of theoretical density. The Rockwell Hardness value varied from R/H 82 to 85 across the various sides of the article. A tensile specimen from the article had an ultimate tensile strength of 21,875 psi and a yield tensile strength of 19,320 psi. The elongation appeared to be about 4.2%. The structure was clean with a precise smooth exterior with virtually no holes therein. When cut in cross section, some elonga¬ tion Of the needles was observed and many fine grains were seen within the individual needles. There was no significant grain growth observed.Example 2Needles produced as above described in connec- tion with Example 1 were loaded as an 8 gram charge into the lubricated, split, tool steel die having the same size of cavity. Using the same conditions above except that pressure which was increased to 100,000 pounds per square inch, the article was found to have the same exterior and observable properties as above described and tested out to an ultimate yield tensile strength of 21,555 psi; a yield tensile strength of 19,205 psi; elongation of 4.4% and a Rockwell Hardness of R/H 81 to - 83 about the article. There was no observable grain growth as the axticle had been allowed to cool quickly below its recrystallization temperature after removal from the die. #Example 3Clean aluminum 7075 machine shop drillings were broken up and loaded into the 1-7/8 inch by 3/8 inch die cavity. An 8 gram charge was heated to 900°F and the preheated swarf particles were hot pressed at. a pressure of 100,000 psi for a period of less than 5 seconds. The ejected article was allowed to air cool immediately to a temperature less than its recrystallization temperature. The compact article was well bonded and had about a 99.1% of theoretical density and an R/H hardness of 94.9. The compact was cleaned by a vibratory cleaner and then ball burnished to a mirror-like finish. Example 4- Needles of the type set forth in Example 1 were made into 250-300 gram charges and placed into a cylin¬ drical die cavity of about two inches in diameter and about two inches in length. The die and the particles were heated to a temperature of 950°F and then the needles were initiallycompacted at a pressure of 4,000 pounds per square inch for about one second to consoli¬ date into a compact particle having a first predetermined low density, for example, about 85% of theoretical densi¬ ty. The low density cylindrical slug was uniform and almost loose in the die with this initially applied pressure principally collapsing-the plastic needles with a gross movementof needles occurring within the die. During this initial hot pressing, no great lubricant re¬ moval from the die walls was seen and no galling appeared to have taken place. This initially hot press slug was removed from the die, the same die relubricated and the low density slug was re-hot-pressed at 950βF at 48,000 psi for 5 seconds. The article was then allowed to air cool quickly below its recrystallization temperature. The final hot pressed article had become significantly more dense as its density shifted from about 85% to about 100% of full theoretical density. Some of the aluminum ex¬ truded into the die clearance during the second pressure application. However, no die galling or slug scoring was evident after the second hot pressing operation. The article finally produced was generally uniform in appear¬ ance and its Rockwell Hardness R/H was varied by only two points along the sides thereof. Similar size slugs of 2 inches in diameter and up to 2 inches in length have been produced with the initial pressing at 950°F and to 85% theoretical density at 4,000 psi. These slugs were removed from the die and then re-hot-pressed in the same die (now relubricated) with a pressure of 24,000 psi for a period of 5 seconds to produce articles having full density. These articles were also air cooled to below their recrystallization temperature.In addition to the above-described examples, further rectangular bars measuring 1.875 inch x .375 inch x .25 inch dimensions were produced generally in accordance with the procedure set forth in Example 1 and examined to determine the effect of variations of temperature and pressure on the formation of the hot pressed article. Photomicrographs of such further examples produced generally in accordance with Example 1 are shown in FIGURES 11-14. As explained, temperature is the main variable and additional pressure beyond that needed to compact the article to 99% or greater of theo-r retical density is relatively unimportant. Generally, the time period was not varied significantly beyond five seconds with most of the articles being formed in only the time it takes to assure actual application of the pressure indicated, e.g., 15 tsi; 30 tsi; or 50 tsi. In actual production of parts on a commercial scale, the time of application need only be that to apply pressure to consolidate the particles and fill all of the die crevices. It has been found that the particle material # flows better at higher temperatures, for example, 900°F, than at lower temperatures, for example 650βF. The • plastic flow characteristic is important in order that the particle material fill the spline, crevices, or narrow cavities as well as to eliminate any internal voids within the article so that the article is dense and relatively leak proof when contrasted with the usual powder metallurgy articles. Another outcome of poor plastic flow is failure to provide a uniform thickness throughout the article when hot pressing the flat rectan¬ gular bar specimens. It was found that when forming these bars at 650°F that the thickness variation was as much as .008 inch, as illustrated in the graph shown in FIGURE 2. By increasing the hot pressing temperature, the plasticity of the heated particles increased and the thickness variation was dropped substantially and to almost zero at 925βF at a pressure of 30 tsi.To provide a better understanding of how the factors of temperature and pressure affected the relative surface finish, the above-described rectangularly-shapedO , A, axticles were made at temperatures of 650°F, 800°F and950°F, and also at three different pressures, namely, 15 tsi, 30 tsi and 50 tsi. A purely arbitrary scale of 1 to10 was chosen with a 10 score being given to surfaces which were smooth, flat and generally solid appearing and with the particle outlines being discernible only with . difficulty. At the other end of the scale, a score of4 or less indicated tht the surface of the rectangular bar was irregular and not smooth and flat with the parti- cle outlines clearly shown. With such poor surface conditions, the particles appear loosely joined rather than fully intermeshed and integrated with one another. Generally speaking, at the lower temperature of 650°F, and particularly at the lower pressures, for example, 15 tsi, the surface finish ratings were low, e.g., 4 and 6, as best seen in the graph of FIGURE 3. At these lower temperatures and pressures, the articles appeared some-, what porous with the needles clearly outlined and not fully meshed together as they are at the higher tempera- ture and pressure. At thehigher t__πaperat_res and pressures of 950°F and 30 tsi plus, the surface finish ratings were 8 to 10; and and the articles appeared, to be fully dense and have zero porosity and have their needles so well integrated that only with some difficulty is it possible to see the outline of the needles, particularly after the articles have been cleaned.If the pressure used is sufficiently high, such .as 30 tsi to 50 tsi, then the surface finish is found to be good, e.g., 8 or greater, even though the temperature is varied from about 650°F to 950°F, as depicted inFIGURE 3. The pressing temperature becomes significant at lower pressures, e.g., 15 tsi, for the reason that the particles will not experience the desired plastic flow at temperatures of less than about 700°F to afford a surface finish of 8 or greater, as depicted in FIGURE 3. Like¬ wise, if a pressing temperature of 650°F is used, good plastic flow is not achieved until a pressure of about30 tsi is used, as shown in FIGURE 4. Sufficient plas¬ tic flow to provide a good surface finish,- i.e., 8 or more, was obtained at temperatures 650°F to 950°F at the higher pressures of 30 tsi and 50 tsi with the best surface finishes being obtained for the higher pressure of 50 tsi, as depicted in FIGURE 3. Thus, it appears ' that higher pressures and temperatures provide more plas¬ tic flow and more dense articles with the best surface finishes, and this is depicted in FIGURES 3 and 4. At the lowest pressures and temperatures illustrated in FIGURES 3 and 4, the articles appear porous with the particles clearly outlined and not fully meshed together. The Rockwell Hardness may be substantially uniform when the article has been pressed to be sub¬ stantially fully dense. As will be explained in connec¬ tion with FIGURES 5 and 6, the differential of about two to four points for a fully dense, hot pressed article is achieved and this is acceptable commercially. Thus, the graph in FIGURE 5 shows that a Rockwell Hardness spread of less than four is obtainable when hot pressing at 950βF with pressures of 15, 30 and.50 tsi. Likewise, for articles hot pressed at 800°F, the Rockwell Hardness spread is below five for each of the pressing pressures of 15, 30 and 50 tsi. On the other hand, when the arti¬ cle is not fully dense as when compressed at 10 tsi and at 650°F, the hardness of the article varies substantial¬ ly from one area to another area, as indicated by the differential of 24 between different Rockwell Hardness readings in FIGURE 5. However, at the higher pressure of 50 tsi and a 650°F pressing temperature, the article may be compacted to be fully dense and provide an accept¬ ably uniformly hard product.It has been found that as density of the arti- cle increases, the Rockwell surface- hardness of the article also increases. As shown in the graph of FIGURE 6, when hot pressing at constant pressure of 15 psi and with an increase in temperature of pressing from about 500°F to 950°F, the density of the product increased and the Rockwell R/H increased from about 75 to 85 R/H. The temperature used during the hot pressing has a significant effect on the tensile strength of the article with the higher tensile strengths being obtained for the higher temperature hot pressing operations when using the constant pressure. This is because the product will be more dense with higher temperature pressings if a low and constant pressing pressure, e.g., 15 tsi, is used. When about 100% density is achieved, the articles had ul¬ timate tensile strengths of 22,700 psi for scrap EC alu¬ minum (with 2 to 3% copper as an impurity pickup) needle hot pressed article, as indicated for a 950°F pressing temperature in FIGURE 7. These articles having the 22,700 psi UTS had a 6.4% elongation and appeared to have microstructures of fully annealed parts although they had not been held at elevated temperatures for a time period sufficiently long enough for an annealing operation to have occurred. The above-described graphs were made from data using these EC aluminum articles.Testing of articles made by hot pressing of• 7075 aluminum swarf articles likewise showed increased tensile strengths obtainable with increased temperature until a temperature exceeded about the solidus tempera¬ ture . More specifically, the ultimate tensile strength increases significantly with an increase in temperature from about 750° to 900°F at 50 tsi. Above 900°F for this alloy, melting of the particles began and this re¬ sulted in a remarkable and significant decline in ten¬ sile strength as shown in FIGURE 10. Specifically, 7075-0 aluminum scrap chips hot-pressed at 900°F and 50 tsi for five seconds had an ultimate tensile strength of 52,000 psi. However, the ultimate tensile .strength dropped to less than 35,000 when these particles were -24- heated to 950βF and hot-pressed at 50 tsi. The 52,000 psi tensile strength is about 160 percent greater than that of bar stock of 7075-0 aluminum. Looking different¬ ly at the ultimate tensile strength of 52,000 psi, this is about two-thirds that which could be obtained for this alloy after a T-6 full heat treatment which involves a solution heat treating at 850βF and aging at 250°F for 25 hours.When the particles are heated and compressed at temperatures above about the. solidus temperature at which some of the particles melt, the hardness average drops rapidly and significantly. Thus, swarf of 7075 aluminum when hot pressed at 50 tsi for two seconds at tempera¬ tures between 900°F to 950°F experiences a rapid drop- off into a range of 95 to 70 average Rockwell E-hardness, as illustrated in FIGURE 9. On the other hand, the Rockwell Hardness average increased substantially with temperature increases from 800°F to 900°F as the arti¬ cles became more dense and hard at the higher tempera- tures u to about the solidus temperature.A photomicrograph of an article formed by hot pressing 7075 aluminum swarf pressed at 900°F at 50 tsi for five seconds is shown in FIGURE 13. The photo¬ micrograph of FIGURE 13 is made of a longitudinal cross section etched at 100 X. A lamellar construction is visible in FIGURE 13 showing the outlines of the swarf particles within which outlines are fine equiaxed grains. Unlike the structures disclosed in U.S. Patent 3,076,706, there is no fibrous character shown in FIGURES 13 or 14 for a metal section. A transverse cross section (not shown) discloses no particular directionality which points up the isotropic property found for these articles.The particle outlines are also visible in the 50 X photomicrograph (FIGURES 11 and 12) of sections taken of articles formed of EC aluminum needle-like particles hot pressed at 950βF and 15 tsi for five seconds in accordance with the method of the invention. FIGURE 11 is a longitudinal section showing sound struc¬ ture with particles fully inter eshed without holes and FIGURE 12 is a transverse section likewise showing visible outlines as shown in the 200 X etched photo¬ micrograph of FIGURE 14 which is a section of an article formed of hot pressed EC aluminum needle-like particles. It should be noted that for each bf the illus- trated photomicrographs the structures are sound with virtually no holes therein. The matrices appear to be clean. This is in contrast to powder metallurgy compacts which are porous and generally show some holes therein. Sound nonporous articles may be used in pres- surized fluid applications whereas porous and leaking articles cannot be used. For instance, dense, hot pressed articles may be used in hydraulic lines or pneu¬ matic lines which must be relatively leak-proof to the pressurized fluids carried therein. Generally speaking, articles made of aluminum by a sintered powder metal¬ lurgy process or by a die casting process have leaked and have not been used in such applications. By way of example only, hot pressed aluminum test samples having only about a 1/8 inch wall thickness were tested and found to be leak-proof to pressurized hydraulic oil at 2500 psi therein and also to pressurized helium gas at 400 psi therein. Such a leak-proof characteristic along with improved strength characteristics make such hot pressed articles (with or without a subsequent forging into shape) usable in applications heretofore not poss¬ ible with conventional die cast or powder metallurgy parts of aluminum.Most of the work has been done with aluminum or aluminum alloy particles. However, such tests have been run to indicate that other metals can also be hot pressed in accordance with the invention and these metalsOMPI include, but are not limited to, magnesium, copper and iron. Further examples will be given for illustrative purposes.Example 5 The substantially pure magnesium was chopped into 1/16 inch to 1/8 inch long pieces with the pieces having a surface area to volume relationship of about360. The split mold used and described above was used with a charge of about 3.105 grams with magnesium. The particles were preheated to about 900°F and the particles were pressed between the top and bottom rings while placed in a stainless steel closed chamber evacuated to 28 inches of mercury vacuum. Bars were pressed in the preheated die at about 900°F and 24 tsi pressure for two seconds. The die was then taken from the chamber and split open with the'compacted article removed and allowed to air cool to ambient room temperature which is below the recrystallization temperature. The surface finish was good. An elongation of 5.2% in 1/4 inch was obtained. The compacted density of about 97.6 and a Rockwell Hard¬ ness on the H scale of 28. A test bar measuring about 1.8 inch in length by .37 inch in width by .15 inch thick¬ ness was pulled and provided an ultimate tensile strength of about 27,200 psi. The structure appeared clean and with virtually no holes therein.When using the same magnesium material and changing only the pressure to 12 tsi, the ultimate ten¬ sile strength was found to be considerably less, namely, 8,960 psi, the hardness 65, and the density 98.9% for a hot pressed magnesium article. FIGURE 15 is a photo¬ micrograph of a section etched at 100 X of the magnesium article pressed at 12 tsi. Example 6A magnesium wire which appears to be of duplex alloy consisting predominantly of magnesium was also hot pressed to form test bars which measured aboμt 1.8 inches TUO in length by .37 inch in width by .16 inch thickness.The bars were also pressed at 900°F under 24 tsi pressure for two seconds. The wire particles had a surface area to volume relationship of about 50. The particles were preheated to 900°F as was the split die. The resulting test bar had a weight of about 3.1 grams and a volume of 1.8 cc. The bar had a smooth exterior surface. An elon¬ gation of 3.2% in 1/4 inch was obtained. The bar had a density of about 102.1% and a Rockwell B Hardness of about 34. This density value of over 100% was caused by the inclusion of oxide in the article being weighed. The tensile specimen from the article had an ultimate tensile strength of about 12,100 psi.When using the same magnesium wire and hot pressing at 900°F for .2 seconds but at a lower pressure of 12 tsi, the magnesium hot pressed articles had a density of 98.2%, a hardness of 41, and an ultimate ten¬ sile strength of 3,400 psi. The structure was generally clean with no holes therein being observable, as can be seen in FIGURE 16, which is a photomicrograph from this magnesium hot pressed article.Magnesium particles having a SA/V relationship of about 180 were also hot pressed as described above in connection with Examples 5 and 6 and the articles formed had a good surface finish 8 and Rockwell Hardness of about 67. The ultimate tensile strength was about 12,970 psi. .The article had an elongation of 2.8% in 1/4 inch. When the same magnesium particles having a SA/V relationship of about 180 were pressed at 900°F for 2 seconds but at 12 tsi, the ultimate tensile strength was found to be only about 1,280 versus the 12,970 psi for the article pressed at 24 tsi apparently due to the less complete welding of the particles when hot pressed at the pressure. In other examples, magnesium powders havingSA/V relationships of about 3500 were hot pressed at 900°F and 12 tons per square inch pressure. These latter articles made from magnesium powder were too soft having Rockwell Hardness ratings of -3 on the H scale. There was a considerable difference in U.T.S. ranging between 1280 and 9860 psi and it appears that the presence of large amounts of surface oxide and other impurities caused this problem. At 24 tsi, the articles made from powder had a hardness of 95, a density of 105.2, an ultimate tensile strength of 18,630 psi and an elongation of 2.0% in 1/4 inch.Generally speaking, it appears that better results can be obtained by hot pressing particulates at higher pressures, e.g., 24 tons per square inch, and with ~ particulates which are more oxide free than the powders used and described above. When increasing the pressure from 12 tsi to 24 tsi, the ultimate tensile strengths generally increased from by 90% to over 900%, while the hardness and density values did not change appreciably. Turning to the hot pressing of copper, in accordance with the invention, a further example is as . follows: Example 7Generally spherical pieces of copper shot of substantially pure copper metal having an SA/V relation- ship of about 100 were preheated to about 950°F and the split mold die was likewise heated to 950°F. A charge of particles weighing 24.03 grams was inserted into the die and* pressed at about 50 tsi for a period of about one second at 950βF. Articles had a surface finish rating of about 7 and these articles had densities of about 96.2%. The hardness on the Rockwell B scale was 23. Test bars havingdimensions of about 1.863 inches in length by 0.381 inch in width by .240 inch in thickness having a volume of about -2.792 cc were pulled. It appears that the copper shot particles had too much oxide and that better results would have been obtained withBVJROM cleaner copper particles. The oxide appears to make the articles more brittle. Also, it appears desirable to hot press the copper particles at higher temperatures than the 950°F used herein. Furthermore, powders of copper were pressed and were found to give good clean looking structures' with densities in the range of about 95.7 to 98.7% and Rockwell B hardnesses of 12 to 51. No tensile test data is available for the hot pressed copper arti¬ cles. A cross section is shown in FIGURE 17. It has been found iron powder may also be hot pressed in accordance with the method of the invention. More specifically, preheated carbonyl powders having an SA/V relationship of 50,800 were hot pressed after being preheated to 950°F at 50 tsi for about one second in a die preheated to 950°F. The density obtained was about95.5 of theoretical full density and the article had a Rockwell hardness on the RC scale of about 48. A tensile specimen weighing about 24,483 grams and having a length of 1.867 inch, a width of 0.380 inch, and a thickness of 0.280 inch was pulled. It appears some excess carbon was picked up in the process making the test specimens ex¬ tremely brittle. The article fractured repeatedly in the test grips of the tensile testing machine; with the gauge length region withstanding pulls of.35,690 psi. A coarser powder of carbonyl having a SA/V relationship of 15,200 was also preheated to 950βF and was hot pressed in a die heated to 950°F under 50 tsi for one second. The articles formed had a density of about98.6 of theoretical density and a hardness of. about 13 on the Rockwell C scale. Tensile test bars of about the same size as described above were pulled to a U.T.S. of 96,240 psi which is high for an essentially pure iron article.The results seem to indicate that particles of iron other than carbonyl iron at higher temperatures of about 1800°F to 2000°F would give satisfactory results.-βU RbΛ TOMPI^ From the work performed, other metal particles such as nickelat 1800βF to 2000βF appear to be capable of being hot pressed to form a wrought nickel article with an isothermal heating of the particles and dies. Also, molybdenum and tungsten particles preheated to about 3000°F should be capable of being hot pressed at dies heated to about 3000°F. The pressures used should be in excess of 12,000 tsi and better results should be obtained with higher pressures of about 50,,000 tsi. To withstand such temperatures and pressures, the die materials will have to be built of refractory materials. The time of high pressure application should be less than several seconds in contrast to the long time sintering processes of the prior art in which the pressure was applied for at least several minutes and as much as one- half hour. As used herein, the term hot pressing refers to a simultaneous application of heat and pressure over a short period of time as distinguished from a longer term sintering process. Likewise, the hot press- ing process should be distinguished from a rolling process for rolling particles in which the particles are extruded or stretched as they go into and through the nip of the -rollers and from a fibrous structure for the metal s described in the aforementioned patent. The hot pressing method disclosed above may be further implemented by adding other materials to either the particles themselves or to the die cavity. For instance, the cost of metal may be lowered by the addi¬ tion of lower cost filler material to the metal prior to formation of the metallic particles. Preferably, such fillers would have a density close to that of the molten metal into which the fillers are added so as to provide a more homogenous- character to the filled metal particles which are to be later hot pressed. Additional strength can be obtained by adding strengthening materials into the die for incorporation into the article. For example. -31- carbon fibers could be added into the mold in layers or groups for being interlocked into the metallic article thereby providing additional strength to the article.Herein, the carbon fibers would remain elongated to give their maximum strength to the article. It is thought carbon fibers of about 10% to 40% of the volume could be added into the mold and hot pressed suitably.The preferred larger size particles usually provide better results than do smaller size powders as evidenced by the higher tensile strengths as hardness obtained when increasing the aluminum particulate size from SA/V of 1500 down to about 3. The SA/V relation¬ ships disclosed herein are all derived by measuring the nominal diameter in inches, for generally rounded parti- cles, and then calculating the surface area and volume. The numbers for the SA/V relationship all have a unit of 10 inch which has not tteen included herein. Of course, if the measurements are made in the metric system then the numbers defining the particle size range will change and the unit will be 10~^ centimeters. Generally, it will be possible to use powders in the process so long as the powder particulates do not sinter weld when pre¬ heated, this being particularly a problem when trying to use extremely fine aluminum powders; and, so long as one can accept a lesser strength, hardness and/or other property. In some instances, a lesser strength or less hard article is adequate and powders may be used in the process of the present invention and fall within the ambit of some of the claims of the present invention. From the foregoing it will be seen that a new process has been found for the production of wrought metal articles having good strength, close dimensional tolerances, and good surface characteristics. The process is economically attractive in that scrap metals may be used and in that alloy metals, such as aluminum alloys, may be used as well as pure metals for the particles. Further, additives may be added to the metal particles, such as carbon fiber additives, to increase the strength of the article or, in the case of filler additives, to decrease the cost of the metal in the article. The process lends itself to high production from a press and the articles, such as preforms, may be immediately transferred from the hot press for further treating, such as a heat treating or a forging thereof in a forging press, while still hot. On the other hand, the hot articles may be allowed to air cool or be quenched to return quickly below their recrystallization temperature to prevent substantial grain growth that would decrease their hardness and tensile strengths.IjU E OM | CLAIMS :1. A method for the manufacture bf hot pressed articles from metal or metallic alloy particles which have been preheated and are pressed in a heated die cavity, said method being characterized by the steps of: providing particles having a dimension in one direction of at least 1,000 microns and having a surface area to volume relationship in the range of between about 3 and about 2,000, preheating the particles to a temperature above the recrystallization temperature for the metal or alloy and close to the solidus temperature for the metal or alloy, heating a die cavity to a temperature suffi¬ cient to maintain the particles at said temperature close to said solidus temperature during subsequent hot pressing, introducing the heated particles into the heated die cavity, hot pressing the preheated particles in the die for a time period of less than 30 seconds while the particles are heated to a temperature close to said solidus temperature at a sufficient pressure to consolidate the particles into a high density article, and removing the article from said heated die cavity.2. A method in accordance with Claim 1 includ¬ ing the further steps of hot pressing the preheated particles within said temperature range with sufficient pressure to form an article having a density of at least 99% of theoretical density for the article and cooling the article to a temperature below the recrystallization temperature before substantial recrystallization and grain growth occurs.3. A method in accordance with Claim 2 in which the hot pressing of the particles comprises an initial low pressure pressing during which the particles are compressed to substantially the final volume for said article followed by higher pressure pressing to the desired density. 4. A method in accordance with Claim 1 in -zhich the metallic particles are aluminum or aluminum alloy particles having at least one cross-sectional ______nsion exceeding 1,000 microns.5- A method in accordance with Claim 4 in *_______ said particles and said die are each preheated to a■temperature in the range of between about 400°C and about 600βC_ δ_ A process in accordance with Claim 5 in which the pressure applied to compress the heated parti¬ cles to their final density is within the range of be- -tsreen about 12,000 and about 100,000 tsi.7. A method in accordance with Claim 1 in which the hot pressing of the particles is effected with¬ in a time of less than about 5 seconds.8. A method in accordance with Claim 1 includ¬ ing the further step of lubricating the walls of said-die before the particles are hot. pressed to prevent*weld¬ ing of the particles or of the article to the side walls of said die cavity.9. A method in accordance with Claim 1 includ¬ ing hot pressing the particles in ambient atmosphere with¬ out a protective atmosphere -thereabout.10- A method in accordance with Claim 1 in which said article is removed from said die cavity at a sufficiently high temperature that said article may be-quenched and including the further step of quickly ■--quenching -the article after removal from said die.11- A- method in accordance with Claim 1 in -which said hot pressing step consolidates said particles to substantially full theoretical density and with substantially no gas porosity.12. A method in accordance with Claim 11 in¬ cluding the step of hot pressing the particles at about the solution annealing temperature for the metal or alloy and subsequently age hardening heat treating said article.OMPIA, 13- A method for the manufacture of closely dimensioned articles from a metallic or metallic alloy particulates which are preheated and in a heated die, said method being characterized by the steps of: pre¬ heating the particulates to a temperature within the xange of between about the recrystallization temperature fox the metal or alloy and the solidus for the metal or -alloy, agitating said particulates to keep the same free flowing when heated and fed to a die cavity', lubricating the walls of a die cavity, introducing the heated partic¬ ulates into a first portion of said die cavity, hot pressing the particulates in said first portion of said die at a first pressure to substantially compress the paxticulates into an article, shifting the article to -another portion of said die, and pressing the article at a second pressure greater than said first pressure.14. A method in accordance with Claim 13 wherein said particulates are aluminum or aluminum alloy particles having a minimum dimension in one direction of -at least 1,000 microns and after the pressing step per¬ forming the further step of cooling said article to below said recrystallization temperature before recrystalliza¬ tion and grain growth (annealing) occurs.15. A method in accordance with Claim 14 in -which said particles and said die are each preheated to a temperature in the range of about between about 400°C and about 600βC.2.6• A wrought metal compact formed from hot pressed metal or metallic particulates with the joined particulates defining a cross section with most of said joined particulates being outlined therein, said compact being characterized by the outlined particulates having grains contained therein iner than said particulates outlined, said particulates being strain hardened and annealed, to form a wrought article without having been subjected to an annealing process, said compact havingIJU EAI/-OMPI substantially no gas porosity and a high density, an exterior surface on said compact being smooth and held to relatively close dimensional tolerances and having a relatively constant surface hardness, said compact having tensile strengths being generally isotropic with the transverse tensile strength being close to the longitu¬ dinal tensile strength.17. A wrought metal compact in accordance with Claim 16 in which-said compact is a precipitation hardened, alloy having solid precipitated solutes.18. A wrought metal compact in accordance with Claim 16 in which said particulates are particles of aluminum or aluminum alloy having a minimum cross-sec¬ tional dimension in-one direction of at least 1,000 microns and in which said compact has a density sub¬ stantially equal to. theoretical density.19. A wrought metal compact in accordance with Claim 16 in which said metal or metallic particu¬ lates are selected from a group consisting of aluminum, copper, magnesium, iron, nickel, zinc, molybdenum and tungsten.j- EAtOMPI V_ -W1P0 -. | IIT RES INST; IIT RES INSTITUTE | STORCHHEIM S |
WO-1979000834-A1 | 1,979,000,834 | WO | A1 | EN | 19,791,018 | 1,979 | 20,090,507 | new | G01N27 | G01N27 | G01N27, G01N33 | G01N 27/30 | SYSTEM FOR ANALYZING CHEMICAL AND BIOLOGICAL SAMPLES | A method and apparatus are provided for analyzing chemical and biological samples, comprising at least one slide (12, 14) having an electrically conductive surface (16, 18) thereof; a sample (24) to be analyzed; means (10, 20) to induce an electro-static field in said sample to cause particles within said sample to selectively re-orient themselves or migrate to a new position; and means (22) to analyze said migrating particles. In one embodiment an electrical field activates a nematic fluid stain (47) for identification of particles within a sample. By altering the electrical characteristics of a sample and passing an electrical waveform through the sample, the resultant change in waveform is indicative of the sample's constituency. | SYSTEM FOR ANALYZING CHEMICAL AND BIOLOGICAL SAMPLESBACKGROUND OF THE INVENTION:The present invention relates generally to a small particle analysis system and, in particular, to a system wherein biological or other colloidal specimens are placed on the specially designed microscope slides described hereinafter and subjected to an electrostatic field and analyzed using a conventional optical microscope or a conventional computer analysis system. The specimen examined with this system need not be stained, may be stained with conventional optical dyes, or, in certain instances, may be stained with special substances which are electrostatically active. The special microscope slides on which the specimens are placed form part of an electrostatic system which activates, changes orientation, or otherwise cause movement of particles or cells within the specimen and to permit viewing or analysis thereof either automatically or with a conventional optical microscope. The interpretation and analysis of specimens, particularly biological specimens, using a conventional light microscope has sometimes proven difficult due to the subjectivity of the human observer involved. In particular, recognition of subtle optical variations is often difficult since biological specimens are optically complex and variable. Many attempts have been made in recent years to automate biological analysis, however, in many instances, this has proven difficult due, in part, to problems associated with the preparation of the biological specimen itself. Furthermore, chemical staining of slides is of times somewhat of a black art with technique varying from researcher to researcher.OMPI . IPO In most instances, biological specimens are placed or mounted on a transparent glass microscope slide and chemically stained prior to processing. To effect chemic staining, well-known dyes or stains such as, for example, Wright's Stain and Giemsa Stain, are used and then the mo is fixed to the slide. The biological specimens uptake the dye in varying ways and when observed optically, rend pathological information to the observer.Traditionally, using a standard optical microscope, the technician scans the slide looking through the microscope and manually counts cell types or looks for specific pathology. Automated systems analyze specimens either in a slide system using a substage which is digitally moved or in a flow through system where the sample is subjected to a series of light beams such as, for example laser beams, while looking for parameters such as absorba transmission and reflectance. Software is programmed to look for certain optical combinations or certain limits. Such automated systems are capable of analyzing a large number of slides or sample streams in short periods of ti and then generate data or histograms which may prove usef in establishing patterns and trends.Sample preparation methodology, on the other hand, is somewhat less clearly defined. The problems in sample preparation are numerous and varied and include an inabil to repeatedly optically stain a sample in the same or similar way; problems with repeatability using stains of different batches due to factors such as chemical composi tion and purity differences of the stain, the amount of stain used, the skill of the technician, the temperature of the environment, the length of the fixing cycles and the appearance of any debris in the sample, etc. The presence of these variables make it sometimes difficult t repeatedly and reliably interpret optical data. This problem is further compounded by the fact that in any given cell population, a wide variety of different cells may occur, each with a subtle variation in physical and optical parameters.Some attempts have been made to replace optical stain systems heretofore used with systems employing non-optical substances to permit examination by non-optical means. For example, radioactive tracer elements have been used to stain specimens for subsequent analysis with a scintillation counter. Difficulties, however, have been encountered in such systems with respect to resolution and system complexity. Still another approach to sample analysis has been an electrophoresis systems.which measures the velocity of particulate or chemical constituents therein when the sample is subjected to an electric current. For example, such systems can measure the membrane potentials of a protein cell or the so called zeta potentials of a colloid and compare it to a known or standard measurement for purposes of identification. Studies have shown that cells have a specific electrical potential known generally as their membrane potential which varies with biological conditions of the particular cell. Similarly, particles in colloidal suspension have a specific electrical potential referred to as their zeta potential. Since different biological or chemical samples have different particle potentials, a system which is capable of inducing and measuring this potential is thus capable of sorting and identifying such cells or particles. Heretofore, two types of methods were used to measure membrane or zeta potential—a direct and an indirect method. The direct method entails the insertion of a pair of needlelike microelectrodes into the cell or particle and then measure its electrical characteristics. An example of such a direct analysis is described in an article entitled Membrane Potential of Mitochondria Measured with Microelectrodes which appeared in Science, Vol. 195, dated 4 March 1977, at page 898-899. Due to the size of such cells, generally in the micron range, an the fact that their membranes must be pierced, such a measurement is extremely difficult to make and the risks of contamination or traumatic shock to the specimen are quite high. The indirect methods heretofore used generally relied on flow through type technique wherein the particles were suspended in a fluid which was then passed through an analyzing chamber upon the introduction of an electrical current which flows through the fluid. Examples of such systems are the Zeta-Meter manufactured by Pen Kem Corporation of Croton-on-Hudson, New York, and the Cytopherometer of Carl Zeiss. See also the discussion of the zeta potential which appeared in the March 9, 1964 edition of Chemical Processing entitled Fast Accurate Measurement of Zeta Potential Proves Boon to Processes . All of these systems directly introduce an electric curre into the specimen and measure the resultant velocity of t moving particles (electrolytic migration) . With particle velocity known, mathematical treatment can then be applie to develop potential information. The disadvantages of such systems include the fact that as the current is induced in the sample or specimen, the sample resistance causes the sample to heat up, thus altering the character istics of the specimen. For example, the velocity of a cell or particle is dependent upon a given fluid viscosit any change in the viscosity can affect the results. Additionally, the electrical current may have an adverse affect on biological specimens. Furthermore, such a system may contaminate the sample since metallic electrod have to be introduced into the fluidized sample to permit the generation of an electrical current. In addition, the size of the samples or specimens analyzed with these systems tend to be rather large, i.e. 20cc to 30cc and processing time can become quite long. Against the foregoing background, it is a primary objective of the present invention to provide an analytic system capable of measuring particle charge including the cell membrane or zeta potentials of a given specimen.It is another object of the present invention to provide an analytic system capable of measuring the membrane or zeta potential of a given specimen using an indirect approach wherein no electrical current is passed through the specimen.It is another objective of the present invention to provide an electrical capacitance analysis system for analyzing biological and small particle samples.It is yet still another objective of the present invention to provide an electrical capacitance analysis system wherein specimens are placed between microscope slides and an electrical capacitance is induced therein.It is still another objective of the present invention to provide a sample staining technique which is based on usage of nematic fluids.SUMMARY OF THE PRESENT INVENTIONTo the establishment of the foregoing objects and advantages, the present invention briefly comprises method and apparatus for analyzing chemical and biological specimers comprised of at least one transparent substrate having at least one conductive surface thereof; a sample to be analyzed; means processing the sample by inducing an electric field in the sample to cause particles within said sample to selectively migrate to a new position or re-orient themselves; and means to analyze said processed sample. BRIEF DESCRIPTION OF THE DRAWINGS:The foregoing and still other objects and advantages of the present invention will be more apparent from the following detailed explanation of the invention in connection with the accompanying drawings wherein:Fig. 1 is an exploded view of a pair of slides and a schematic showing of an electrical circuit connected thereto;Fig. 2 is a side elevational view of the slides of Fig. 1 in juxtaposition and a schematic showing of an electrical circuit connected thereto;Fig. 3 is an exploded view of a pair of slides provided with electrically conductive areas, a specimen under test and an insulator member;Fig. 4 is a side elevational view of the members of Fig. in assembled condition;Fig. 5 is a partially sectioned elevational view of a pair of slides provided with a well for receiving a sample;Fig. 6 is a top plan view of the upper slide of Fig. 5;Fig. 7 is a top plan view of the lower slide Of Fig. 5;Fig. 8 is a bottom plan view of the lower slide of Fig. 5;Fig. 9 is a side elevational view of a slide system connected to a power supply;Fig. 10 is a schematic showing of the position of charged particles without a voltage applied to the system of Fig. Fig. 11 is a schematic showing of the position of charged particles with a DC potential applied to the system of Fig. 10;Fig. 12 is a schematic showing a slide system in which the AC transfer characteristics of the sample are measured;Figs. 13-14 are a schematic showing of slide systems employing nematic stains in the sample wherein in Fig. 13 there is no potential applied to the sample and in Fig. 14 there is a potential applied; andFig. 15 is a schematic showing of a system of this invention employing a ladder type electrode arrangement.DESCRIPTION OF THE PREFERRED EMBODIMENTS:The present invention constitutes a system for analyzing and identifying charged particles such as are found in biological samples involving cells, colloidal suspensions and other fluid samples. All of these samples contain some form of charged particle (for example, cell membrane potential or zeta potentials) or particles whose behavior is altered in the presence of electric fields. The sample involved is placed in a special microscope slide system and then subjected to an electric field (DC or AC) in order to create movement of the particles or changes of state within the particles. A microscope is then used to observe the change, or, alternatively, an automated, computerized method of determining sample change may also be employed.In Fig. 1 there is shown the basic preferred form of the invention utilizing a DC power supply 10 and employing electrostatic energy for the movement of the particles. Two standard glass or transparent plastic microscope slides 12,14 are employed, each of which has, on oneOMPI ». WIPO surface, an optically clear, etched conductive electrode 16,18 composed of tin oxide or similar material. The position of these optically clear conductive electrodes is such that when the two slides are pressed together, the circular upper electrode 16 is physically directly on top of the circular lower electrode 18. These two electrodes 16,18 are then connected to a stable, high voltage DC supply 10 whose output can be precision controlled by a voltage divider 20 and the voltage appearing across the slide system is measured by a voltmeter 22. It can be seen from Fig. 1 that when these two slides are pressed together and connected to a DC pow supply, a capacitor is formed with the slides 12,14 as we as any material between the slides, forming part of the dielectric. A drop of the sample 24 to be examined is placed on the bottom slide and the slides are then presse together, as shown in Fig. 2, resulting in a very thin fi of sample 24 sandwiched between the two microsope slides 12,14 and subjected to the electrostatic field existing between the conductive electrodes on the top and the bottom of the slides.A small capacitor will form between the two conductive circles facing each other. It is irrelevant as to the extent to which the sample spreads along the surface between the two slides since this excess of sample does not form part of the capacitance system. The same pressu is to be applied to each test in order to keep uniform the thickness of the sample film. It will be noted that the conductive leads to the capacitor plates are not opposite each other and, accordingly, do not form part of the capacitor.When a controlled DC voltage is applied to the electrodes the particles within the sample will begin to move upward, providing that the polarity of their own charge is opposite to the polarity of the upper electrode. TheO , W electrostatic force which is exerted on the charged particles is determined by a number of complex parameters including voltage, dielectric constants of the materials used, thickness of the slides, amplitude of the particle charge, fluid viscosity and others. Furthermore, the velocity with which the particle moves towards the oppositely charged electrode is also dependent upon numerous factors including voltage impressed across the system, distances involved, sample viscosity, etc. It will be understood that the velocity of charged particle movement could be increased if the voltage across the system is increased or if the electrodes are brought closer to the particles. Consequently, another embodiment of this system is shown in Figs. 3 and 4 where the two optically clear conductive electrodes 34,35 are etched on the microscope slides 32,33 on the side thereof adjacent to the sample. Since this system is a capacitor system, the flow of current must be prevented and, accordingly, a very thin insulator such as a 0.001 thick mylar sheet 30 is placed between the sample 36 and the upper slide. Consequently, as shown in Figs. 3 and 4, the sample in this particular embodiment of the invention electrically becomes a part of the bottom electrode 35, the mylar sheet 30 serves as the dielectric, and the upper electrode 34 attracts the oppositely charged particles through the mylar sheet. The movement of the particles are studied by means of microscope M.Figs. 1, 2, 3, and 4 disclose versions of this invention in which a droplet of the sample is formed into a thin film (a few microns thick) when the two slides are squeezed together. Another embodiment of this invention is shown in Figs. 5-8 which uses the optically clear conductive electrode slide system the same as previously described. However, in this embodiment of the invention the bottom slide contains a small well 40 in which the drop of sample is placed. In this embodiment of the invention the drop is subjected to electro¬ static forces rather than the thin film previously described. The actual operation of the system using DC potentials is shown in Fig. 9. The sample is placed between the two slides which are then squeezed together forming a thin fi as previously discussed. (In the well type slide, the entire sample remains in the well.) The system is then connected to a precision DC power supply 21 whose output can be controlled and measured in a precise fashion. Thi slide sandwich is then placed into a standard optical microscope which is focused in such a manner that the foc point of the microscope falls on the top surface of the film or the well sample formed within the sandwich slide system. Point F. When no voltage is applied, as shown in Fig. 10, the charged particles P are evenly distributed throughout the sample or may even be at rest within the sample film favoring the bottom slide. As soon as a DC potential is applied to the system, a capacitor is formed and an electrostatic field is generated within -the sandwi This field causes particles P to move upward toward the upper slide providing that their charge is opposite to th charge of the upper electrode. The velocity with which these particles move is of course dependent on the factors which have previously been discussed and include power su voltage and dielectric properties of the sandwich. After short period of time, certain charged particles will migr into the focal point F of the microscope where they can b visually analyzed by the observer. Consequently, using t technique, samples containing charged particles which are distributed at random can be sorted and analyzed by struc ing an electrostatic slide system as shown.Hereinabove there has been described a slide system for t analysis of charged particles using a DC power supply. Y another embodiment of the invention is a system in which DC power supply is not used. An embodiment of this inven is shown in Fig. 12 where the sample is placed into the sl system as previously discussed. However, in this embodime an AC signal 49 consisting of a sine wave, a square wave. or some other complex AC wave shape, is injected into the system. This causes the system to look like an AC fed capacitor in series with the load resistor 51. The AC fed capacitor consisting of the slides 12 and 14 with their conductive electrodes 18 and 16 and the sample 47 which forms part of the dielectric system. An oscilloscope 53, or similar measuring device, is then used to observe the AC transfer characteristics of the sample. Consequently, internal conditions and changes in the sample could be observed, for example, if the input signal was a sine wave 49 which was distorted into a pulse 55. In this manner, a number of electrical parameters of the sample can be measured, including the sample's impedance, biological changes when subjected to pulses, ability to produce harmonic distortion in sine wave inputs, to name only a few. Such an AC transfer technique can be applied to a wide variety of biological and chemical samples, and staining may or may not be used.Another embodiment of this invention requires an AC power supply, but in this embodiment the sample must be stained by a special stain which alters the electrical character¬ istics of the sample. A typical stain that would achieve this effect is composed of a nematic fluid (liquid crystals— Schiff bases) including but not limited to compounds as marketed by Eastman Kodak, Rochester, New York, such as Methoxybenzylidene-p-butylaniline; p-ethoxybenzylidene-p- aminobenzonitri (PEBAB) ; and anisylidene-p-aminophenylacetate (APAPA) . The molecules of such compounds are in a particular molecular arrangement and alignment in the absence of an AC field. As soon as an AC field is impressed across such compounds, the molecules lose their ordered alignment and give the nematic fluid an opaque appearance. Such nematic fluids (commonly termed liquid crystals ) have found widespread use in indicia displays in wristwatches and electronic instruments to indicate digits and alphanumerics. As previously stated, and as Fig. 13 shows, a sample 47 i stained with such a nematic fluid and then placed into th sandwich slide system. Using the microscope previously described, the sample 47 will be randomly clear or trans¬ lucent as in Fig. 13 when no AC voltage is applied across the system. In Fig. 14 an AC voltage is shown applied across the system. Those cells or particles which are prone to selectively uptake the nematic stain become opaque within the sample itself. Using such a technique, the optical microscope M can then be used to identify those particles which as a result of staining have taken up the nematic fluid.With reference to Figs. 1-11 there has been discussed the application of DC fields to fluid samples. In all of these instances, where the sample was within a DC field, the motion of the particles was in a vertical direction. That is, when a DC field is applied the particles migrate from the bottom slide to the upper slide in the event tha their charge is opposite to the charge of the upper electrode.An additional embodiment of the invention shown in Fig. 1 utilizes a slide where the motion of the charged particle is in a horizontal direction. In this system a series of optically clear conductive coatings are etched in the for of stripes 61, 62, 63, 64 on the bottom slide 60. Each o these lines are connected to a different DC potential provided by a voltage divider 65 connected across a high voltage DC power supply 66. The sample 67 is placed on a mylar sheet 68 at the end of the slide nearest the lowest potential electrode. As soon as the DC power is turned o the particles begin to move toward the oppositely charged series of electrodes. Over a period of time a sorting of the particles will take place dependent upon their own charge as well as the potential gradient formed by the slide system. At the end of such time period the slideOM/j. WIP system can be scanned with a microscope in the horizontal plane to examine the various populations of charged particles which have gathered at the various potential gradient points.The system of the present invention may be applied to a number of applications and is useful for medical or bio- medical diagnostic techniques such as, for example, the analysis for sickle cell anemia, determination of male/ female cells in animal husbandry and in pathological fields such as cancer detection. In the chemical industry, the system has applications for checking the efficacy of colloidal suspensions and in the analysis of bond integrity by measuring the degrees of coagulation. Additionally, the system can be used for analyzing chlorinated water.The system of this invention is adapted to process unstained specimens, as well as those stained with traditional optical dyes and with substances whose electrical characteristics change in the presence of an electric charge.Thus, it has been shown that the particles are charged to varying degrees permitting the particles to move up or down or horizontally or to be re-oriented responsive to an electrostatic field. By altering the electrical character¬ istics particles may be differentiated by means of an oscilloscope or other electronic measuring means.Having thus described the invention with particular reference to the preferred forms thereof, it will be obvious that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.- URE ^O PI_ ~~ | WHAT IS CLAIMED IS:1. Apparatus for the analysis of specimens containing particles of matter responsive to electrical potentials comprising:(a) a first substrate;(b) a first electrically conductive member carried by said substrate;(c) a second electrically conductive member positioned above said substrate and spaced therefrom providing a cavity or surface for receiving a specimen to be analyzed, the specimen is part of the dielectric of the capacitor formed by the first and second electrically conductive members, the specimen being supported on said first substrate;(d) means connected to said electrically conductive members for creating an electric potential or field between said conductive members for physically altering the specimen; and(e) means to analyze the specimen.2. The apparatus of Claim 1 wherein the first electrically conductive member is on the surface of the said substrate.3. The apparatus of Claim 1 wherein the second electrically conductive member is transparent.4. The apparatus of Claim 3 wherein the second electrically conductive member is carried by a transparent substrate.-^ΌREΛ 5. The apparatus of Claim 1 wherein said first substrate has a well for receiving a specimen.6. The apparatus of Claim 1 wherein said means for creating an electric potential generates signals of a repetitive shape and includes means for detecting and displaying said signals after passing through the specimens.7. The apparatus of Claim 1 including an electrically non- conductive member interposed between said first and second electrically conductive members.8. The apparatus of Claim 3 wherein said substrate is composed of glass and said second conductive member is comprised of tin oxide.9. The apparatus of Claim 1 wherein the first electrically conductive member is composed of a plurality of electrically, isolated elements connected to said means for creating a potential and wherein said last named means provides a higher potential to each successive element.10. Apparatus for analyzing specimens containing particles susceptible to response to electrical potentials, said apparatus comprising:a pair of substrates in juxtaposition to each other, the opposing faces having electrically conductive surfaces;a specimen to -be analyzed positioned between said opposing surfaces; means for applying an electrical potential to said electrically conductive surfaces whereby an electric differential will exist between said surfaces so as to cau particles within said specimen to selectively re-orient; ameans to analyze said re-oriented particles.11. The apparatus of Claim 10 wherein said substrates are composed of glass and said conductive surface is comprised of tin oxide.12. The apparatus of Claim 1 wherein said means to analyz comprises a microscope focused at the resulting re-oriente particles.13. The apparatus of Claim 10 wherein the particles of said specimen are stained with a dye.14. The apparatus of Claim 10 wherein the particles of said specimen are stained with an electrically active compound.15. The apparatus of Claim 14 wherein said electrically active compound is a nematic fluid.16. Apparatus for analyzing chemical and biological samples containing particles responsive to electric potential, said apparatus comprising:at least two slides in juxtaposition to one another, each of said slides containing on their inner surface at least one electrode in electrical connection with an external power source; sa ple to be analyzed, said sample adapted to be placed between said electrodes;means to introduce an electrical charge to said electrodes to cause particles within said sample to migrate to a new position; andmeans to analyze said migrating particles.17. The apparatus of Claim 16 wherein a DC current is introduced into said electrodes.18. The apparatus of Claim 16 wherein an AC signal is introduced -in said sample.19. The apparatus of Claim 18 wherein said AC signal is a harmonically rich wave.20. The method of analyzing biological and chemical samples containing particles responsive to electrical signals, said method comprising:mounting a sample on an electrically conductive slide sandwich structure;inducting an electrical charge in said structure to cause particles within said sample to re-orient; andanalyzing the resulting re-oriented particles.21. The method of Claim 20 wherein the particles are stained to render them electrically responsive. 22. The method of Claim 21 wherein said particles are stained with a nematic fluid.23. The method of Claim 20 wherein said particles are subjected to a DC potential.24. The method of Claim 20 wherein said particles are subjected to an AC signal.25. The method of Claim 24 wherein the AC transfer characteristics of the particles are determined.26. The method of Claim 24 wherein the AC signal is a harmonically rich wave. | HIGH STOY TECH; HIGH STOYTECHNOLOGICAL CORP | HAHN S |
WO-1979000835-A1 | 1,979,000,835 | WO | A1 | XX | 19,791,018 | 1,979 | 20,090,507 | new | B01J1 | null | A62D3, A62D101, B01J19, B09B3, C07C1, C07C45, C07C51 | A62D 3/176, A62D 3/37, B01J 19/12D2, C07C 1/26+15/14, C07C 45/65, C07C 51/377+63/16, K62D 101/04, K62D 101/22, K62D 203/04 | DEHALOGENATION OF HALOGENATED COMPOUNDS | Chemical process for degrading halogenated organic compound having at least one C-halogen group and preferably a plurality of such groups to remove halogen atoms from said compound by treating it with ultra-violet (UV) radiation (2) and hydrogen (6) preferably, though not necessarily in alkaline liquid solution. Process for degrading such compound which is capable of forming alkali metal salts by treating it in aqueous alkaline solution with UV radiation (2). The process can be used generally as a means for dehalogenation and is particularly useful in the treatment of contaminated effluent wastes from manufacturing processes or from contaminated water, soil, sludges or other wastes already present in the environment. An example of a compound effectively treated by the processes of the invention is kepone, decachloropentacyclo (5.3.0.02,6.03,9.04,8) decan-5-one. | DEHALOGENATION OF HALOGENATED COMPOUNDS TECHNICAL FIELDThe invention relates to chemical processes for removing halogen atoms from halogenated organic compounds having at least one C-halogen group and preferably a plurality of C-halogen groups. The invention is particularly applicable to the degradation of toxic halogenated organic compounds, which are resistant to environmental degradation, by removing halogen atoms therefrom. BACKGROUND ARTMany organic halogenated compounds are employed for a variety of practical uses, e.g., as pesticides, soil fumigants, solvents, etc. Many escape into the environment, as for example in manufacturing or application wastes and spills. Some, such as pesticides, are applied in such a manner as to become part of the environment. It has been found that a number of such compounds, particularly though not neces¬ sarily polyhalogenated compounds, are toxic to plant and animal life. Although some of the compounds are bio- and/or photo-degradable so that they soon disappear from the environment, a substantial number are resistant to environmental degradation and remain in poisonous form for periods as long as many months or years. As a result, a good deal of research has been done to find reliable and economical treat¬ ment methods to degrade such compounds into environmentally safe pro¬ ducts. Some work has been done with treatment of certain halogenated organic compounds variously with UV radiation or with UV radiation and oxygen, air or ozone. To inventor's knowledge, there have been no prior teachings of the use of a chemical reduction treatment employing UV and hydrogen free from any added oxidizer, such as air or oxygen per se, or the use of UV alone in which the compound is in aqueous alka¬ line solutions. U.S. patent 3,977,952 teaches the required use of oxygen (or air) plus UV, preferably in the presence of HC1 catalyst. In column 1, the patent mentions the use of carbon dioxide, water vapor, air or hydrogen as carrier gases for gas phase reaction. The reference to hydrogen appears to be inadvertent since no one skilled in the art would use hydrogen within the context of an oxygen oxidation process. The hydrogen would oxidize to water and present a serious hazard of explosion.OMPI DISCLOSURE OF INVENTIONThe treatment of a halogenated organic compound having at least one C-halogen group with UV radiation and hydrogen in the absence of any sub¬ stantial amount of oxidizing agent reduces the compound by breaking the carbon-halogen linkage and producing halogen ions, thereby at least part¬ ially dehalogenating the compound (in the case of a polyhalogenated com¬ pound). The treatment may also result in further degradation of the at least partially dehalogenated compound. The process may be employed with monohalogenated compounds, but will more generally be used to treat poly- halogenated compounds because of their generally greater toxicity and resistance to environmental degradation.The process can be used generally as a means for dehalogenation and is particularly useful in the treatment of contaminated effluent wastes from manufacturing processes or from contaminated water, soil, sludges or other wastes already present in the environment.The dehalogenation mechanisms which occur in the process are gen¬ eric in nature. They are operative regardless of the structure of the compound or the presence of other substituents or molecular components, such as oxygen, sulfur, nitrogen, metals or the like. The effect of these variable manifestations is primarily in the energy of the C-halogen bond and can be compensated for by employing higher or lower energy UV radiation within the stated range. The halogen substituents can include chlorine, bromine, fluorine, and iodine. The different C-halogen groups generally differ in bond energy. C-F groups, for example, generally have particularly high bond energies as compared with the other C-halo¬ gen groups and require more energetic UV wavelengths in the dehalogen¬ ation process.Examples of compounds which are particularly suitable for treat¬ ment by the UV plus H„ process of the invention because of their demon- strated or potential toxicity include but are not limited to kepone (and its gemdiol) decachloropentacyclo(5.3.0.0 ' .0 ' .0 ' ,)decan-5- one; halogenated biphenyls; halogenated cyclodienes, such as aldrin, dieldrin, and hexachlorocyclopentadienes; dibromochloropropane; halo¬ genated phthalic anhydrides, such as polybromophthalic anhydride; tet- rachloroethylene; polychlorodioxins such as tetrachlorodibenzodioxin; halogenated organic phosphates, such as 2,2-dichlorovinyldimethyl phos¬ phate (Dichlorvos) .The process can be employed in gaseous phase where the halogenated organic compound is gaseous or in the form of a finely divided liquidOMPI or so . n suc case, e y rogen ac s as ue , carr er, an reactant. Where the compound is in liquid or solid form, it is gener¬ ally desirable to dissolve it in a suitable solvent which preferably is substantially transparent to the particular UV wavelengths. Use of a solvent is particularly advantageous where the compound is a contami¬ nant which must be separated from other materials, such as sludge or mud.The particular solvent used is determined by the solubility char¬ acteristics of the particular halogenated compound. It can be, for example, water, methanol, ethanol, 1-and 2-propanol, hexane, cyclohex- ane, acetonitrile, and preferably their alkaline solutions.An aqueous alkaline solution, where alkalinity is preferably pro¬ duced by the presence of alkali metal ions and preferably by means of an alkali metal oxide or hydroxide (to minimize potentially obstructive anions) , such as sodium or potassium oxides and hydroxides, is partic¬ ularly useful in the case of halogenated organic compounds which have substituents that react to produce soluble alkali metal salts. Examples include but are not limited to kepone (which normally hydrolyzes to the gem-diol in the presence of water or atmospheric moisture) ; aryl com- pounds having aryl-OH substituents, e.g., phenol-type compounds; diol- type compounds; carboxylic acids; anhydrides, such as phthalic anhy¬ dride-type compounds; sulfonic acids; and the like.Compounds which are not soluble in aqueous alkaline solutions can generally be adequately solubilized by means of a suitable organic sol- vent. Preferably, though not essentially, the organic solvent is rend¬ ered alkaline, e.g. , by addition of an alkali metal oxide or hydroxide, since it has been found that an alkaline pH can result in more rapid and greater degradation. Methanol is a preferred solvent because of its good solubilizing capability, its good UV transmission properties, and its relatively low cost which is of particular importance in the case of large scale application.The UV radiation, as aforementioned, should be in the range of o about 1800 to 4000 A. Preferably, it is in the shorter wavelength o portion of this range, namely up to about 2537 A. Wavelengths of about o o 2537 A and 1850 A are particularly preferred because of the generally high absorptivity of halogenated organic compounds at these wavelengths.The hydrogen input, quantitatively, should be sufficient, during the time of the treating procedure, to be in stoichiometric equivalency to the number of halogen atoms to be removed, or in excess thereto. In -4- the case of liquid phase solvent treatment, the effective limiting value is the saturation concentration of the hydrogen in solution. Continued input of hydrogen to maintain saturation provides the optimum amount.The process can be carried out at ambient temperature in relatively simple apparatus. The halogenated organic compound should receive max¬ imum exposure to the UV radiation. This can be accomplished by such state-of-the-art expedients as minimizing the distance that the radiat¬ ion needs to travel to or through the treatment volume; recirculation of the treatment medium; turbulence-creating means such as baffles or rotors; and the like. The process can be designed for batch or contin¬ uous treatment.It has also been found that substantial degradation cart be obtained by treatment of the halogenated compound in aqueous alkaline solution by treatment with UV radiation within the stated broad and preferred ranges of wavelength. Such treatment is limited to compounds, as aforedescribe which are soluble in aqueous alkaline solution without requiring additi¬ onal use of an organic solvent. In all other respects, the aforediscus- sion of various aspects of the process and generic application regardles of compound structure and substituents are applicable to such process using UV radiation alone.The processes of the invention are in general more effective and efficient than the prior art treatments, as is shown in comparative tests infra.BRIEF DESCRIPTION OF DRAWINGS Figure 1 is a schematic drawing of apparatus used in the process.Figure 2 shows comparative percent degradation of kepone in methano solution with treatment by UV plus H„ and in alkaline methanol solution with treatment by UV alone, UV plus 0» and UV plus H„.Figure 3 shows the comparative percent degradation of kepone in aqueous alkaline solution by UV alone, UV plus 0. and UV plus H_.Figure 4 shows the comparative percent of maximum chloride ions released from kepone in aqueous alkaline solution by treatment with the three methods.Figure 5 shows the comparative total percent degradation of Aroclor 1254 in basic methanol by UV alone, UV plus 0„, and UV plus H„. Figures 6, 7 and 8 show the percent degradation of the individual components of Aroclor 1254 by treatment with UV alone, UV plus 0„ and UV plus H„ respectively.Figure 9 shows the percent degradation of TBPA in basic methanol by treatment with UV alone, UV plus 0 , and UV plus H„.Figure 10 shows the percent of maximum bromide ions released from TBPA using the three treatment methodologies. BEST MODE FOR CARRYING OUT THE INVENTION Figure 1 shows a schematic drawing of a reactor as employed in exper¬ imental evaluation. U-shaped UV tube 2 is positioned longitudinally in reactor chamber 3, and is held in air-tight position by Teflon plug 4, and is connected by wires 5 to a transformer (not shown) . Hydrogen gas is pumped in via inlet tube 6. Reaction solution is pumped in via inlet tube 7 and is continuously recirculated by a pump (not shown) via out¬ let tube 8. Vent 9 provides for the exit of volatiles.As used in the experiments below, the reactor diameter was 4 inches (10.15 cm). Capacity was 1.5 1. The lamp size was 15-1/4 inches (38.74 cm) in overall length with an arc length of 24-1/2 inches (62.23 cm) and tube diameter of 11/16 inch (1.75 cm). Lamp input was 30W and out- o put intensity was 10.4W. UV wavelength was 2537 A.Example 1 Kepone Treatment: Kepone, which has been used as an insecticide, has posed formid- able problems because of its great toxicity and resistance to bio- and photo-degradation in the environment. It is highly toxic to normally- occurring degrading microorganisms. Although it can undergo some photo- decomposition when exposed to sunlight to the dihydro compound (leaving a compound having 8 Cl substituents) , this degradation product does not significantly reduce toxicity. Kepone was made up into three different stock solutions: a. 212ppm in methanol; solution pH6. b. 237ppm in methanol alkalized to pHIO with NaOH. c. 230pρm in water containing 51- NaOH. 1.5 1 quantities of the kepone stock solutions were variously o treated in the apparatus aforedescribed (UV λ = 2537A) with UV alone, UV plus 0„ at an ozone flow rate of 0.41 1/min. and UV plus H„ at a hydrogen flow rate of 0.75 1/min. Samples were prepared for quantitative gas chromatographic analysis in the following manner.1. Measured volumes of the samples were neutralized with ULTREX (Cl-free) nitric acid, if basic.2. The samples were evaporated to dryness.3. The dried sample was diluted to 100 ml with 67« methanol in benzene. The resulting solutions were analyzed on a 5750 with electron capture detector. The following conditions were used: injection port temperature - 300°C detector temperature - 300CC oven temperature - 250°C gas flow - 50 ml/min Ar/CH, column - 107. DC 200 on Chromosorb HP 100/200 The aqueous NaOH solutions were analyzed on a Hewlett-Packard 3880 using the following conditions: injection port temperature - 200°C oven temperature - 180°C gas flow - 45 ml/min AR/CH, column - 57= OV-210 on 100/120 GCQ Chloride ion concentration was also determined on all of the samples An Orion solid state chloride ion electrode was used for this purpose. Samples in methanol were prepared by neutralizing 5 ml of the sample wit ULTREX nitric acid. Following evaporation to dryness, the samples were dissolved in 8 ml of distilled water. In the case of the squeous sodium hydroxide solutions, 10 ml samples were neutralized with ULTREX nitric acid before the analyses. Chloride ion concentrations were determined by comparison to standard curves generated from sodium chloride stand¬ ards containing equal amounts of sodium nitrate as the samples.During the course of the experimental runs, samples were taken at 15, 30, 60, 90 and 120 min. (+180 min for aqueous NaOH solution treated with UV plus H„) to determine rate of degradation with time. Table I gives the results obtained in terms of the remaining con¬ centration of kepone at the end of the indicated time period and the percent degradation.TABLE IInitial Cone. Sample Treatment Conditions Final % Degra¬ Ppm Conditions Gas Time Cone. dation o212 Methanol pH 6 2537A Hydrogen 120 min. 177 ppm 16.57c237 Methanol pH 10 2537A 120 min. 155 ppm 34.67c237 Methanol pH 10 2537A Ozone 110 min. 190 ppm 19.87c o237 Methanol pH 10 2537A Hydrogen 120 min. 115 ppm 51.57c230 57c Aq.NaOH Sol. 2537A 120 min. 140 ppm 39.17c pH > 14230 57o Aq.NaOH Sol. 2537A Ozone 120 min. 181 ppm 21.37c pH > 14OMPIA TABLE I (continued)InitialCone. Sample Treatment Conditions Final 7c Degra- ppm Conditions Gas Time Cone. dation230 57« Aq.NaOH Sol. 2537A Hydrogen 120 min. 37 ppm 83.97c pH > 14230 57o Aq.NaOH Sol. 2537A Hydrogen 180 min. 12 ppm 94.87c pH > 14Table I and Figure 2 show the substantially higher 7- degradation at two hours by the basic methanol treatment with UV plus H„ as compared with the other treatment methodologies. They also indicate that, although the UV plus H- treatment with non-alkalized methanol (pH 6) gives appreci¬ able reduction, the alkaline methanol gives very considerably improved results. Figure 2 also shows the considerably higher rate of reduction by the UV plus H_ treatment.Table I and Figure 3 show the very substantially higher rate and percent degradation produced by the UV plus H_ treatment in aqueous NaOH as compared with the UV alone and UV plus 0, treatments. At the end of 3 hours, the UV plus H_ treatment almost completely removes the kepone. These degradation results are substantially verified by Figure 4 which shows the percent of free Cl ions released as a function of time for the UV alone, UV plus 0_, and UV plus H_ treatments. After_3 hours only about 26.57o of the chlorine appears to remain in C-Cl group combination in chlorine-degraded products. At 120 minutes about 50.5% of the chlorine has been transformed into free ions by UV plus H2, about 237= (less than one-half) by UV, and only about 16.57c by UV plus 0_. These results indi¬ cate that as many as 6 to 8 chlorine atoms are removed from the kepone molecules by the UV plus H~ treatment.It should be noted that although the results obtained with UV alone in aqueous alkaline solution are not as good as those produced by the UV plus H„ treatment, substantial degradation is obtained, so- that this treatment can be useful in the case of halogenated organic compounds which are substantially soluble in aqueous alkaline solution as afore¬ described.Example 2 Treatment of Polychlorinated biphenyl (PCB) :Aroclor 1254 is a mixture of the higher chlorinated biphenyls con¬ taining 547o chlorine by weight (an average of 4.96 chlorine atoms per molecule). A typical analysis of Aroclor 1254 is presented in Table II (Versar Inc., 1976). TABLE IIEmpirical Molecular No. of Chlorine Wt. 7c No. of Weight Formula Weight per Biphenyl Chlorine Isomer 7c154 0 0 1 <0.1C12H10C12H9C1 188 1 18.6 3 <0.1C12H8C12 222 2 31.5 12 <0.5256 3 41.0 24 1C12H7G13290 48.3 42 21C12H6C14 4C12H5C15 324 5 54.0 46 48C12H4C16 358 6 58.7 42 23392C12H3C17 7 62.5 24 6C12H2Clg 426 8 65.7 * 12 <0.01Aroclor 1254 is slightly soluble in water, having an overall sol- _2 ubility of 1.2x10 mg/1. Solubility of the various components varies from 0.0088 mg/1 for the hexachlorobiphenyls to 5.9 mg/1 for the mono--5 chlorobiphenyls. The vapor pressure for the 1254 mixture is 7.7x10 mm Hg. Theoretical half-life from a 1--meter water column has been cal¬ culated as 1.2 minutes. Thus Aroclor 1254, like many other slightly soluble chlorinated compounds, is readily vaporized from the surface of water. Such vaporized compound could, therefore, escape degradation treatment.Aroclor 1254 was dissolved in methanol alkalized to pH 11 with NaOH to make a 10.92 ppm stock solution. 1.5 1 portions of this stock solution were treated with UV alone, UV plus ozone at an ozone flow rate of 0.411/min. , UV plus hydrogen at a hydrogen flow rate of 0.75 1/min. for 120 minutes each in the reactor aforedescribed. Samples of ~ 8 ml each were taken every 15 minutes. Analyses were performed on the 15-, 30-, 60-, 90-, and 120-minute samples.Quantitative analyses for the PCBs were performed on a Hewlett-63 Packard 3880 gas chromotograph with an EC-Ni electron capture detectorG.C. conditions were as follows: injection port temperature - 200°C detector temperature - 300°C oven temperature - 220°C gas flow - 50 ml/min Ar/CH,Column - 157, OV-17, 1.957» QF-1 on 100/120 GCQ The samples were prepared for analysis by neutralizing a known volume with ULTREX nitric acid, followed by evaporation of the solution to dry- ness at room temperature. The samples were brought up to 10 ml with BUROM - ■ pesticide grade hexane. Stock solutions were treated IH the same manner to ensure that there was no loss from evaporation.Areas under the individual peaks were measured with an electronic integrator and compared to standard curves to determine the concentrat- ion. Peaks 1-9 in the chromatogram were monitored individually as well as the total area under peaks 1-9. No attempt was made to identify the individual components.The results of the G.C. analyses of the Aroclor 1254 degradation samples were presented in Figures 5-8. Figure 5 shows the total concen- tration of chlorinated biphenyls remaining as a function of time for the three treatment methodologies. As indicated in this figure, the UV plus H„ treatment is more effective than either UV alone or UV plus 0 . The initial rate for the UV plus H„ treatment is significantly faster than the other treatment methodologies even though the final amount degraded for the UV alone and the UV plus H~ after 2 hours is approxi¬ mately the same.Figures 6-8 show the concentration of the individual chlorinated biphenyl components as a function of time for each treatment methodology. Retention time increases with the percentage of compound chlorine. In- spection of these figures shows the rapid degradation of the high chlor¬ inated biphenyls (peaks 5-9) with all treatment methodologies. The lower chlorinated biphenyls disappear at a slower rate and even increase in concentration in the UV alone and UV plus 0„ treatments. These curves are consistent with known mechanisms for photodegradation of PCBs. Table III shows the total final concentrations of all of the PCB components and their total 7o degradation at the end of two hours.TABLE III ppm Final 7cTreatment Concentration DegradationUV 0.93 91.5UV+H2 0.5 95 uv+o3 3.49 68Tests of the stock solution treated with hydrogen gas only, showed that substantially none of the PCB was lost by volatilization. The de- gradation test results, in fact, show an increase in the more volatile components (low chlorinated species) which is indicative of photochem¬ ical reaction. Example 3 Treatment of tetrabromophthalic anhydride (TBPA):TBPA is a high melting white crystalline material which is insolubl in water and sparingly soluble in methanol. In basic methanol, e.g., methanol rendered alkaline with NaOH, the anhydride functional group is reactive, forming the sodium salts and the methyl esters.A weighed amount of TBPA was dissolved in methanol alkalized to pH 11 to make a 100 ppm stock solution. 1.5 1 portions were treated with UV alone, UV and ozone at an ozone flow rate of 0.41 1/min. , and UV and hydrogen at a hydrogen flow rate of 0.75 1/min. in the reactor aforedescribed. Samples of each treatment methodology were taken at 15, 30, 60, 90 and 120 minutes for analysis.The analyses were made using a Waters high pressure liquid chroma- o tograph with a 2537A detector. The carrier solvent was methanol and the flow rate was 1 ml/min. Samples were injected into the LC without any pretreatment. The TBPA concentration of the treated samples was obtained by comparison to a standard curve.Bromide ion concentrations were measured with an Orion bromide elec trode. Samples were prepared by neutralizing 5 ml of each solution with ULTREX nitric acid. The resulting methanolie solution was evaporated to dryness and then diluted to 8 ml with distilled water. Bromide ion con¬ centrations were calculated by comparison with a standard curve con¬ structed from NaBr standards of known composition.The results obtained from the LC analysis of the TBPA concentration of the samples are presented in Figure 9. The UV alone and UV plus 0„ data appear to be very erratic. This erratic appearance is due to the formation of decomposition product, probably the tri- or di-brominated product which is not separated from the original TBPA peak. Figure 10 shows the comparative formation of Br ion as a function of time for. the three methodologies and is a more accurate indication of debromination than in Figure 9.The bromide analysis correlates well with the LC analysis of TBPA when treated with UV plus H„. Upon treatment with UV plus H_, the TBPA is decomposed extremely rapidly during the first 15 minutes, after which TBPA degradation and bromide formation slow down. The lowest TBPA con¬ centration obtained (~ 167» of the original) coupled with the highest bromide concentration obtained (~ 50 ppm) indicate that the molecules were completely debrominated. An equilibrium is that established be¬ tween the TBPA and the resultant phthalic anhydride. To bebrominate the remaining TBPA, this equilibrium must be shifted. Both the UV alone and the UV plus 0 approach the three bromine removal level but at much slower rates. With these treatment methodol¬ ogies, several other compounds also appear in significant quantities on the LC chromatograms. These substances did not appear in substantial quantities when the TBPA was treated with UV plus H~.Thus, the UV plus H_ treatment in basic methanol not only results in significantly more rapid degradation of TBPA than UV alone or UV plus 0„ but in different decomposition products.It is clearly apparent from all of the foregoing data that degrada- tion of halogenated organic compounds by treatment with UV plus H„, pre¬ ferably in alkaline solution, provides an effective and economical means for removing such compounds from manufacturing effluent and/or the environ¬ ment. It has also been shown that the treatment of such compounds with UV alone in aqueous alkaline solutions also provides significant degra- dation. By UV alone , as used in the specification and claims, is meant treatment with ultraviolet radiation without additional chemical treat¬ ment other than the use of a solvent for the halogenated compound. The term aqueous alkaline solution means a solvent free from additional organic solvent. Although this invention has been described with reference to illus¬ trative embodiments thereof, it will be apparent to those skilled in the art that the principles of this invention can be embodied in other forms but within the scope of the claims.OMPI | 1. In a process for degrading a halogenated organic compound having at least one carbon-halogen group in such manner as to remove halo¬ gen from said compound by treatment with ultraviolet radiation, the improvement comprising: treating said compound with ultraviolet o5 radiation in the range of about 1800 to 4000A and hydrogen .in the absence of any substantial amount of oxidizing agent.2. Process of Claim 1 in which the compound has a plurality of carbon- halogen groups.Claims 3 through 18 (cancelled)10 19. In a process for degrading a halogenated organic compound having at least one carbon-halogen group in such manner as to remove halogen from said compound by treatment with ultraviolet radia¬ tion, the improvement comprising: said compound being of the type which forms alkali metal salts when treated with an aqueous alkaline15 solution containing sodium and/or potassium ions, said solution being substantially free from organic solvent, with ultraviolet o radiation in the range of about 1800 to 4000A substantially in the absence of other compound treating agent.20. Process of Claim 19 in which the compound has a plurality of 20 carbon-halogen groups.21. Process of Claim 19 or 20 in which the solvent is a solution of sodium and/or potassium oxide and/or hydroxide.22. Process of Claim 19 or 20 in which the ultraviolet wavelength o range is about 1800 to 2450A. 25 23. Process of Claim 21 in which the ultraviolet wavelength range o is about 1800 to 2450A.24. Process of Claim 20 in which the compound is kepone.25. Process of Claim 21 in which the compound is kepone.26. Process of Claim 22 in which the compound is kepone. 30 27. Process of Claim 23 in which the compound is kepone.28. Process of Claim 1 in which the compound is in liquid solution. (new)29. Process of Claim 2 in which the compound is in liquid solution. (new)30. Process of Claim 28 in which the solution comprises an organic solvent, (new)35 31. Process of Claim 29 in which the solution comprises an organic solvent. (new)32. Process of Claim 28 in which the liquid solution is alkaline, (new)33. Process of Claim 29 in which the liquid solution is alkaline, (new)34. Process of Claim 30 in which the liquid solution is alkaline, (new) 35. Process of Claim 31 in which the liquid solution is alkaline. (new)36. Process of Claim 32 in which alkalinity is produced by sodium and/or potassium oxide and/or hydroxide, (new)37. Process of Claim 33 in which alkalinity is produced by sodium 5 and/or potassium oxide and/or hydroxide, (new)38. Process of Claim 34 in which alkalinity is produced by sodium and/or potassium oxide and/or hydroxide, (new)39. Process of Claim 35 in which alkalinity is produced by sodium and/or potassium oxide and/or hydroxide, (new)10 40. Process of Claim 30 in which the organic solvent is methanol. (new)41. Process of Claim 31 in which the organic solvent is methanol. (new)42. Process of Claim 34 in which the organic solvent is methanol. (new)43. Process of .Claim 35 in which the organic solvent is methanol. (new)44. Process of Claim 38 in which the organic solvent is methanol. (new) 15 45. Process of Claim 39 in which the organic solvent is methanol. (new)46. Process of Claim 32 in which the compound is of the type which forms alkali metal salts when treated with an aqueous alkaline solution containing sodium or potassium ions and the solvent comprises an aqueous alkaline solution containing sodium and/or20 potassium ions, said solution being substantially free from organic solvent, (new)47. Process of Claim 33 in which the compound is of the type which forms alkali metal salts when treated with an aqueous alkaline solution containing sodium or potassium ions and the solvent25 comprises an aqueous alkaline solution containing sodium and/or potassium ions, said solution being substantially free from organic solvent, .(new)48. Process of Claim 46 in which the solvent comprises a solution of sodium and/or potassium oxide and/or hydroxide, (new)30 49. Process of Claim 47 in which the solvent comprises a solution of sodium and/or potassium oxide and/or hydroxide, (new) 50. Process of Claim 1, 2, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, or 49 in which the oUN wavelength range is about 1800 to 2540 A. (new) 35 51. Process of Claim 29, 31, 33, 35, 37, 39, 41, 43, 45, 47, or 49 in which the compound is kepone. (new) 52. Process of Claim 51 wherein the UV wavelength range is about 1800 to 2540A. (new) 53. Process of Claim 31, 35, 39, 41, 43, of 45 in which* -the compound is polyhalogenated biphenyl. (new)54. Process of Claim 53 wherein the UV wavelength range is about o1800 to 2450A. (new) 55. Process of Claim 53 in which the compound is polychloro- biphenyl. (new)56. Process of Claim 55 wherein the UV wavelength range is about o1800 to 2450A. (new)57. Process of Claim 31, 35, 39, 41, 43, or 45 in which the compound is polybrominated phthalic anhydride, (new)58. Process of Claim 57 wherein the UV wavelength range is about o1800 to 2540A.OMPI | ATLANTIC RES CORP | KITCHENS J |
WO-1979000838-A1 | 1,979,000,838 | WO | A1 | XX | 19,791,018 | 1,979 | 20,090,507 | new | A01N5 | A01N9 | A01N25, A01N61, B65G65 | A01N 25/32, A01N 61/00+M, B65G 65/44 | NEW PLANT TECHNIQUE | The effect of certain agricultural chemicals, viz. fungicides, herbicides, insecticides, nematocides and plant-growth regulators, is improved by co-administration of them with one or more of the following additives: carbohydrates, organic acids (particularly fatty acids and acids of the Krebs tricarboxylic acid cycle), vitamins and co-enzymes, purine and pyrimidine nucleosides and nucleotides, naturally occurring fats and oils, certain amino acids and (but not when the agricultural chemical is itself a plant-growth regulator) plant-growth regulators. The invention provides compositions containing one or more of the said agricultural chemicals and one or more of the said additives, and methods of improving the harvest of a given crop by applying to it one or more of the said agricultural chemicals and one or more of the said additives, either simultaneously or within up to about ten days of one another. | NEW PLANT TECHNIQUEThis invention relates to agricultural chemicals, which term is used herein to mean fungicides, herbicides, insecticides, nematocides and plant-growth regulators, and to methods of using them and compositions containing them. The present invention is concerned with altering the performance of such chemicals. The conventional approach to this involves altering the chemical structure to a greater or lesser degree without altering the class or basic chemical type to which the compound belongs, and/or altering the physico-chemical pro- perties of a formulation containing the chemical, e.g. by the addition of chemicals to facilitate coating of the target organism with the agricultural chemical or to improve the adhesion and rainfastness of the agricultural chemical. The literature (including patents) is full of examples of how the conventional approach may be carried out. In particular, it is known that addition of wetting agents can enhance the effect of many agricultural chemicals.The invention is based on the discovery that the efficiency of agricultural chemicals can be markedly improved and that such chemicals can in some cases be used in new and different ways by modifying the organism to which the agricultural chemical is applied, such modification being effected by means of a second chemical herein called an additive. The additive acts in either or both of the following ways, viz., it modifies the way in which the organism takes up and/or moves or internally distributes the chemical, and/or it modifies the metabolism of the organism without affecting take-up or distribution of the chemical, thereby5 achieving the desired action or improvement in action of the agricultural chemical.The invention provides an agricultural formulation com¬ prising an agricultural chemical as hereinbefore defined together with an additive as hereinafter defined. Such formulations may10 be in concentrate form, needing addition of, for example, water to make them ready for use. The invention also provides a method of applying an agricultural chemical to a target organism, in which an additive as hereinafter defined is also applied either simul¬ taneously with the agricultural chemical or not more than 15 days15 (preferably 10 days) before or after. When the application is simultaneous, the agricultural chemical and additive may be supplie in a single formulation or may be mixed _in situ in a spray or other chemical-applying apparatus.The additives used in the formulations and methods of the20 present invention are defined as belonging to one of the following classes (a) to (h), although two or more such additives in the same or different classes may be used, as may two or more agricultural chemicals :(a) a carbohydrate source, (e.g. glucose, hydrolysed25 starch, sucrose, fructose, glycerol, glyceraldehyde, erythrose, ribulose, xylulose and arabinose and their esters and glycosides and metabolic equivalents of carbohydrates), which will normally be applied at 10 to 10,000 g/ha (grams per hectare), to function as(1) A source for the production of high energy bonds as ->~ in adenosine triose phosphate (ATP) production,(2) For the formation of reduced nicotinamide adenine dinucleotide (NADH) and reduced nicotamide adenine dinucleotide phosphate (NADPΞ) and (3) As precursors of amino acids and.nucleotides;(b) an organic acid, particularly one o the Krebs Tricarboxylic Acid Cycle and. their metabolic precursors, (including citric, succinic, malic, pyruvic, acetic and fumaric acids), which will normally be applied at similar rates to and used for similar functions as the carbohydrate source;(c) a vitamin or coenzyme, e.g. thiamine, riboflavin, pyridoxine, pyridoxamine, pyrido al, .nicotinamide, folic acid, or a precursor, thereof including nicotinic acid, which will normally be applied at 0.01 to 0 g/ha to stimulate metabolic processes dependent on enzymatic action;(d) a purine or pyrimidine nucleoside, nucleotide or a metabolic precursor thereof, e.g. adenine, adenosine, thymine, thymidine, cytosine, guanine, guanosine, hypoxanthine, uracil, uridine or inosine, which will normally be applied at 1 to 500 g/ha to act as structural precursors for nucleic acid synthesis;(e) a fatty acid of a type found in natural saturated and unsaturated fats, e.g. butyric, lauric, palmitic, stearic, oleic and iinoleic acid, which will normally be applied at 10 to 10,000 g/ha to act as precursors of molecules required in growth process and through their degradation to provide a source of ATP and NADPH as with a carbohydrate source;(f) a naturally occurring fat or oil including olive, soya, coconut and corn oils, which can be degraded by living organisms to fatty acids and which will normally be applied at (g) an amino acid of a type that occurs naturally in plant proteins, e.g. glycine, alanine, valine, leucine, isoleucine, serine, threonine, cysteine, methionine, aspartic acid, glutamic acid, glutamine, asparagine, lysine, hydro ylysine, arginine, histidine, phen lalanine, tyrosine, tryptophan, proline or hydroxy- proline, which will normally be applied at 1 to 500 g/ha to act as structural units for newly formed proteins or by their degradation to function in a similar manner to fatty acids and carbohydrates; (h) a naturally occurring plant-growth regulator(provided that the agricultural chemical itself is not a plant--BUREATOMPI .A.- W1PO growth regulator) of the type that affects the basic metabolic processes of a plant so as to render an applied pesticide more effective, e.g. indole-3-ace ic acid and gibberellic acid^which are normally used in amount such that the final concentration in a spray applied to the crop is 0.5 to 1000 parts per million by weight.The additives in groups (a) to (g) above are especially effective in enhancing the plant-growth-regulating effect of quaternary ammonium compounds of the formula Er-N(CH_)_-Y in which Y is a non-phytoto ic anion and E is a lower aliphatic radical(e.g. a C, Q or C, r aliphatic radical) containing a non-ionizing nucleophilic group or atom, e.g. haloalkyl, -alkylene, haloalkylene, cyanoalk l, mercaptoalkyl, alkoxyalkyl, alkylthioalkyl or epithio- alkyl. Such compounds are defined in more detail in U.S. Patent No. 3 15 ^ and. a specific example of such a compound is chloro- choline chloride, which has the systematic chemical name β-chloro- ethyl trimethyla_πmonium chloride. It is also known as chlormequat or CCC. The known action of such compounds when applied as a foli spray includes the ability to shorten and strengthen the stems of wheat, oats and rye, though not of barley or rice. Such a shorten and strengthening is sometimes, though not consistently, accompanie by the formation of a better developed root system and the survival of a higher proportion of the tillers or side shoots. While such effects on roots and tillers where they occur may be beneficial in themselves, the principle use of a chlormequat or similar treatment has been to prevent the 'lodging' or collapsing of the cereal plant as the result of strong winds. Such lodging being known to result in loss of yield and difficulty in harvesting.The use of compositions in accordance with the present invention can enhance the effectiveness of chlormequat, especially under poor growing conditions, for example, where the temperature for some days after application of the growth regulator does not exceed 10 C. This condition is commonly encountered during the time at which a cereal plant is reaching the end of the growth lϊΛf OM stage in which tillers are produced (Growth Stage 4-5)• It is frequently desirable to apply the growth regulator at this stage, because certain fungicides and herbicides are also desirably applied before Growth Stage 6, and because crop damage is more likely to occur when the plant has been treated during Growth Stage 6 (at which stage the first 'node' or joint has formed on the tiller) and then encounters a check to growth, as for instance the result of drought.The normal range of application times is from Growth Stage 4 - Growth Stage 6, all of which occur early in the year when the temperatures may be low.In addition to improving on the known action of chlor¬ mequat on stem, roots and tiller survival in wheat, oats and rye, compositions of the present invention may also be used to obtain an action on other cereal plants where chlormequat on its own has failed to give a useful result, as for instance with barley and rice, and to reduce the application rate of chlormequat.Such additives may also be beneficially used with other cereal-growth regulators to obtain effects similar to those obtained by their use in conjunction with chlormequat. Such cereal-growth regulators include, but are not limited to, the following growth regulators used singly or in combination, including combinations with the quaternary ammonium growth regulators described above :- 1. Haloalkyl phosphoric acids (particularly β-haloalkyl- phosphoric acids and especially acids in which the halogen is chlorine) and compounds of the general formula 1 2 where each o R, R and R , which are identical or different, is a hydrogen atom or a C_ alkyl radical. Examples of non- phytotoxic anions are chloride, bromide, methosulphate, sulphate and phosphate. A particularly useful example is 2-chloroethyl phosphoric acid. (CEPA). Such compounds are defined in detail in U.K. Patent No. 1,483,915- 2. Chlorphonium chloride, i.e. tributyl -2,4 - dichloro- benzyl - phosphonium chloride. 3. Mepiquat chloride.4. A diphenyl - 1H - pyrazolium salt of the formulawhere R- is methyl; R^ is alkyl C,-C. ; X is an anion with a charge of 1 to 3; f ϊ'j Z and Z' are hydrogen, halogen, methyl or methoxy; and m is an integer from 1 tc 3; provided that only one phenyl ring can be substituted on the carbon para to the pyrazolium ring with a substituent other than hydrogen. These compounds are defined in detail in U.K. Patent No. 1 466 634. Such compounds also act as specific herbicides selectively con¬ trolling wild oats in wheat and barley crops. The said additives may also be used to enhance this, herbicidal action. JfcLbKBICIDES (Substances for killing and/or controlling unwanted plan A number of herbicides check the growth of weeds so rapidly that the target plant has its metabolism so reduced that the herbicide does not completely kill it. Thus, after an interval during which the herbicide is degraded or suffers a change of form or is removed from those sites where its lethal action is exerted, the weed may then re-commence growth. A particular problem in agriculture is the control of wild oats, where a number of commonly used herbicides show such an effect, especially where the wild cat has become a well established plant. By stimulating growth and uptake of applied chemicals it is possible to enhanceO r the activity of a number of herbicides, especially against older more established weeds.Herbicides that may benefit from applications in con¬ junction with those substances comprising the subject of this 5 patent include, but are not limited to, those herbicides listed below. The names used are those trivial names used in the Pesticide Index :1. Barban 18. Asulam2. Benzoyl-propethyl 19. Nitrofen 10 3. Chlorfenprop-methyl 20. Desmetryme4. Chlortoluron 21. Propachlor5. Difenzoquat 22. Propyzamide6. Diclofop-methyl 23. Diallate ~. Flamprop-ispropyl 24. Triallate15 8. Fla prop methyl 9. Isoproturon10. Atrazine11. Simazine12. Linuron20 13. Trifluralin14. Hormone type weedkillers including MCPA, 2,4-D, MCPB, 2,4-DB, Mecoprop, Dichlorprop, Ioxynil, Bromoxynil, Benazolin, Bentazone, Cyanazine, Dicamba, Dinoseb-a ine, Dinoseb-acetate25 1 • - Dalapon16. Phenmedipham17. GlyphosateA further aspect of this invention is the use of the substances forming this invention to enable a herbicide to be 30 sprayed later than would otherwise have been possible. This is important since :-(a) A period of weather unfavourable to spraying may allow weeds to grow beyond the stage or size at which they may be satisfactorily controlled.-BUREAT;OMPI fa W1P0 (b) By making it possible to treat older weeds a longer period is allowed for other weeds to germinate and become susceptible to the action of a foliar (leaf-applied) herbicide. (c) By enabling spraying to take place later, it may enable the crop to become better established and less ' at risk to damage from the applied agricultural chemical. A particular example of the use of such substances to enable spraying to be delayed is their use in conjunction with chlortoluron,C N - ( 3 - chloro - 4 - methylphenyl) - N,N dimethyl urea_,such that it will control wild oats (Avena spp) that have passed the two—leaf stage (ZCK 12) and blackgrass (Alopecurus spp) that has passed the five—leaf stage (ZCK 1 ). Known formu- lations will give only a poor control of wild oats up to the two- leaf stage and negligible control thereafter. Blackgrass will be controlled satisfactorily only up to the five—leaf stage. Since blackgrass and wild oats germinate over an extended period it is possible to have late-germinating weeds emerging while early- germinating weeds have passed the stage at which they may be controlled. For this reason chlortoluron is used primarily as a soil-applied chemical acting through the weed roots. By extending the period at which emerged weeds may be controlled a useful alternative method of application independent of soil conditions is provided. In the autumn conditions may be unsuitable for soil application either because of excessive water or excessive dryness.A specific aspect of this invention involves the enhancement of the herbicidal activity of bipyridyliu herbicides. The metabolism of a target weed organism may be modified in a specific manner by modifying a distinctive biochemical pathway or reaction in order to enhance the activity of an agricultural chemical.The lethal action of the bipyridyl herbicides paraquat (l,l -dimethyl-4,4 dipyridylium salt) and diquat (l,l -ethylene- 2,2 dipyridylium) is the result of the formation of hydrogen per¬ oxide when the paraquat or diquat ion, having been reduced to the free radical by the photosynthetic electron flow, is re-oxidized by molecular oxygen, thus re-forming the paraquat or diquat ion and Ε. ~ As this can happen very rapidly (especially in bright sun¬ shine) it is possible for the herbicide to destroy superficial leaf cells where droplets of herbicide solution have fallen and thus prevent its own continued uptake into the bulk of the plant cells. The speed of the lethal action may be slowed down by providing an alternative oxidation/reduction system. Thus the use of oxidized glutathione (GSSG) in conjunction with a bipyridyl herbicide can be used to re-oxidize the reduced free radical while forming reduced glutathione (GSH). If this syte is coupled with another system or systems to re—oxidize the reduced glutathione then the glutathione will act in more than a simple stoichiometric relationship with the herbicide.One such system is the enzymic re-oxidation of reduced glutathione in conjunction with nicotine adenine dinucleotide phosphate (NADP), which may be stimulated by the use of an NADP precursor such as nicotinamide or nicotinic acid, and a further system is that of ascorbic acid/dehydroascorbic acid catalysed by the enzyme ascorbic acid oxidase, which may be stimulated by the use of ascorbic acid. Ascorbic acid is initially added and converted in the plant to dehydro scorbie acid-(5) below. The reactions that take place with paraquat and GSSG are thus : light Paraquat ion ~ reduced free radical -t- _ϋ (l) reduced free radical + 0_ ÷ Hp0 ^Paraquat ion + Hp0 (2) reduced free radical + GSSG .Paraquat ion + GSH (3)GSG + dehydroascorbic acid ^ascorbic acid + GSSG (4) oxygen Ascorbic acid ^ Dehydroascorbic acid (5) ascorbic acid oxidaseThus some of the free radical from the paraquat is temporarily mopped up, and the formation of H O effectively slowed down while re-forming the paraquat ion.-BUREATTO PI. Am W1PO - FUNGICIDES AND INSECTICIDES (i.e. substances for killing and/or controlling fungi and insects).The beneficial activity of these materials can be enhanced in accordance with the invention. Thus by stimulating the metabolism the fungus is less able to resist the toxic effects of the chemical by having its growth temporarily restricted while a systemic fungicide or insecticide which must penetrate through the plant for maximum effect may more readily do so.The insecticides and fungicides where effects be beneficially modified in accordance with the invention include, but are not limited to, the following :-FungicidesCaptan MancozebCaptafol VinclozinDimethirimol ZinebBenodanil ThiramManeb ChloropyriphosTridemorph TriazophosTriadimephon BinapacrylThiabendazole BupirimateTriforine DitalimfosCarbendazim SulphurDodineThiophanate methylPyrazophosEthirimolInsecticidesDemeton-S-methyl Piri iphos-methyl LindanePyrimicarb DDT FonofosVamidothion Azinphozmethy1 DN0CDemephion TrichlorphonMenazon TriazophosDimethoate MalathionDimefox PhosaloneFenitrothion CarbarylPhosphamidon In a further aspect of this invention, the activity of an agricultural chemical not containing an additive as hereinbefore described as a metabolic stimulant will have its own activity stimulated or otherwise beneficially modified as the result of being applied in conjunction with an agricxiltural chemical formu¬ lated with such a substance.The toxicity of compositions in accordance with the present invention may be reduced by including in the mixture a compound that acts as a purgative or emetic or that acts to delay uptake of the material in the alimentary canal. Suitable purgatives include phenolphthalein, senna extract and castor oil. Apomorphine is a useful emetic, whose effect is enhanced by the presence of ethyl alcohol. The amount of emetic that is added (e.g. to paraquat) is such that if sufficient agricultural chemical is ingested to cause a toxic response, sufficient emetic is ingested to cause e esis.References in the specification to growth stages in weeds are those defined in the Weed ControlHandbook , ed J D Fryer and R L Makepeace, Blackwell Scientific Publications, e.g. in the 6th Edition.The following are illustrative Examples of compositions in accordance with the invention. 225 litres of spray solution iε normally used per hectare.Example Additives per 225 litres of spray solutionGlycerol 75 ml.Alkyl phenol eth lene oxide condensate (wetting agent) 175 ml.Nicotinamide 3 g.Pyridoxine 1.5 g.Yeast extract 3 g.II Glucose syrup 500 g.Triton - X 100 (wetting agent) . 250 ml.Yeast extract 80 g. Example Additives per 225 litres of spray solutionIII Glycerol 100 ml.Alkyl phenol ethylene oxide condensate (wetting agent) 300 ml.Citric acid 100 g«Sucrose 150 g-IV Glycerol 300 ml.Gibberellic acid 50 g.Alkyl phenoleethylene oxide condensate (wetting agent) 200 ml.Yeast extract 200 g.Asparagine 20 g.Methionine 15 g-Cysteine 15 g«VI Ascorbic acid 60 g«Nicotinamide 10 g-Glycerol 100 ml.Glutathione 25 g-Alkyl phenol ethylene oxide condensate (wetting agent) 200 ml.VII Corn oil 1000 ml. Nicotinamide 5 g- Pyrido ine 5 g« Yeast extract 10 g- Glycerol 75 ml. VIII Corn oil 750 ml.Gibberellic acid 5 g- Glucose syrup 250 g.IX Olive oil 500 ml.Alkyl phenol ethylene oxide condensate (wetting agent) 500 ml.Sucrose 200 g-Yeast extract 10 g'OS , W WIIPP Example Additives per 225 litres of spray solutionX Corn oil 250 ml. Nicotinamide 5 g. Yeast extract 30 g- Methionine 5 g-Glycerol 60 ml.Alkyl phenol ethylene oxide- condensate (wetting agent) 200 ml.XI Corn oil 1000 ml. Chlorocholine chloride 800 g- Nicotinamide 5 g-Pyridoxine 5 - Yeast extract 10 g« Glycerol 75 ml.XII Sucrose 100 . Yeast extract 5 g«Citric acid 25 g«Asparagine 10 g.Alkyl phenol ethylene oxide condensate (wetting agent) 50 ml.XIII Ascorbic acid 60 g« Nicotinamide 10 g«Glycerol 100 ml.Glutathione 25 g-Alkyl phenol ethylene oxide condensate (wetting agent) 200 ml.Ethyl alcohol 60 ml. The following experimental data show effects produced by certain compositions and methods in accordance with the present invention and compare such effects with those of the prior art. In this connection, it should be noted that the further addition of a wetting agent to a standard commercially obtainable formu- lation of a pesticide is known in some cases to improve its efficacy. Therefore in comparative trials a wetting agent corres- ponding to that in the combination of additives was also used with the application of the standard formulation.In comparing the quantities of materials used, it is to be understood that where amounts of agricultural chemical, additive or wetting agent are given per hectare, this means amounts per 225 litres of solution, always expressed in terms of the active ingredi In Experiments 1 to 4, the Standard is a Standard commercially obtainable formulation with additional wetting agent of the type' and in the amount shown in Example I, and the Standard + Additive is the same Standard formulation with additives as shown in Example I.EXPERIMENT 1 Low Temperature - WheatThis is a comparison of a standard commercially available formulation of Chlormequat, viz. Mandops Chlormequat 46, with the same formulation to which additives as in Example I have been added, with respect to their abilities to shorten the stems of wheat when the temperature does not rise above 7 C for 5 days before and for 5 days after application. Results are expressed as an average of 250 measurements.Stem Height Reduction cmControl (untreated) 96.4 -Standard 88.3 8.4Standard + Additives 83.9 13.0 The application rate is equivalent to 7-16 g. ofChlormequat per litre sprayed to run-off on pot-grown plants of Maris Huntsman at Growth Stage 5« The plantswere maintained for 5 days before and after spraying at below 7 C, and were then moved to field conditions. EXPERIMENTS 2(a) AND 2(b)BarlevThis is the effect on stem height in (a) spring barley and (b) winter barley of 1.6 kg per hectare of chlormequat + additive as in Example I. Application is made at Growth Stage 6 (1st Node Stage) in 225 litres per hectare of water. Results are expressed as average of 250 measurements.Stem Height °/o Reduction cm (a) Spring barley (Mazurka)Control (untreated) 87.4 -Standard 86.2 1.4Standard + Additives 76.3 12.7Winter barley (ieri)Control (untreated) 91.2 -Standard 90.2 1.1Standard + Additives 80.9 11.3EXPERIMENT 3Rice A standard commercially available formulation of chlor¬ mequat is compared with the same formulation to which additives (as in Example i) have been added.°io Reduction in stem heightControl (untreated) - Standard 1.1Standard + Additives 11.3Rate of application is equivalent to *1 g. of Chlormequat per litre sprayed to run-off onto plants 20 cm in height.EXPERIMENTS 4(a) AND 4(b) WheatA standard commercially available formulation of chlor¬ mequat is compared with the same formulation to which additives (as in Example i) have been added, with respect to their abilities to shorten the stems of wheat (var. Maris Huntsman). Average of 250 measurements Stem Height °/o Reduction cm(a) Control 94.2 — Standard 83.6 11.3 Standard + Additives 80.4 14.6(b) Standard 82.3 12.6 Standard + Additives 79.8 15.3Rate of application is equivalent to 1.2 kg of chlormequa per hectare (Standard (a)) and to 1.6 kg per hectare (Standard (b) applied in 225 litres per hectare at Growth Stage 6 (1st Node Stage).EXPERIMENTS 5(a) AND 5(b)Effect of Chlortoluron on Wild OatsThis is a comparison of a commercially available formu¬ lation of chlortoluron, viz. that sold under the trade mark Dicurane , with the same formulation to which additives as in Examples VII and XI have been added with respect to their abilities to control wild oats.The application rate is equivalent to 3«6 kg Chlortoluron per hectare in 225 litres of water. (a) Wild Oats sprayed at 5-leaf unfoldedStage (ZCK 15) jo kill of wild oatsStandard formulation with additional wetting agent of the type and in the amount shown in Example VII 15Standard formulation with additives as shown in Example VTI 62Standard formulation with additives as shown in Example XI 80 B^ (b) Wild Oats sprayed at 7-leaf unfolded stageStandard formulation with additional wetting agent of the type and in the amount shown in Example VII 5Standard formulation with additives as shown inExample VII 48 Standard formulation with additives as shown in Example XI 71EXPERIMENTS 6(a) AND 6(b) Effect of Paraquat A standard commercially available formulation of paraquat, viz. Gramoxone, is compared with the same formulation to which additives as in Example VI have been added with respect to (a) to their abilities to destroy an old grass sward and (b) to kill a population of mixed and broad leaf and grass seedling weeds at from 2 - 5 leaf stage. In this experiment the Standard is a Gramoxone with additional wetting agent of the same type and in the same quantity as in Example VI and the Standard + Additives is Gramoxone + Additives as shown in Example VI. (a) The application rate is equivalent to 1.1 kg of paraquat per hectare in 400 litres of water. The kill of sward is assessed 4, 8 and 12 days after application.Score (0 = nil effect, 10 = 100^ kill)4 days 8 days 12 daysTrial 1. Standard 4 6 7Standard + Additives 2 4 9Trial 2. Standard 2 5 6Standard + Additives 1 3 8 (b) Application rate is equivalent to 0.25 kg of paraquat per hectare in 200 litres of water. Control assessed at 2, 6 and 10 days after application. io Control2 days 6 days 10 daysStandard 5 6 6Standard + Additives 3 7 8EXPERIMENT 7GlyphosateA standard commercially available formulation, viz. that sold under the trade mark Roundup , is compared with the same formulation to which additives as in Example XII have been added. A mixed week population (grasses and broad leaf weeds) was sprayed and assessed after 2 weeks (0 = nil effect, 10 = complete kill).Weed controlRoundup (θ.7 Kg/ha glyphosate) with wetting agent.of the type and in the amount shown in Example XII 7Roundup (θ.7 Kg/ha glyphosate) with additives as shown in Example XII 7Roundup (θ.5 Kg/ha glyphosate) with additives as shown in Example XI 9EXPERIMENT 8Fungicides Standard commercially available formulations of(a) captan (b) thiophanate-methyl and (c) dodine were compared with the same formulations to λΛiich additives as in Example X have been added, with respect to their abilities to control black spot of roses. (a) Captan • jo Control (14 days after sprayiStandard (Mandops Captan 83) 8Standard + Additives 95r The rate of application is equivalent to 100 grams of captan per 100 litres of water sprayed to run-off.(b) Thiophanate-methyl. °/o Control (14 days after spraying)Standard (Benlate) 72 Standard + Additives 90Rate of application is equivalent to 46 g. of thiophanate per 100 litres of water sprayed to run-off.(c) Dodine jo Control (14 days after spraying)Standard (Mandops dodine 65) 84 Standard + Additives 96The rate of application is equivalent to 60 g. of Dodine per 100 litres of water sprayed to run-off.In this Experiment, the Standard is the indicated standard commercially obtainable formulation with additional wetting agent of the type and in the quantity used in Example X and the Standard + Additives is a standard commercially obtainable formulation with additives as shown in Example X The word Benlate is a trade mark.EXPERIMENT 9 Effect of carbendazim on evespot of wheatA standard commercially available formulation of carbendazi.m, viz. that sold under the trade mark Bavistin, is compared with the same formulation to which additives as in Example X have been added with respect to their abilities to control eyespot disease of wheat (var Maris Huntsman).°/o Control of Eyespot leaf Infestation in Julv(a) Bavistin together with additional wetting agent αf the same type and in the same quantity as used in Example X 64Bavistin with additives as shown in Example X 75O PI 5-> Control of Eyespot leaf Infestation in July(b) Bavistin together with additional wetting agent of the same type and in the same quantity as used in Example X 76Bavistin with additives as i shown in Example X 90Application rate is equivalent to 250 grams of carbendazim per hectare' in Standard (a) and 500 grams of carbendazim per hectare in Standard (b). Application was made at Growth Stage 5-EXPERIMENT 10InsecticidesComparison of a standard commercially available formu- lation(a) demeton-S-methyl, viz. Mandops Demeton-S-Methyl 50, and(b) Dimethoate, viz. Mandops Dimethoate 40 with the same formulation to which additives as in Example IX have been added, with respect to their aphicidal action on potatoes.<fi control of aphids24 hours after spraying(a) Mandops Demeton-S-methyl with additional wetting agent of the same type and quantity as inExample IX 82 Mandops Demeton-S-methyl 0 with an additive as shown in Example IX 95(b) Mandops Dimethoate 40 with additional wetting agent of the same type and quantity as in Example IX 75Mandops Dimethoate 40 with additives as shown in Example IX 88The ratesof application were, for demeton-S-methyl, 22 gms/lOO litres of water and for dimethoate, 33.6 gms/lOO litres of water.BU OWI EXPERIMENT 11Toxicity Studies on chlormequatThe additives used in accordance with the present invention can have an effect on the toxicity of chlormequat even without the addition of purgatives or emetics. For example, in young adult rats the LD_._. of aqueous chlormequat corresponding to the formulation used in Experiments 1 to 4 is 600 mg/kg, but it becomes 820 mg/kg by the addition of 47 ml of glycerol and 109 ml of alkylphenol ethylene oxide condensate per 1 kg of chlormequat. | CLAIMS1. A method of applying an agricultural chemical that is a fungicide, herbicide, insecticide, nematicide or plant-growth regulator, characterized in that an additive that modifies the metabolism of fungi, plants, insects or nematodes is also applied to the same locus as the agricultural chemical not more than 15 days earlier than or more than 15 days later than the agricultural chemical, whereby the desired effect of the agricultural chemical is enhanced.2. A method as cle_imed in Claim 1 in which the additive is a carbohydrate, a fatty acid, an acid of the Krebs Tricarboxylic Acid Cycle or a metabolic precursor thereof, a vitamin or coenzyme, a purine or pyrimidine nucleoside or nucleotide or a precursor thereof, a naturally occurring fat or oil, an amino acid or (except when the agricultural chemical is a plant—growth regulator) a naturally occurring plant-growth regulator.3. A method as claimed in Claim 2 in which the agricultural chemical is chlorocholine chloride and it is applied to wheat, oats or rye to produce its known effect of shortening and strengthening the stems and the additive is such as to enhance that effect and possibly improve the root system and side shoots.4. A method as claimed in Claim 2 in which xhe agricultural chemical is chlorocholine chloride and it is applied to rice orO V barley, the additive acting to cause the chlorocholine chloride to shorten and strengthen the stems and possibly improve the root system and side shoots.5. A method as claimed in Claim 2 in which the agricultural chemical is a herbicide and is being applied to established weeds.6. A method as claimed in Claim 5 in which the herbicide is of the bipyridylium type and the additive is such as to affect the • oxidation of the bipyridylium free radical.7. A method as claimed in any one of Claims 1 to 6 in which the agricultural chemical and the additive are applied by spraying onto plants or insects.8. A method as claimed in any one of Claims 1 to 7 in which an agricultural chemical not containing an additive as defined in Claim 1 is applied not more than 15 days before and not more than 15 days after a mixture of an agricultural chemical and an additive as defined in Claim 1.9. An agricultural composition suitable for application, either as such or diluted, to plants, characterized in that it contains an agricultural chemical as defined in Claim 1 together with an additive as defined in Claim 1.10. A composition as claimed in Claim 9 in which the additive is as defined in Claim 2.11. A composition as claimed in Claim 10 in which the agri¬ cultural chemical is chlorocholine chloride.12. A composition as claimed in Claim 10 in which the agri¬ cultural chemical is a herbicide of the bipyridylium type and the additive is such as to affect the oxidation of the bipyridylium free radical. 13. A composition as claimed in any one of Claims 9 to 12, that also includes a purgative or emetic to decrease its toxicity hazard to mammals.14. A composition as claimed in any one of Claims 9 to 13 in the form of a sprayable liquid.15. A composition as claimed in any one of Claims 9 to 14 also mixed with a second agricultural chemical whereby toxic risk to mammals is reduced. | SAMPSON MICHAEL JAMES; SAMPSON M | SAMPSON MICHAEL JAMES; SAMPSON M |
WO-1979000839-A1 | 1,979,000,839 | WO | A1 | EN | 19,791,018 | 1,979 | 20,090,507 | new | B42C9 | null | B42B5, B42C9 | B42C 9/00 | METHOD OF AND APPARATUS FOR THE AGGLUTINATION OF SHEETS | A method for the agglutination of a plurality of sheets (2), more particularly of paper, arranged in a stack. A punching mechanism (1) provided with a channel through which melted or dissolved adhesive can be dispensed is passed through the stack to cut a throughgoing hole (9). Said hole is formed by U-shaped, serrated or corrugated slits presenting in each sheet one or more tongues (10) which the downward movement of the punching mechanism causes to bend away from their original positions while at the same time adhesive is introduced into the hole. The retraction of the punching mechanism causes the tongues to unbend and return to their original positions, which has the effect of introducing the adhesive between the individual sheets and accomplishing the agglutination. The invention further relates to an apparatus for the embodiment of the method according to the invention. The apparatus comprises a support (3) for holding a stack of sheets (2) and a cutting mechanism (1) with an end face (13) of an angular or corrugated cross section. Said cutting mechanism is provided with a hollow shaft (6) and means (14, 15, 17, 18, 19) for depositing adhesive on the punched-out tongues. Furthermore, the apparatus is provided with means (12, 16) for returning after the application of adhesive to the tongues and retraction of he punching mechanism the bent-down tongues to their original positions. | Method of and Apparatus for the Agglutination of SheetsThe invention relates to a method for the agglutination of sheets, more particularly of paper, but also of materials such as card¬ board, textiles, foils, or the like, irrespective of vhether the said sheets are of the same material or of different materials, and a-n apparatus for the embodiment of the method.A videly used means for in erconnecting a number of sheets of pa¬ per or other materials, especially where the sheets have to be folded after the interconnection, as for example in the case of catalogues and magazines, is metal staples. Other methods invol sewing or welding. However, agglutination is also used, for exa pie in newspaper production where strips of glue the entire length of the newspaper are used for joining the individual pa¬ ges. But agglutination of sheets of paper, especially of a plur lity of sheets, seems to be industrially advantageous in partic* lar where it is possible to apply a flexible adhesive to a free edge of a stack of paper sheets. This is the method used for ex ample in the production of writing pads. But the agglutination accomplished by this method has only limited strength as the individual sheets of the stack partake only of a very narrow strip of glue.According to British Patent No 1,305. *+8 a number of paper shee may be interconnected in the vicinity of the edge of the stack punching holes in the stack and in the same operation introduci: an adhesive into the hole, from which the adhesive is then sup¬ posed to spread between the individual sheets. A very similar π* thod for interconnecting the sheets of a stack of paper by punc ing a hole for the introduction of glue is known from Vest Ger¬ man OS No 2' 055 127.The agglutination of superposed sheets can be improved by fa-nni: the sheets before subjecting them to adhesive. This method is known from the specification of British Patent No 681,858.French Patent No 1,016,027 states a method for agglutinating sheets of paper by which fairly long tabs in the shape of narro tongues are punched up out of a line in the sheets and then ben back completely and subjected to adhesive whereafter said tongu are unbent again and made to combine into an interlace which if? secured to the outermost surface of the stack. This agglutinati of interlaced tongues serves to interconnect outside the actual stack of sheets not only the individual sheets of the stack but also the stack and similar consecutively arranged stacks of fol ed paper, for example for bookbinding purposes.The problem underlying the present invention is to provide a mβ thod which permits, better than any hitherto known me*ϋ«_rt ^-rτca pid, economical and tear-resistant agglutination, especially in the case of sheets that have to be folded after the interconnect¬ ion. There seems to be no method in existence by which for ex¬ ample far larger numbers of sheets may be joined in one opera¬ tion than is possible by means of the commonly used staples, and which implies less risk of tearing out of individual sheets than by methods involving the use of staples.The specific character of the present invention is described in the characterising part of Claim 1.In one embodiment of the invention it is proposed to provide a means for applying a thin strip of cardboard or the like to the strip of adhesive on the uppermost sheet immediately after adhes¬ ive has been applied and the tongues bent back. This permits the agglutinate stack of paper sheets to be transferred, folded or in any other manner further processed, even before the adhesive de¬ posited on the sheets is dust dry, still less thoroughly hardened,The method according to the invention provides strong and tear- proof agglutinations. Furthermore, it can be automated and is economical in terms of consumption of time and adhesive. The pre¬ sent invention makes it possible to agglutinate even very large numbers of sheets in one operation, since the punched-out tongues can be very short and yet permit an effective agglutination. The fact that the final hardening or setting of the adhesive takes place inside the stack with the tongues returned to their origin¬ al positions and with adhesive deposited between the slits of all the sheets provides a strong reinforcement of the hole where the agglutination takes place, preventing that any of the sheets become detached or can be torn put very easily. Thus agglutina¬ tion of sheets of a wide variety of materials becomes a new alter native to methods of interconnection by means of staples, sewing, welding, etc. , and opens up the possibility of new industrial ap¬ plications for example agglutination of textiles.In the following the invention will be more specifically descri¬ bed with reference to the accompanying drawing in which figure 1 is a perspective view of one embodiment of an _8,_Ej *r-*.*tus according to the invention figure 2 shows examples of the shapeε of the punched-out slits figure 3 is a longitudinal section through a combined punching and adhes ve-applying mechanism figure shows another embodiment of the adhesive-applying me¬ chanism figure 5 shows yet another proposed embodiment of sameFigure .1 shows the lower part of two suitably interconnected co: bined punching and adhesive-applying mechanisms in a position where they have been moved vertically down towards and now just touch a horizontally positioned stack of paper sheets 2 resting on a support 3- Other directions of movement and other angles between the surface of the stack and the direction in which the punch is introduced are also possible, but an angle of approxi¬ mately 0 seems preferable. The dot-and-dash line h on the she of paper suggests a line along which the stack of sheets may be folded after the agglutination. The agglutination can also adva: tageously be performed along an outer edge of *the sheets. By means of a suitably flexible and movable tube 7 the shaft 6 of the punching and adhesive-applying mechanism is connected to a container 8 for adhesive, which can advantageously be temperatu and pressure controlled to ensure convenient and even feed of a' hesive.The solid lines in figure 2 show a number of many possible shap of the slits 9 punched out in the sheets, whereas the dot-and- dash lines show how the tongues 10 presented by the punch are bent down by the punching and adhesive-applying mechanism. The hatched areas represent the hole produced in the sheets by the punching operation. It is apparent that by choosing for example a serrated or corrugated slit it is possible to adjust the leng of the strips of adhesive so that even in a limited area fairly long strips can be obtained and thus adapted to the type of she to be agglutinated.The punched-out tongues 10 need only be of very as will be apparent from figure 3. since the width of the strip of adhesive 11 deposited on the underlying sheets is determined by the degree of displacement of the bent-down tongues. Beyond a very narrow limit depending on such factors as the thickness of the sheets and on the angle of bending increasing the length of the tongues does not increase the displacement. Furthermore, ΓΘ- la-fcively short tongues are advantageous in that they are capable of being more rapidly and conveniently returned to their original positions after the adhesive has been applied to them. Returning of the tongues can for example be effected by means of the two spring-loaded plates 12 situated in the support 3- However, the individual tongues need not be returned to their exact original positions. A certain degree of overlapping might even be advan¬ tageous. Such overlapping can be aided by letting the tongues be of a suitable shape, for example S-shaped, cf the last example shown in figure 2. By the method according to the present inven¬ tion an effective agglutination of a fairly high stack of paper sheets can be accomplished without the tongues having to be long enough to be secured outside the stack. On the contrary, if the tongues are too long there is a risk that they may become entan¬ gled and thus form an obstruction preventing the complete passage of the adhesive-applying mechanism through the stack.In the simple embodiment of the combined punching and adhesive- applying mechanism shown in figure reference number 13 designa¬ tes the punching tool, which is attached to a suitably hollow shafi 6 provided with channels 14 through which melted, dissolved or dispersed adhesive can be fed evenly to a pad 15. The pad 15 can be made of felt, foam rubber or any other porous material and can have a cross section corresponding to the hatched areas in figure 2 which represent the holes formed in the stack of paper sheets and to whose sides the adhesive is applied.Returning of the bent-down tongues 10 to their original positions can for example be effected by means of two underlying spring- loaded . plates 12, the contiguous edges of which can advantageous¬ ly be adapted to the shape of the slit and thus to that of the tongues. As the punching and adhesive-applying mechanism passes through the stack the spring-loaded plates 12 are pressed down to positions which form an angle approaching 0 with their ori g±nal positions. In the retraction of the combined mechanism, •which follows immediately on the punching operation the springs l6 cause the spring-loaded' plates 12 to return to their origin; position at the same time forcing the entire column of tongues i* wards to take up positions in the vicinity of their original po sitions in the stack where the final setting or hardening of th> adhesive takes place. The fact that by the displacement of the tongues relative to each other adhesive has been distributed ovi the surface of each individual tongue ensures that when the ton gu.es are returned the adhesive will spread well when it is pres¬ sed out between all the sheets of the stack. If desired, the pressure on the sheets can be increased by letting the spring- loaded plates 12, which can advantageously be provided with a coating of an adhesive-repellent substance for example teflon bι controlled, instead of by the springs 16, by a special clamping mechanism, which advantageously can be coordinated with- the mech. nism for applying to the tacky areas on the uppermost sheet soπ-i means for inhibiting the adhesive effect, for example at least one piece of thin cardboard or plastics film, a powder or the like.Figure shows another possible embodiment of the adhesive-appl ing mechanism, in which the porous pad 1 is replaced by a kind of brush. Approximately at right angles to the direction of ope¬ ration are mounted a number of fairly stiff hairs or the like 1' The upper part of figure 4 shows an alternative to the brush, i_ the form of short, small-bore tubes 18 allowing the passage of adhesive. This form of the invention may provide an even better spread of the adhesive between the individual sheets of the sta< and furthermore the subsequent retraction of the adhesive- apply¬ ing mechanism will aid the returning of the bent-down tongues.As shown in figure 5 t .e introduction of adhesive can also be accomplished by means of a solid stick of adhesive 19, which cai for example be slightly tapered at one end to ensure a gradual ^ newal. This form of the invention might be particularly ad anta- geous for a smaller and simpler embodiment of an apparatus accor¬ ding to the invention, which could replace for example small sta¬ plers for metal staples.The abovementioned adhesive inhibitor of cardboard may be needed in particular for the uppermost sheet, which is the first to be touched by the adhesive-applying mechanism, adhesive being appli©1 to the entire area indicated in figure 2 by hatching. A similar passivation may be required for the adhesive applied to the ne¬ thermost sheet of the stack, for example in the form of a powder such as talc, which can prevent any undeεired adhesion to other surfaces. Alternatively, a kind of simple passivation can be ob¬ tained by folding the sheets immediately after the agglutination for example along the dot-and-dash line 4 in figure 1. A further advantage gained by passivating at once any inappropriately adhes¬ ive surfaces is that it permits the use of more slow-drying ad- hesiveε, with for example water as disεolving or dispersing agent and thus less harmful to the working environment. | CLAIMS1. Method for the agglutination of sheets of paper, cardboard, textiles, foils, leather or other materials wherein a punch¬ ing mechanism is passed through the sheets to be aggluti¬ nated to punch out at least one slit, and thus a tongue or tongues, of serrated, corrugated or any other suitable cross section permitting that in the passage of an adhesive-ap¬ plying mechanism, preferably associated with the punching mechanism, a suitable hole is established through the sheets, while at the- same time adhesive is applied to the tongues which are bent and fanned in the formation of the hole, whereafter said tongues, are returned to substantially their original positions in or after the retraction of the punch¬ ing and adhesive-applying mechanism so that the final agglu¬ tination is effected inside the stack of sheets.2. Method as claimed in claim 1, wherein directly in connection with the application of adhesive at least one strip of thin cardboard or plastics foil, a powder or any other adhesive- inhibiting means is applied to the adhesive areas of the upp. surface of the uppermost sheet or sheets of the agglutinate stack.3_ Apparatus for carrying out the method claimed in claim 1, wherein are provided a support for supporting a stack of sheets and further a punching mechanism for being passed through the stack of sheets in the direction of the support and which includes a leaf-shaped cutting tool with an end fat for example of angular or corrugated cross section and a sha. on the surface of which are provided means for applying adhe. ive to the tongues punched out of the sheets by the cutting tool, and further a means for returning as the cutting tool is retracted the bent-down tongues to substantially their or: ginal, mutually parallel positions. 4. Apparatus as claimed in claim 3. wherein the support is pro¬ vided with at least one movable plate suitably adapted to the cross sectional shape of the cutting' tool end face and capable of yielding when acted on by said end face as it passes throug] the stack and further capable of springing back at the same time causing the punched-out and bent-down tongues to return to substantially their mutually parallel positions.5. Apparatus as claimed in claim 3. wherein the dissolved, melted or dispersed adhesive is fed from a container which can advan¬ tageously be pressure and temperature regulated to pass throug] movable tubes into the hollow shaft of the punching mechanism from where it passes on through channels in the shaft to be deposited on the porous pad or the brush or the equivalent thereof of the adhesive-applying mechanism or the adhesive can pass out through fine tubes connected with the channels of the shaft and arranged preferably at right angles to the direction of travel of the shaft.6. Apparatus as claimed in claim 3, herein the adhesive is ap¬ plied by means of a solid stick of adhesive which advantageous¬ ly can be associated directly with the punching mechanism.7. Apparatus as claimed in claim 3. wherein is provided a means for carrying out the method as claimed in claim 2. | GRAM O; GRAM O AS | GRAM O |
WO-1979000841-A1 | 1,979,000,841 | WO | A1 | XX | 19,791,018 | 1,979 | 20,090,507 | new | G01H9 | A61B1 | A61B1, G01H9 | A61B 1/227, A61B 1/267B2, G01H 9/00C2 | SPECKLE INTERFEROMETRIC MEASUREMENT OF SMALL OSCILLATORY MOVEMENTS | Measurement of small oscillatory movements of an irregular surface (12) involves the production of a speckle pattern therefrom by coherent light illumination, and the arrangement of a photodetector (14) for direct response to such pattern, variations in photodetector output component at the frequency of the surface movement representing that movement. Another, stationary, illuminated irregular surface (13) can be involved to produce a speckle interference pattern for response of the photodetector (14) thereto and, in the case where the two surfaces (12, 13) are closely adjacent, a single beam can be used to illuminate the first and other surfaces predominantly and by stray light, respectively. This common beam illumination can be used in prior speckle interferometry. The first surface (12) can be an eardrum oscillated by a sound wave, suitably of swept frequency or impulse form, with detection of the photodetector variations respectively being in synchronous manner or by Fourier analysis, respectively. | SPECKLE INTERFEROMETRIC MEASUREMENT OF SMALL OSCILLATORY MOVEMENTSThis invention concerns the measurement of small movements and more particularly the measurement of movements, typically vibrations, having magnitudes less than the wavelength of light. Interferometry is a well-established technique for making such measurements and a more recently developed technique of this kind is that known as laser speckle interferometry. This last technique derives from the finding that the scattering and reflexion of coherent light from an irregular surface produces a field which can be imaged as a speckled pattern of relatively light and dark areas, and that two such fields from respectively different surfaces can interfere to produce a pattern which is modulated in phase upon movement of one of the surfaces in the direction of the incident light.It is to be noted that a speckle pattern itself will be subject to variation together with movement of the surface from which it is derived, but this variation has previously been considered too random and/or fine grained to be of direct use. Indeed, early opinions of speckle pattern phenomena regarded the same as undesirable noise effects associated with laser illumination.In any event, laser speckle interferometry as so far practised has entailed discrete recording in various ways of an imaged interference pattern created by one relative disposition of the two surfaces for comparison therewith of the directly corresponding pattern created by a changed disposition of the two'BUREOMPI </ATl surfaces in order to obtain a measure of the movement leading from one disposition to the other. The recording step of this procedure necessarily involves a complexity of equipment and/or processing compared to an intrinsically instantaneous measurement technique.Also, laser speckle interferometry as so far practised has entailed the provision of separate beams of coherent light, ofte derived from a common laser source, to respectively illuminate the two surfaces. This involves a complexity of optical equipme and, possibly more important, can render difficult or impracticable the application of the technique to surfaces to which access is difficult.In contrast to the situation just described the present invention provides laser speckle interferometry techniques, and related techniques, which require no discrete recording of interference patterns and which can be operated with a single coherent light beam. The presently proposed techniques in fact have two aspects respectively associated with the advantages just mentioned and these two aspects are preferably, but not necessarily, deployed together in application of the invention.According to one of these aspects of the invention there i provided a method of measuring the movement of an oscillating irregular surface, which comprises illuminating that surface with coherent light, arranging a photodetector for direct response to scattering and reflexions of said light from said surface, and employing from the output of said photodetector variations in the component thereof at the frequency of saidC frT. movement to represent such movement.This aspect of the invention derives from the finding that the photodetector has an amplitude-modulated component which corresponds to the surface movement. This finding arises when the oscillating surface is employed alone or in association with a similarly illuminated stationary surface, the photodetector being located in corresponding fields of both surfaces in the latter case, and also when the photodetector has a near or far field location relative to the surface or surfaces. While a detailed analysis of this phenomenon has yet to be finalised, it is at present considered that the relevant modulated output component results from mixing at the photodetector of the scattered and reflected fields as these are converted to electrical signal form. Certainly, in the case when two surfaces are involved, the presence of an interference effect has been confirmed by employing a piezoelectric crystal as one surface and vibrating the same at known frequency and amplitude, to find that the relevant output component successively increases and decreases in sinusoidal manner with linearly increasing amplitude of vibration.Also, another factor which is thought to be relevant to the above aspect of the invention in some circumstances is that the aforementioned random and fine-grained nature of speckle patterns involves a presumption that the originating surface is fully random in its irregularity, whereas in fact surfaces involved in many practical measurement situations will have a partially ordered structure by virtue of the way in which they are formed. This factor can heighten the optical relationships .which give rise to the modulated component of interest.The provision of apparatus adapted to carry out the above proposed method is also contemplated within this first aspect of the invention.A second aspect of the invention derives from the consideration that, in the case where two surfaces are involved, detection of the output component of interest can be effected when this component constitutes as little as 0.1% of the total photodetector output signal and that the provision of separate illuminating beams of similar intensities for the two surfaces is not necessary. Indeed, since the photodetector employed according to the invention in its first aspect converts the light patterns incident thereon from an electric field representation to an electric current representation, the contribution to the patterns from one of the surfaces can be as little as the order of 10 -6 times that from the other surface.Moreover, this consideration can be equally relevant to previous known forms of laser speckle interferometry, and particularly those which employ a discrete pattern transducer such as a television camera tube for the purposes of the recording step.Given this consideration the present invention, in its second aspect, provides a laser speckle interferometry method or apparatus in which one of the two irregular surfaces is illumina by stray coherent' light from a beam thereof directed predominant at the other of said surfaces.■_ Λ ty .' J In order that the above discussed aspects and other preferred features of the invention may be more fully understood, the same will now be described by way of example with reference to one embodiment thereof which is schematically illustrated by the accompanying drawing.The illustrated embodiment in fact represents apparatus employed in initial development of the invention in a study of the dynamics of the amphibian middle ear.The embodiment comprises a polarised He-Le laser source 10 of 2mV power output and wavelength, /. , of 632.8nm having its output beam directed at an object 11 which includes a vibratable surface 12 and an adjacent or surrounding, relatively fixed surface 13- In the initial development the surface 12 has been the tympanum of a frog, and the surface 13 the surrounding tissue covering the adjacent bone structure. The laser beam is directly predominantly at the surface 12 but has sufficient divergence for stray light to be incident on an area of the surface 13.Scatter and reflexion from both surfaces is monitored by a photodiode 14, this light field being applied to the photodiode by way of a fibre optic light guide 15 having its collecting end located in the near field of the surfaces 12 and 13.A beam splitter l6 is located near the output mirror of the source 10 and directs a proportion, suitably about 10 , of the output beam on to a second photodiode 1 . The photodiode outputs are applied, through respective current-to-voltage amplifiers 18 and 19, to a voltage divider 20 which divides the first photodiode output by the second. This operation reduces the effective amplitude fluctuations of the laser source by greater than 100-fold.The divider output is applied to a spectrum analyser 21 or some other means for detecting, among others, the output compone at the frequency of vibration of surface 12.In the use. of the illustrated embodiment the resonance characteristic of the frog's middle ear has been determined by application of successively different sound frequencies to vibra the eardrum and employing the output component at the correspond frequencies from the spectrum analyser as a measure of the amplitude of vibration.The present view of the basis for this procedure is that, when the surface 12 undergoes sinusoidal vibrations with amplitude a at angular frequency w , the current at the o a photodiode l4 is represented as electric fields at the photodiode respectively due to the surfac12 and 13, and 0 is an arbitrary phase between these fields due the vibrations. The last term of this equation can be expanded a series of Bessel functions and the component at the fundamenta frequency w can be determined by the analyser such that aI(w ) = t_ ]βe ! - I E I J„( 7fa ) ) sin w t . sin 0 a _ I S j J r I 1 o j^» a J where J is a Bessel function of the first kind and first order 1 with argument TTa l _Λ . The average value of sin 0 after full rectification by the analyser is 2/7} ,, and the function J has a maximum value at argument 1.841 radians and is zero at 3-84 B _ cfry. 5 radians. Thus, the output component of interest will be a maximum for vibration of the surface 12 with a peak-to-peak displacement of l85nm, and a minimum for peak-to-peak displacement of 386nm. This analysis is considered to be correct within 5% provided that the angle between the incident and scattered beams is less than 36 .As noted earlier the present theoretical consideration of the invention has been confirmed by the use of a piezoelectric crystal as the vibrating surface. In fact this has been done with the crystal and its surrounding structure in place of the surfaces 12 and 13 of the illustrated embodiment, and this has verified the above predictions. Moreover, from a series of measurements using the crystal, it has been concluded that the limit of resolution is about 0.2nm, and that the response is approximately a linear function of displacement up to l/lO of the wavelength of red light.While the invention has clearly been developed initially for the purposes of an academic study, it is not limited thereby. Indeed the introductory discussion above makes it equally clear that the invention offers advantage relative to existing laser speckle interferometry and the invention is obviously applicable in at least similar circumstances to those of the prior techniques.However, it is to be noted that further development' of the invention concerns application thereof for clinical audiometric purposes to monitor tympanic membrane movement and assess inner ear condition. The invention is well suited to this application in that it can provide a procedure which, contrary to existing procedures, requires little or no cooperation or comprehension on the part of the patient. Moreover, again in contrast to existing procedures such as tympanic acoustic impedance measurement, application of the present invention does not05 require sealing of the external ear canal or any other such operation which applies an abnormal constraint to the middle e in other words the invention can be employed to measure wholly unconstrained tympanum displacement in response to applied sou Naturally in the application of the invention under10 discussion, some means will be provided for applying sound into the ear. This can take any suitable form, but in one preferre form involves a sound source operable at successively changing frequency by a swept oscillator or equivalent device. In this event the output detector should be of locked variable frequen15 form, such as a spectrum analyser/tracking generator combinatio or a sweep generator/dynamic lock-in detector system. In an alternative arrangement the sound stimulation for the ear can b applied as a short impulse with the detector effecting Fourier analysis. This alternative may be advantageous in involving a20 shorter exposure of the ear to the laser source, and also in providing output signals indicating the damping properties of the middle ear in addition to resonant properties.The necessary apparatus interfacing with the patient may conveniently comprise an earphone-like structure housing a25 miniature sound source of the kind such as used in hearing aids or a spark gap or other form of sonic impulse generator. The fibre optic guide can extend through this structure between the external ear canal and photodiode, and a further such guide can be employed to pass the laser beam into the canal, or the structure can be apertured for this purpose.The outgoing light guide can comprise a single fibre or a multiple fibre system. In the latter case the fibres or sub-sets thereof can be directed to respectively different photodiodes to enhance the detected signal or to allow analysis to be effected in respect of additional output signal components such as those at harmonics of the frequencies of interest. Similarly, any in-going light guide can comprise a single or multiple fibre system, and in the latter case the proximal ends of the fibres can be employed to direct light on to respectively different areas of the vibrated and stationary surfaces. This may improve the output signal by the effective application of separate beams on to the two surfaces, and/or it may allow differential assessment of the condition of the tympanum by effective application of a plurality of beams on to respectively different areas thereof.1 jRtA £OMPI ^SNATIO | C AIMS1. A method of measuring the movement of an oscillating •irregular surface, which comprises illuminating that surface with coherent light, and detecting variations caused by said movement in a speckle pattern produced by scattering and reflexions of said light from said surface, characterised by arranging a photodetector for direct response to said pattern, and detecting from the output of said photodetector variations thereof at the frequency of said movement to represent such movement. 2. A method according to Claim 1 which comprises illuminating another, stationary, irregular surface with coherent light, and detecting variations in a speckle interference pattern produced by scattering and reflexions from both said surfaces, character by arranging said photodetector for direct response to said intereference pattern.__ . A method according to Claim 2 characterised in that said surfaces are closely adjacent, and in that said other surface i illuminated by stray coherent light from a beam thereof directe predominantly at the first-mentioned surface. 4. A method according to Claim 1, 2 or 3 characterised in that the first-mentioned surface is a tympanum oscillated by a predetermined sound wave applied thereto.5» A method according to Claim 4 characterised in that said sound wave is of swept frequency form and said variations are detected in a locked-frequency manner. 6. A method according to Claim 4 characterised in that said sound wave is of impulse form and said variations are detected by Fourier analysis. 7- A method of measuring the movement of an oscillating surface, which comprises illuminating that surface and another, stationary, irregular surface with coherent light, and detecting variations in a speckle interference pattern produced by scattering and reflexions from both said surfaces, characterised in that said other surface is illuminated by stray coherent light from a beam thereof directed predominantly at the first- mentioned surface.8. Apparatus for measuring the movement of an oscillating- irregular surface, comprising a coherent light source for illuminating that source, and means for detecting variations caused by said movement in a speckle pattern produced by scattering and reflexions of said light from said surface, characterised in that said detecting means includes a photodetector arranged for direct response to said pattern, and a detector respdnsive to amplitude variations in the output of said photodetector at the frequency of said movement.9. Apparatus according to Claim 8, characterised by another photodetector for direct response to light from said source, and a signal divider responsive to said photodetectors to supply the input for said detector. 10. Apparatus according to Claim 8' or 9 characterised by a sound generator for applying a predetermined sound wave to oscillate said surface. 11. Apparatus according to Claim 10 characterised in that said sound generator is of swept frequency form, and in that said detector is operably frequency-locked with said generator.12. Apparatus according to Claim 10 characterised in that said sound generator is of impulse form, and in that said detector effects Fourier analysis.13. Apparatus according to Claim 10, 11 or 12 characterised by an earphone-form device housing at least part of said sound generator to apply the output thereof to a tympanum. l4. Apparatus according to Claim 13 characterised in that said device has at least one fibre optic guide passing therethrough to convey said illuminating light to said surface and/or said pattern to the first-mentioned photodetector. | ANSON M; CHUNG S; NAT RES DEV; PETTIGREW A; NAT RES DEV CORP | ANSON M; CHUNG S; PETTIGREW A |
WO-1979000855-A1 | 1,979,000,855 | WO | A1 | EN | 19,791,101 | 1,979 | 20,090,507 | new | E21B43 | G01B7, G01N27 | E21B47, G01D9, G01N27, G01V3 | E21B 47/00C, E21B 47/09B, G01D 9/42, G01N 27/72, G01V 3/10B2 | METAL TYPE DETECTOR | A combination of magnetics and a special geometric environment is employed to distinguish whether an instrument is positioned within a pipe formed of magnetizable or non-magnetizable material, and is the bases, in part, for a method and an apparatus used in controlling picture taking at the bottom of a well bore. A coil (20) is energized repetitively in a circuit (98, 118, 20) in which the voltage across the coil (20), or the current that flows through the coil (20), can be measured. Whether the coil (20) is in a magnetic (12) or non-magnetic (14) environment is determined by the magnitude of the change in coil voltage or current. | METAL TYPE DETECTORThis invention relates to methods and means for determining whether a metallic enclosure, in particular, a drill pipe, is made of magnetic or non-magnetic material, and it relates to an instrument having that capability for controlling illumination of the light source in the photo- graphing of compasses at the bottom of drilled wells.OMFI BACKGROUND OF THE INVENTIONWhile not limited to that application, the in¬ vention is particularly useful in connection with the tak of photographic pictures of a compass, or inclinometer, o both, at the bottom of a well bore. Well drillers can control the direction of deep wells by control of the drilling tools. But control is accomplished in terms of adjustment to change from current direction as drilling proceeds. That means that the driller must know the well current direction from time to time. Current direction i determined by lowering a compass inclinometer to the bott of the well and then photographing the compass assembly to record its direction in azimuth and inclination. The task of photographing a compass at the bottom of a well i both complicated and expensive.The compass needle is acted on by the earth's magnetic field. To permit that, the compass must be dis¬ posed in a non-magnetic section of pipe at the time that the photograph is taken. Current practice is to include a short length of non-magnetic pipe at or near the lower end of the drill pipe. That length of pipe is ordinarily made of Monel and it is called a collar. The compass must be disposed in that section when it is photographed. Care must be taken to ensure that the compass assembly is not in motion at the time that the photograph is taken. Current practice is to include a detector which detects absence of motion and a means for precluding exposure of the film for some selected time interval measured from th last action which could cause movement of the compass needle.To prevent premature exposure, it has been necessary to ensure that instrument motion does not stop until the instrument has reached the position at which the photograph is to be taken. To overcome that require- ment, a conventional clock has been used so that photo¬ graph taking occurs at some fixed time after the clock is started at the well head. That solution is subject to failure if, for any reason, the time required to lower the instrument is other than the predicted time.This invention relates to the problem of en¬ suring that the compass is in the non-magnetic collar and to the problem of postponing picture taking until the compass needle has settled down before the film is ex- posed. To pull the drilling tools from a deep well is very costly. It is important to be able to determine reliably and with a high degree of certainty whether the compass is, or is not, in the non-magnetic section of the drill pipe.Another object is to provide an improved well compass position detector and compass picture taking controller.These and other objects and advantages of the invention are realized in part by the provision of a coil which is energizable to create a magnetic field and of a means for holding the coil within an enclosure such that the field of the coil will be substantially confined by the enclosure, in the event that the enclosure is made of magnetizable material, and which will induce substantial circulating currents, enough to present a heavy load per¬ mitting current flow in the coil in excess of the current that would flow if the coil was located in free space, in the event that the enclosure is made of non-magnetizable but electrically conductive material.OMPI fh WΪPO That kind of a coil is used in conjunction with a means for measuring the voltage across, or the current through, the coil when energized. The voltage or current is indicative of whether the coil is disposed in a magneti or non-magnetic pipe or other enclosure, and it is used to develop an indicating signal which indicates the nature of the enclosure. In preferred form, the coil is energized through a transistor whose control electrode is subjected to a periodically varying voltage wave form.It is a feature to change from analog to digital measurement by switching if the voltage or current ex- cursion exceeds some value that indicates that the coil is in one kind of enclosure and not the other. It is anot feature to house the coil in a non-magnetic casing in whic case the instrument'can detect when it is in a magnetic environment and in a non-magnetic environment whether elec trically conductive or not.It is a further feature to use the indicating signal to control initiation of interrelated timing circuiThese and other features and advantages of the invention will become clear upon a reading of the specific tion which follows. THE DRAWINGSe drawings:Figure 1 is a schematic representation of an instrument in which the invention is embodied in a section of drill pipe shown in cross-section;Figure 2 is a diagram illustrating part of the operation of the invention when detecting pipe of magnetic material;Figure 3 is a diagram illustrating part of the operation of the invention when detecting pipe of non-magnetic but metallic material; andFigure 4 is a circuit diagram of a preferred embodiment of the invention. DESCRIPTION OF THE PREFERRED EMBODIMENT OF THE INVENTIONIn Figure 1, the numeral 10 designates a sec¬ tion of drill pipe including a fragment of the lower end of a magnetic steel pipe 12 and a fragment of the upper end of a pipe 14 of non-magnetic metal. The two are interconnected at threaded region 16. Disposed within th pipe is an instrument 18 whose purpose is to photograph the position of a compass assembly on a film.Sometimes the compass serves as an inclinometer as well as a compass, and in some cases a separate invert plumbob is added to indicate inclination. Those elements form no part of the invention, nor does the film which is placed on one side of the compass and inclinometer com¬ bination, or the lamp that is placed on the other side. The invention is concerned with illumination of the lamp and with illuminating the lamp only when the compass is in the non-magnetic, metallic portion of the pipe, after sufficient time has elapsed to allow the compass needle to become steady.To perform those several functions, the instru¬ ment of the preferred embodiment includes a metal type detector, timers, a power source in the form of batteries, lamp, lamp circuit, a compass and inclinometer,:; and a film. In the preferred form, these elements are housed i a non-magnetic case which may be formed of electrically conductive material such, for example, as Monel metal.. The diagram of Figure 4 includes the batteries, metal type detector, timers, and terminals for connection to the lamp circuit. The metal type detector includes a sensing coil 20 and its operation will be explained in connection with Figures 2 and 3.. In preferred form, the sensing coil 20 is wound about a straight elongated form, preferably about an elongated ferrite core. It is housed in the instru¬ ment case 18 so that the axis of the coil is parallel to, and preferably coincident with, the axis of case 18. The case is arranged so that its axis can be expected to be substantially parallel with the axis of the drill pipe. The requirement, in the preferred embodiment, is that the axis of the coil be more parallel than transverse to the axis of the drill pipe. The reason for that arrangement is explained in connection with Figure 3.In Figure 3, the coil and its core 22 are dis¬ posed within a Monel pipe 23. When current flows through the coil a magnetic field is established around the coil. That field is represented, in accordance with con¬ vention, by closed loops 25, 26, 27 and 28 shown as dashed lines which extend through the core, and than out at one end and around and back into the core at the opposite end. No loop crosses any other according to convention. Since the permeability of Monel is near unity, the flux lines pass through the pipe walls in a pattern similar to what would be expected in air. As the flux field builds, the flux lines cut the pipe wall and that movement of magnetism interacts with the free electrons in the elec¬ trically conductive pipe to cause a motion of those elec¬ trons according to the right hand rule. The electrons flow around the circumference of the pipe so that the pipe acts as a single shorted turn secondary winding of large cross sectional area. The resistance of the pipe is low so that it presents a heavy load to the primary winding 22 which draws a heavy current. Current flow is represented in Figure 3 by the flow away and flow toward symbols 30 and 32, respectively.' OMPI Returning to Figure 4, the coil 20 is in series with the emitter-collector circuit of a transistor 118 and a load resistor 98. The transistor is cut off during part of each cycle so the result is a large current chang and a large voltage change at the collector of transistor 118 when the coil 20 is in Monel pipe.If the coil 20 was oriented so that its axis was normal to the pipe axis, the flux direction would be changed by 90 degrees and so would the direction of the induced current. The current would flow in the longitu¬ dinal direction of the pipe and the pipe would act as a secondary winding in much lesser degree determined pri¬ marily by dissymetry in the magnetic field.Sensitivity is also effected by conductivity of the protective case 18. That case must be made of non- magnetic material so that the magnetic field will not be confined to the case but can reach the pipe. Sensitivity of the instrument is reduced in the sense that a portion of the current change in the coil results from current flow in the case. However, it will be seen that that effect does not lessen ability of the instrument to dis¬ tinguish steel pipe from a non-magnetic pipe.Magnetic lines of flux follow the path of least reluctance, and when the coil 20 is disposed within a pipe 34 of magnetic material, the flux lines will extend from one end of core 22 through the non-magnetic case of instrument 18 into and along the magnetic pipe and then back through the case of instrument 18 to core 22. There will be less cutting of the pipe by flux lines. A current will be induced in the pipe wall as it was in theMonel pipe of Figure 3, but higher resistance, eddy curre and other losses and phase stifling effects serve to mini- mize that current. Further, the greater magnetic effi¬ ciency in the magnetic circuit results in a stronger field, collapse of more flux when transistor 118 cuts off cur¬ rent, and it creates a greater counter-electromotive force in coil 20. The result is a lesser current swing. That is true notwithstanding the circulating current around the case of instrument 18 and the load it represents.The end result is that presence of coil 20 within the steel pipe results in a magnetic action which produces a counter-electromotive force in the coil and an opposition to current change which substantially nullifies the effect of the instrument case of a shorted tirn. There is no such nullification when the instrument is housed in a non-magnetic pipe so current change is large whether it be the result of the instrument case or the pipe, or both, acting as a shorted turn.There is another effect to be accounted for. Lenz's Law describes that counter-electromotive force has a magnitude that depends upon the rate of change of magnetic flux. At very low frequencies, the counter-electromotive force opposing flow in coil 20 is very low notwithstanding that the coil is disposed within the steel portion of the pipe. Thus, at very low frequencies, the signal output at the collector of transistor 118 will be relatively high when the coil is housed in steel. That signal strength diminishes rapidly when the frequency is increased. An opposite effect occurs at low frequencies when the coil 20 is disposed in the Monel portion of the pipe. At low frequencies the flux change is slow and the magnitude of the circulating current in the shorted turn pipe is small. That means that the load is small and the self-inductance of coil 20 is ade¬ quate to limit current flow. Accordingly, the voltage excursion at the collector of transistor 118 is relatively small. However, the signal magnitude increases rapidly with frequency. In an actual circumstance, the non- magnetic collar has an inside diameter of about three inches and a wall thickness greater than one inch. The instrument case has an outside diameter of about two inc and a wall thickness on the order of one-quarter inch. The lower frequency limit for operation of the instrument will be about 300 cycles. At frequencies below that it becomes impossible to distinguish Monel from steel, or t results are unreliable. As frequency is increased above 300 cycles per second, the differential in magnitude between the signal in steel and the signal in Monel is increased until some optimum frequency is reached. For the dimensions given, that frequency will fall in the ran of 400 to 800 cycles per second. Above that, the current variation in coil 20 is diminished when the coil is dis¬ posed in Monel. The effect of self-inductance in the coil overtakes the effect of the heavy loading so that at about 800 cycles per second, for the values given, the magnitude of the signal is reduced to the point where detection becomes difficult and unreliable. Accordingly, there is a frequency window in which the metal type detec tor must be operated. That window can be shifted by changing the characteristics of the coil 20, but the preferred embodiment employs the component values listed below, and a frequency of operation between 400 and 600 cycles per second. In the particular case shown, the frequency is 500 cycles per second.At the upper portion of Figure 4, line 106 is connected to positive terminal 104 and power Line 108 is connected to ground. The circuit includes an oscillator 110 whose frequency is relatively low, and it need com¬ prise no more than a series of three inverters and some feedback resistors and a capacitor. Its output is connec ted to the base of NPN transistor 112. Its collector is connected to the positive line 106. Its emitter is con- nected to ground through the series combination of a resistor 114 and an electrolytic capacitor 116. The junc¬ tion of the resistor and the capacitor is connected to the base of a NPN transistor 118 whose collector is con¬ nected to the positive line 106 through resistor 98, men- tioned earlier. The emitter of the transistor is con¬ nected through the sensing coil 20 to ground line 108. The output of transistor 118 is taken from its collector and applied to the base of an NPN transistor 120 whose collector is connected to the positive line through a load resistor 122 and to the base of an PNP transistor 124. The emitter of transistor 120 is connected to ground through resistor 126, and it is connected to the emitter of a transistor 128 whose collector is connected to the positive line through load resistor 130. The base of transistor 128 is connected to the junction between two resistors, 132 and 134, which are connected between the positive line and the negative line in series, in that order. The emitter of transistor 124 is connected to the positive line 106 and its collector is connected through a diode 136 to a line 138 and a terminal 140. A capacitor 142 and a resistor 144 are connected in parallel between line 138 and the negative line 108. Another output line 146 is connected from line 138 to the D input terminal of a. D-type flip-flop 148.Except for the D-type flip-flop, the circuit thus far described is the metal type detector. Its func¬ tion is to apply a positive signal to the D terminal of the flip-flop when coil 20 is located within the Monel section of the pipe and to apply a negative signal to the D input of flip-flop 148 when the sensing coil 20 is located within a steel portion of the drill pipe. To do' O PI that, the output of oscillator 110 is applied to the base terminal of amplifier 112. Current flowing through the collector-emitter circuit of the transistor flows through resistor 114 to charge capacitor 116. The capa¬ citor discharges through the base-emitter circuit of the following transistor 118. The result is the application to the base of transistor 118 of the voltage that appears across capacitor 116. That input voltage causes a corres ponding flow of current in the emitter-collector circuit of transistor 118, except as that current flow, and count electromotive force, develops an opposing voltage across the sensing coil 20 in the manner previously described. The output signal of that transistor is applied to the ba of transistor 120 whose bias is controlled by current flo through transistor 128. The base of the latter is biased to a fixed value by the voltage divider formed by the com bination of resistors 132 and 134. Current flowing throu the transistor 128 flows through re'sistor 126 in the emit circuit of transistor 120. Only when the base voltage of the transistor exceeds a value determined by the volta across resistor 126 does current flow in transistor 120. The output of that transistor is taken from its collector and applied to the base of switching transistor 124 which, when turned on, permits current flow through the diode 13 into capacitor 142 so that the output line 138 becomes positive. The capacitor is discharged through resistor 144. The effect is that line 146 will remain positive while the coil 20 is disposed within the Monel collar, but the line will return to its negative state when the coil 20 is disposed within the steel pipe. In the latter case, the voltage at the base of transistor 120 is in¬ sufficient, in view of the voltage across resistor 126, to permit current flow through transistor 120 for the tur ing on of transistor 124. Accordingly, the charge on cap citor 142 will leak off through resistor 144 and line 146 will be returned to a low state and will remain low.*g3^T The edge clocked flip-flop 148 initiates a counting and control cycle when a high signal is applied to its D input by line 146 from the output line 138.Clock signals for the digital portion of the circuit are generated in an oscillator 150 whose output signals are applied by a line 152 to the clock pins 3 and 13 of JK flip-flops 154 and 156, respectively. Clock signals are also applied to the clock pin 3 of flip-flop 148 and to pin 2 of each of three counters, 158, 160 and 162. The counters are cleared and preset when a low signal is ap¬ plied to their number 1 pins from the Q-bar output of flip-flop 156. Counting begins when a high signal is applied to the enable pin, number 9, of each of the counters from the Q output of flip-flop 148.The circuit is arranged so that two counting functions are performed. Counters 158 and 162 are connected together as one counter called the exposure time counter, and counters 158 and 160 are connected together as a second counter called the settling time counter. The first of those counters is used to control the time during which the camera light source, the lamp, is illuminated. The second of the counters introduces a time delay between the time when coil 20 has sensed that it is disposed within the Monel section of pipe and the time when energization of the lamp excitation circuit is permitted. Output of the exposure time counter is taken from pin 15 of counter 162, and the output of the settling time counter is taken at pin 15 of the counter chip 160. Pin 15 of counter chip 162 is connected to the K input of flip-flop 154 and to the J input of flip-flop 156. The output of counter chip 160 at pin 15 is applied to the J input of counter 154.Turning to the output end of the circuit, the lamp excitation circuit is connected to terminals X, YtJREΛOMPI IPO mty *. !. Ul Ul to to P4 P4Ui 0 Ui O Ul 0 UiP-at 0. When that counter reaches maximum count, a high appears at pin 15 and that is applied to the count enable pins 10 of both of the counter chips 160 and 162. Flip- flop 154 has been reset. A high appears at the Q-bar terminal and that is applied to pin 7 of counter 160 which is thereby enabled. A low is applied to pin 7 of counter 162 which is connected to the Q output of flip-flop 154. That means that the counter 162 is inhibited. When counter 160 reaches maximum count, a high signal appears at its pin 15 and that signal is applied to the J input of flip- flop 154. The K input of that flip-flop, and the J input of flip-flop 156 are low because they are connected to pin 15 of counter 162 which is inhibited. When counter160 reaches its maximum count, a positive signal is applied to pin J of flip-flop 154 and that flip-flop changes state. A high appears at its Q output, thereby turning on the transistor 170 in the lamp excitation circuit and also enabling the counter 162. When counter 162 reaches full count, a positive signal from pin 15 of counter chip 162 is applied to the K input of flip-flop 154, and the J side of flip-flop 156. Flip-flop 154 resets and fl-ip-flop 156 sets. Accordingly, the Q output of flip-flop 154 goes low to turn off the transistor 170 in the lamp exci¬ tation circuit. The Q-bar output goes high, terminating the signal to counter 160. The K input of the flip-flop 156 is at ground potential, so the appearance of a high at the end of the interval count at terminal J of flip- flop 156 changes its state so that a low appears at the Q-bar output. That low is applied to clear all of the counters.The circuit of Figure 4 is arranged so that a photograph will be taken automatically as soon as the compass photographing instrument is positioned so .that coil 20 is within the Monel collar, and a time has elapsedOMPI WIPO sufficient to ensure that the compass assembly has stopped fluctuating.In a representative circuit, the components may have the following values:Transistors 112, 120, 118, 170 are type 2N3703; Transistor 124 is type 2N3703;D-type flip-flop 148 may be type MC 14013B; Three counter chips are type MC 14163B; Flip-flop 154 is type MC 14027B; Flip-flop 156 is type MC 14584B; Capacitor 176 has a value of .01 mf;Capacitor 142 has a value of 1 mf; Capacitor 116 has a value of 2 mf; Resistors 122, 130 and 144 are 100K ohms; Resistors 126 and 134 are 10K ohms; Resistor 114 has the value 300 ohms;Resistor 98 has the value 2700 ohms.The circuit uses six inverters packaged in chip MC 14069B. Three of those are connected in series to for oscillator 150. In each case, the first inverter in the series is connected in parallel with the series combi nation of a 1 megohm and a 2 megohm resistor. The juncti between the two resistors is connected to the junction between the- second and third inverters of the series through a capacitor which, in the case of oscillator 107, has the value .001 mf. The value of the capacitor in oscillator 150 is much larger. Oscillator 150 serves as the clock for the settling time counter and for the expos time counter. The length of the settling time and exposu will depend upon the characteristics of the film and of the damping characteristics of the compass. Because of that, the value of the clock frequency controlling capa- citor 134 is not specified and the counter-connections (number of counts) are not shown in the diagram. To select them in a given case requires no more than very ordinary skill. Settling time might be anything up to about 1.5 minutes, and the exposure time anything up to forty-five seconds, depending upon which ones are selected of the films and lamps and compasses that are currently in use.The coil 20 has an inductance of about 233 micro¬ henries. The core material of the coil is magnetic but is non-conductive. The frequency of oscillator 110 is at or near 500 Hz.In some applications of the invention, when used as a metal detector, or in conjunction with other instru¬ ments, it may be desirable to work with analog signals, and, for that purpose, the preferred embodiment includes a terminal 202 at the collector of transistor 118. That terminal could be positioned at any point where the voltage or current variation in coil 20 can be measured, but the collector position is now preferred.While a preferred embodiment of the invention has been described, other embodiments of the invention are possible. A list of variations would include changes in coil configuration, changes in the type of non-magnetic material in which the coil was housed, and changes in housing configuration and, of course, other changes are possible within the invention.OMPI | What is claimed is:1. The method of determining whether a coil disposed within a pipe, part of whose length is magnetic and part of whose length is non-magnetic, is in the mag¬ netic or non-magnetic part of the pipe, which method comprises the steps of: a) energizing said coil from a source of electrical energy whose voltage varies periodically such that a magnetic field is alternately created and collapsed around said coil and such that said field extends into said pipe; and b) measuring the magnitude of the change in current flow through said coil.2. The method defined in Claim 1 which includes the further step of orienting said coil such that the direction of the magnetic field at the center of the coil is closer to parallel than it is normal to the axis of the pipe./j, 3. The method defined in Claim 1 in which the frequency of the variation in source voltage is be- tween 300 and 800 cycles per second.4. The method defined in Claim 3 in which the frequency of the variation in source voltage is be¬ tween 400 and 600 Hz.OMPI h. IPO 5. In an instrument whose purpose is to determine whether a given position within a pipe is within a magnetic or non-magnetic section of the pipe, in combination: a) a coil energizable to create a magnetic field; ■ b) means for holding the coil oriented with its magnetic axis pointing in a direction having a component parallel with the axis of the pipe; c) means for energizing said coil suffi¬ ciently to create a magnetic field on which the pipe can exercise an affect; and d) means for measuring the magnitude of the change in at least one of the current through said coil and the voltage across said coil.6. The invention- defined in Claim 5 in which said means for energizing said coil comprises means for repetitively altering the magnitude of the current that is permitted to flow through said coil. 7. The invention defined in Claim 5 in which said means for energizing said coil comprises an active device having a current flow path in series with said coil and a control element responsive to variation in the magnitude of voltage applied to it to control the magnitude of current made available to flow through said coil.8. The invention defined in Claim 5 in which said means for energizing said coil comprises a means for applying a sinusoidal wave form of voltage to said con¬ trol element.OMPI 9. The invention defined in Claim 5 in which said means for measuring the change in current through, or voltage across, said coil comprises means for measurin the voltage at a point in series circuit with said coil and which further comprises means for providing an indi¬ cating signal indicative of whether the voltage variation across said coil is greater than a selected voltage vari- ation.10. The invention defined in Claim 9 which further comprises means for providing an output signal for a preselected period beginning at the end of a given period following provision of an indicating signal indi- eating that the voltage variation across said coil exceed some voltage variation.___ hT 11. The invention defined in Claim 5 in which said coil comprises coils of electrical conductor wound upon a magnetizable electrical insulator.12. The invention defined in Claim 6 in which said means for energizing said coil comprises means for connecting said coil to a source of electric current and altering the magnitude of current permitted to flow through said coil repetitively at a frequency between 300 and 800 Hz. 13. The invention defined in Claim 5 in which said means for energizing said coil comprises, in series with the coil, a resistor and the primary current path of a transistor device and which further comprises a mean for applying a periodically varying potential to the control element of said transistor device.14. The invention defined in Claim 13 in which said coil comprises a coil of wire wound upon a straight core of magnetizable., non-electrically conductive materia and in which said means for holding the coil comprises an enclosure of non-magnetic material and means for holding the coil with its magnetic axis more parallel than normal to the axis of a pipe in which it is disposed when so disposed. 15. The invention defined in Claim 14 in which said means for measuring the magnitude of change in cur- rent flow through, or voltage across, said coil comprises means for actuating a switch in response to change greater than a selected magnitude to provide an indicating signal indicating that the change was greater than said selected magnitude.ΓREOMPI^ n 16. The invention defined in Claim 15 which further comprises: a) means in the form of a switching cir cuit for controlling application of energy to a lamp; b) said switching circuit comprising a first flip-flop, two counters, and a second flip-flop; c) said first flip-flop being responsiv to said indicating signal to initiate operation of one of said counters; d) said one of said counters being effe tive, at a given count, to alter the state of said secon flip-flop to a state in which application of energy to t lamp is permitted and also to initiate operation of the other of said counters; e) said other of said counters being effective, at a given count, to alter the state of said second flip-flop to a state in which application of energy to the lamp is .precluded.J fb 17. The method of controlling photograph taking at a selected position in a well bore with photographic equipment which comprises the steps of: a) lowering the photographic equipment to said position; b) initiating a clock timer only when said photographic equipment is disposed at said position; and c) operating said photographic equipment at the end of a predetermined interval following initia¬ tion of said clock timer.18. The invention defined in Claim 17 which comprises the further step of detecting when said photo¬ graphic equipment is disposed at said position by detecting the character of material at said position.• ' OMPI fo IPO | PYATT L; THOMPSON R | PYATT L; THOMPSON R |
WO-1979000857-A1 | 1,979,000,857 | WO | A1 | XX | 19,791,101 | 1,979 | 20,090,507 | new | A24B3 | A23B4, A23B3, A21D13, A23L1 | A24B3 | A24B 3/18B | METHOD AND APPARATUS FOR EXPANDING TOBACCO | A tobacco expansion medium which does not cause environmental pollution or is costly. The invention disclosed is a method and apparatus for expanding particles of cured tobacco (16) by means of liquid and gaseous carbon dioxide which is sprayed (18, 20) into a mass of the tobacco in a closed pressure vessel (12, 14). The thus treated tobacco is removed from the vessel and heated (36) such that rapid release of the carbon dioxide effects expansion of the tobacco. | DescriptionMethod And Apparatus For Expanding TobaccoTechnical FieldThe present invention relates to a method and apparatus for expanding tobacco by spray impregnating cut tobacco par¬ ticles in a pressure vessel with liquid and gaseous carbon dioxide following which the impregnated tobacco particles are heated to effect rapid release of the carbon dioxide with corresponding expansion of the particles.Background ArtThe tobacco art has long recognized the need to effect the greatest possible degree of expansion of tobacco while maintaining desirable handling and smoking characteristics. Correspondingly, numerous attempts have been made in the art to effect such expansion of tobacco, frequently by treatment of the tobacco with an agent which expands greatly during evaporation or after a decrease in pressure.One attempt in the prior art to expand tobacco is dis¬ closed in United States Patent No. 1,789,435 wherein a method is described for expanding the volume of tobacco in order to make up the loss of weight caused in curing the tobacco leaf. The tobacco is contacted with a gas such as air, carbon dioxide, or steam under pressure and, upon release of the pressure, the tobacco tends to expand limitedly between 5% and 15% by volume.Prior art disclosures are also available which teach that tobacco may be expanded by addition of water to the tobacco which causes the tobacco to swell following which the contained moisture is evaporated to set the expansion.Another attempt to expand tobacco has been by use of carbohydrates as a means to improve puffing of tobacco stems. in this process, the tobacco stems are soaked in an aqueous solution of carbohydrate following which they are heated to set the tobacco expansion.Volatile organic liquids have also been disclosed in the prior art as means to effect expansion of tobacco.Methods have also been proposed in the prior art to effect tobacco expansion by use of ammonia and carbon dioxide gases. Carbon dioxide has also been used in the liquid state as a means of expanding tobacco and other organic substances. Typically, such processes require immersing the organic sub¬ stance or tobacco in a pool of liquid carbon dioxide wherein tobacco particles are steeped in the liquid carbon dioxide following which the tobacco particles are heated, preferably using super-heated steam to effect expansion. These methods, however, invite various disadvantages by requiring large quantities of liquid carbon dioxide relative to the amount of carbon dioxide which is impregnated within the tobacco parti¬ cles. Furthermore, components of the tobacco such as flavoring materials may be extracted by the use of excess liquid carbon dioxide.Although numerous attempts have been made in the prior art to expand tobacco by various means, these attempts have achieved limited success by either requiring expanding agents which have been alleged to cause environmental pollution or are otherwise costly or cumbersome to operate. It has now been found that, by practice of the present invention, tobac¬ co may be expanded by means of liquid carbon dioxide in a simple, efficient and highly economical manner.Disclosure of InventionGenerally stated, the present method for expanding tobacco requires spraying tobacco particles with carbon diox¬ ide in a pressure vessel and thereby effecting impregnation of the tobacco with carbon dioxide following which the impreg nated tobacco is removed from the de-pressurized vessel and heated to effect rapid release of the carbon dioxide and cor¬ responding expansion of the tobacco particles. 1The apparatus of the present invention includes a ver¬ tically disposed vessel having inlet and outlet pressure containing valves and a liquid carbon dioxide conduit having a multiple number of outlets along the body portion which causes a liquid spray of carbon dioxide to pass into a mass of tobacco particles contained within the vessel. The liquid carbon dioxide conduit is connected to appropriate valve and pressure regulators to an external source of liquid carbon dioxide.Practice of the present invention will become more readily apparent from the following detailed description taken in conjunction with the drawings.Brief Description of Drawings15 Figure 1 diagrammatically illustrates the method and apparatus of the present invention wherein the pressure vessel is depicted in half-section; Figure 2 is a cross- sectional view of the pressure vessel of Figure 1 taken along lines 2-2; and, Figure 3 is a chart reflecting pressure ^°versus temperature for the results of Example 15.Best Mode for Carrying Out the InventionFigure 1 illustrates pressure reaction vessel 10 slightly tapered outwardly from an upper vessel location 12 to a lower vessel location 14, the taper serving as a convenient means for removing tobacco 16 following processing. It is found that the taper allows easy removal of the processed tobacco. The tobacco is sprayed by liquid and gaseous carbon dioxide passing from a convenient source (not shown) through tubing 3018 by way of control valve 20 to a location within the pres¬ sure vessel where the tubing joins elongated conduit 22 hav¬ ing a large number of exit outlets 24 for spraying liquid carbon dioxide throughout the mass of contained tobacco.A particularly suitable form of conduit for introducing35 the liquid carbon dioxide into the mass of tobacco consists ofOMPI. A ^- P porous tubing made of sintered stainless steel which may be obtained from Mott Metallurgical Corporation or Pall Trinity Micro Corporation. Tubing with a variety of pore diameters is available, but one having approximately 20 microns pore diameter produces a fine fog or mist of carbon dioxide that allows unusually uniform impregnation of the tobacco with carbon dioxide. While it is preferable that the sparge tube extend into the mass of tobacco as illustrated schematically in Figure 1, good results may also be realized when this spray unit is situated above the tobacco bed.Although one conduit member 22 is illustrated, it is recognized that a plurality of such spray units may be in¬ cluded depending upon the diameter of the vessel as well as the degree of saturation desired when spraying the liquid carbon dioxide throughout the contained mass of tobacco.In operation, lower ball valve 26 is initially in the ■closed position illustrated and tobacco is introduced into the pressure vessel 10 by means of ball valve 28 when in phantom position illustrated by lines 30. After the tobacco has been introduced, ball valve 28 is returned to the closed position illustrated as shown in Figure 1. The amount of tobacco introduced into the pressure vessel 10 may vary as desired. It is recognized that a pre-weighed amount is desirably introduced so that the proportion of liquid carbon dioxide sprayed onto the tobacco can be controlled.After ball valve 28 is closed, the vessel is pressurize either by introducing liquid and gaseous carbon dioxide into the vessel or by pre-pressurizing using an inert gas as the pressurizing medium. The liquid and gaseous carbon dioxide is introduced by spraying liquid carbon dioxide into the mas of tobacco within pressure vessel 10. Following the sprayin sequence, the pressure within the vessel is held for a perio and then reduced to a suitable level by means of valve 17 in pressure release vent 19 at which time the vessel may be opened for release of the tobacco by lower ball valve 26 whe BUR£4OMPI /? ATlO in phantom position 32. The removed tobacco having carbon dioxide impregnated therein is passed by line 34 to a heater 36 from which the expanded tobacco is received by line 38.Figure 2 further illustrates the sequence of operation of Figure 1 taken along section line 2-2 depicting the spray¬ ing of liquid carbon dioxide by lines 40 into the mass of tobacco 16 within pressurized vessel 10,The internal pressure and temperature.of the vessel used to contain the tobacco during spray impregnation of liquid carbon dioxide may vary. The pressure, for example, may vary from as low as about 250 psig. to as high as about 600 psig. Preferred pressures range from about 325 psig. to about 460 psig.The internal temperature of the vessel will vary from about -8°F. to about 56°F. and preferably about 7°F. to about 28°F.After the liquid carbon dioxide impregnated tobacco is removed from the vessel, it is transferred to a dryer to effect rapid release of the carbon dioxide. In order to avoid premature release of the carbon dioxide, it is neces¬ sary to limit the transfer time between removal of the to- *• bacco from the vessel and the heat processing step. A transfer time within about 30 minutes has been found suffi¬ cient and desirably less than about one minute is preferred. The desired temperature of the heating fluid within the dryer is dependent upon the residence time for the tobacco. Using a gas-fired dryer with a residence time of up to two minutes, heating fluid temperatures of about 200°F. to 450°F. have been found to be sufficient.Typical moisture contents of the tobacco vary between about 10% and about 26% by weight. Also, advantage may be realized by including a volatile organic liquid solvent such as methanol, ethanol, methyl acetate, ethyl acetate, or the like in the tobacco. These volatile organic liquid solvents^ not only aid in causing larger amounts of liquid and gaseous carbon dioxide to be impregnated into the tobacco but also lower the freezing point of the fluids within the tobacco tissue permitting impregnation at lower temperatures and pressures without the tobacco freezing. They also impart 5 better handling characteristics to the final product.The amounts of volatile organic liquid solvent which may be used vary from 0 to 23% or more by weight of the tobacco being processed.After the liquid and gaseous carbon dioxide has been sprayed into the mass of tobacco, it has been found that a holding period of time prior to release of pressure from the vessel permits greater absorption of the carbon dioxide and correspondingly larger expansion.The amount of carbon dioxide which is sprayed into the 15 tobacco may be varied. It is found that treating the tobacc with about 80% to about 200% by weight of liquid and gaseous carbon dioxide provides an optimum range for practice of the present method in a pressure vessel having a volume of approximately 4.4 cubic feet. in^υ It is also possible to add' selected humectants to the tobacco prior to treating it with carbon dioxide. Examples of useful humectants include glycerin, propylene glycol, triethylene glycol and the like in amounts up to 8% by weigh of the tobacco. These also tend to lower the freezing point of the tobacco.Selective surfactants or the like may be added in amounts up to 3% by weight to the tobacco prior to effecting expansion. Preferably the surfactants are added in amounts less than 1% by weight. Representative examples of such sur factants include octanol, Tergitol (a nonionic surfactant made by Union Carbide Corporation representing a class of polyethylene glycol ethers of linear alcohols) , lauryl alcohol, and Tween 20 (a nonionic surfactant by ICI America, Inc., representing polyoxyethylene sorbitan monqlaurate) or the like. Practice of the present invention will become more apparent from the following examples wherein all parts are given by weigh unless otherwise indicated.5Example 1A 120 g. charge of shredded tobacco, at 14% moisture, was introduced into a two liter pressure vessel (Parr) and sealed. The vessel was purged by running carbon dioxide through the vessel at a pressure of 100 psig. for one minute.10 Carbon dioxide was supplied from a Dip Tube type cylinder and introduced into the vessel through a vertical perforated sparge tube that extended to within 2 cm. of the bottom of the vessel. After purging, the pressure was released to atmospheric and the exit vent closed. Carbon dioxide was15 sprayed on the tobacco, by means of the sparge tube, until a pressure of 400 psig. was reached. The vessel was main¬ tained at 400 psig. for three minutes before venting to atmospheric pressure. During venting solid carbon dioxide snow or frosted tobacco formed and this was passed into a20 gas-fired Jetstream dryer having a fluid temperature of 250°F. A residence time of about 0.5 seconds was s'ύfficient to achieve an expansion of 145% when measured by apparent specific gravity using tetrahydrofuran as the immersion liquid.25Example 2A 120 g. charge of tobacco at 12.8% moisture with 20% added alcohol was treated with carbon dioxide in a pres¬ sure vessel as described in Example 1. The purge time was30 30 seconds, pressure was 400 psig., holding time was 3 min¬ utes, and dryer fluid medium temperature was 300°F. Expan¬ sion was again measured by the apparent specific gravity technique and found to be 145%.35 Examples 3-11The procedure of Example 2 was repeated except that ingredients added, purge time, hold time and dryer fluid medium temperatures were as shown in Table I. TABLE ITobacco at 12.8%Example Msisture PlusNo. Listed Ingredients 3 10% Water + 5%Propylene Glycol 200 30 3 324 5% Water + 5%Ethanol 250 30 3 1105 5% Water + 5%Ethanol 250 0 3 1056 10% Water + 10%Ethanol 250 0 3 867 17% Water + 3%Glycerin 250 30 5 608 17% Water + 3%Glycerin 300 30 3 1089 15% Water + 5% Ethanol + 3%Glycerin 300 30 3 70 .10 20% Water + 5%Glycerin 350 30 5 13711 20% Ethanol + 3%Glycerin 250 30 3 141Example : 12 «The procedure of Example 4 was repeated except that tobacco having a moisture content of 11.5% and a ϋ -type gas-fired dryer such as shown in United States Patent No. 4,044,780 were used. The hold time was shortened to 2.5 minutes. Expansion under these conditions as measured by apparent specific gravity was 104%.Example 13Twenty-five pounds of cut blended tobacco having a moisture content of 15% and an ethanol content of 5% was in¬ troduced into a 4.4 cubic foot tapered pressure vessel suchOMP 7fy WIP as that shown in Figure 1. During about 30 seconds the vessel was purged with 5 to 8 pounds of carbon dioxide while maintaining 100 psig. pressure. Carbon dioxide was supplied from the two Dip Tube type cylinders and introduced into 5 the pressure vessel by means of a vertical perforated sparge tube that extended to within four inches of the lower ball valve 26. The pressure was reduced to atmospheric pressure after purging. The exit vent was closed and about 30 pounds of carbon dioxide was sprayed into the tobacco by^ means of the sparge tube while the pressure increased to about 400 psig. This pressure was maintained for approxi¬ mately 15 minutes before venting to the atmospheric pressure. During the time required for venting, about 30 seconds, solid carbon dioxide was formed. The tobacco frosted with solid'5 carbon dioxide was placed in a rapidly moving conveyor and fed into the gas-fired U -type dryer of Example 12 having a fluid temperature of about 400°F. Heat from the dryer imme¬ diately vaporized the solid carbon dioxide, thereby expand¬ ing the cut tobacco by about 94% as measured by the change20 in apparent specific gravity.Example 14The procedure of Example 13 was repeated except that the tobacco contained 15% moisture, 3% ethanol, and 2% 25 glycerin. The tobacco expansion was 104% as measured by the change in apparent specific gravity.Example 15The procedure of Example 14 was repeated except that30 2% propylene glycol was substituted for the 2% glycerin. In this experiment temperature and pressure measurements were followed for a period of 15 minutes. Results are shown in Figure 3. The addition of 30 pounds of carbon dioxide during 1.5 mins. ( A to B ) .gave a pressure of 330 psig. The35 temperature dropped rapidly to C as equilibrium conditions -ιo-were approached. Then as the vessel was slowly allowed to warm-up, the pressure and temperatures increased as antici¬ pated following the temperature-vapor pressure curve D - I reaching I after 15 minutes lapsed time. After the vesse was vented to atmosphere the final temperature of the frosty tobacco was -39°F. as indicated by J . Expansion measured as indicated above was 84%.Example 16Twelve pounds of cut blended tobacco containing 21% moisture and 5% glycerin was introduced into a 4.4 cubic foot pressure vessel. The vessel was purged with carbon dioxide at 70 psig. for 45 seconds and then brought to atmospheric pressure. Then carbon dioxide was supplied and introduced into the vessel as described in Example 13. Aft purging, sufficient carbon dioxide was added to give a pres¬ sure of 450 psig. which was maintained for three minutes. The vessel was vented to atmospheric pressure and the frosty tobacco fed into the ϋ -type dryer of Example 12 maintained at 400°F. Expansion was 51%. Tobacco analyses for the tobacco before and after expansion are shown below:Sample SampleBefore Expansion After ExpansionTotal Volatile Bases as Ammonia (%) 0.56 0.55Total Alkaloids asNicotine (%) 2.52 2.47Total Reducing Sugars as Dextrose (%) 7.4 7.3Ash (%) 17.65 17.40 pH 5.5 5.5 These results show no significant changes in major tobacco components as a result of the expansion.Example 17Twenty-five pounds of cut blended tobacco at 18% moisture and containing 5% addedethanol was introduced intoOMP^?NAP _ -ii- I' a 4.1 cubic foot tapered pressure vessel similar to Figure 1. The vessel was pre-pressurized to 250 psig. with gaseous carbon dioxide before spraying 34 pounds of liquid carbon dioxide onto the tobacco by means of the sparge tube as described in Example 13. Carbon dioxide was stored in a six-ton refrigerated tank system that was capable of supply¬ ing both gas and liquid to the pressure vessel. A pressure of 370 psig. was obtained and the tobacco held under pressure for three minutes before venting to the atmosphere. The tobacco was removed from the pressure vessel and fed into the U -type dryer of Example 12. In this manner an expan¬ sion of 98% was obtained when measured by the change in apparent specific gravity.Example 18Twenty-five pounds of cut blended tobacco at 18% moisture and containing 5% added ethanol was introduced into the pressure vessel described in Example 17. The vessel was purged and pressurized as described in Example 13 except that 34 pounds of carbon dioxide was used to give a pressure of 470 pfsig. Carbon dioxide was supplied by the refriger¬ ated system described in Example 17. The temperature of the in-going liquid, was maintained at about 10°F. (between 0° and 20°F.). The tobacco was held under pressure for six minutes before decreasing pressure to atmospheric and heating as described in Example 12. These conditions were sufficient to impart an expansion of 92% when measured by the change in apparent specific gravity.Example 19Thirty pounds of cut blended tobacco at 15% moisture and containing 5% added ethanol was introduced into the pressure vessel described in Example 17. The vessel was pre-pre,ssurized to 200 psig. with gaseous carbon dioxide before 57 pounds of liquid carbon dioxide was added through _-12-a 1-1/2 inch by 6 inch sintered stainless steel sparge tube located above the tobacco. This sparge tube delivers the carbon dioxide to the tobacco in the form of a fine fog or mist. Carbon dioxide was supplied by the refrigerated system described in Example 17. The vessel pressure was395 psig. immediately after the addition of carbon dioxide and rose to 450 psig. during a nine minute hold time. Car¬ bon dioxide then was vented, the pressure decreased to atmos pheric, the tobacco was removed from the pressure vessel and heated as described in Example 12. Tobacco expansion was112% as measured by the change in apparent specific gravity. While the invention has been described in connection with the preferred embodiments, it is not intended to limit the invention to the particular forms set forth, but, on the contrary, it is intended to cover such alternatives, modifi¬ cations, and equivalents as may be included within the spiri and scope of the invention as defined by the appended claims | AMENDED CLAIMS(received by the International Bureau on 10 September 1979 (10.09.79))1. A method for expanding tobacco tissue which comprises impregnating tobacco tissue with carbon dioxide by con¬ tacting the tobacco tissue with a mist of carbon dioxid within a confined vessel wherein the internal temperatu is about -8°F. to about 56°F., removing the impregnated tobacco tissue from the confined vessel, heating the impregnated tobacco tissue to effect rapid release of the carbon dioxide, and recovering expanded tobacco tissue.2. The method of Claim 1 wherein the tobacco tissue is con fined in a pressurized vessel and the carbon dioxide is sprayed onto or into a mass of tobacco tissue.3. The method of Claim 1 wherein the mist of carbon dioxid is effected by spraying liquid carbon dioxide.4. The method of Claim 1 wherein the mist of carbon dioxid is effected by spraying gaseous carbon dioxide or a$ mixture of liquid and gaseous carbon dioxide.5. The method of Claim 1 wherein the tobacco is introduced into the vessel by means of a pressure containing valve and wherein the impregnated tobacco is removed from the vessel by means of a pressure containing valve.6. The method of Claim 1 wherein the vessel is pre-pressur ized by means of an inert gas.7. The method-of Claim 1 wherein the vessel is pressurized between about 250 psig. to about 600 psig.8. The method of Claim 7 wherein the pressure is about 325 psig. to about 460 psig._Q-V.PI 9. The method of Cla,im 1 wherein, the internal temperature of the vessel is about 7°F. to about 28°F.10. The method of Claim 1 wherein rapid release of carbon5 dioxide from the impregnated tobacco tissue is effected within 30 minutes following release from the vessel.11. The method of Claim 10 wherein the rapid release is effected within 1 minute following release from the10 vessel.12. The method of Claim 1'wherein the temperature during heating the impregnated tobacco tissue is about 200°F. to 450°F,1513. The method of Claim 1 wherein the moisture content of the tobacco is about 10% to about 26% by weight.14. The method of Claim 1 wherein the tobacco is treated with 20 about 80% to about 200% by weight of carbon dioxide.15. An apparatus for expanding tobacco tissue which comprises in combination a vertically disposed vessel having an inlet pressure containing valve and an outlet pressure25 containing valve, a source of carbon dioxide having interconnecting means disposed to communicate with a plurality of outlets positioned within the vessel, and a mass of tobacco particles disposed within the vessel in communication with said outlets.3016. The apparatus o ^Cftaim.1*5' herein the vessel is tapered outwardly from an upper vessel location to a lower vessel location.3517. The apparatus of Claim 15 wherein the inlet pressure containing valve is positioned near the top of the vessel and the outlet pressure containing valve is positioned near the bottom of the vessel.18. The apparatus of Claim 15 wherein the plurality of out lets are disposed about a vertically positioned condui within or above the mass of tobacco. STATEMENTUNDERARΗCLE19This letter is in reply to the International Search Report of 16 July 1979 (Form PCT/ISA 210).In furthering the prosecution of the International application, kindly substitute pages 13, 14 and 15, including claims 1-18, for those pages carrying the same page number in the International application. The replacement pages are submitted herewithin duplicate.As noted, the applicants have amended claims 1 and 4 to include the recitation of a range of temperature within the vessel and have set out that the mist of carbon dioxide includes carbon dioxide in both a liquid and a gaseous state, respectviely.-BUREAtTOMPI | AMERICAN BRANDS; AMERICAN BRANDS INC | COGBILL E; GLASS J; HIBBITS C; KELLY J; PRICE B |
WO-1979000861-A1 | 1,979,000,861 | WO | A1 | XX | 19,791,101 | 1,979 | 20,090,507 | new | D21C9 | D21C9 | D21C9 | D21C 9/00, D21C 9/10F | A METHOD OF REFINING CELLULOSE PULPS | A method of refining cellulose pulps by bleaching or extraction is disclosed, in which the pulps at a consistency of 10 - 65% and in a finely divided form are treated with chemicals at a temperature of 10 to 250`C. The finely divided pulp is fed, impregnated with chemicals and at a consistency of 30 to 65% continuously into a processing apparatus in which an excess system pressure of 5 to 400 kPa prevails and which includes an atmosphere substantially consisting of steam having an oxygen content of less than 1% by volume and a temperature of 100 to 150`C. The pulp is moved rapidly, but without alteration of its fibre characteristics, continuously through the processing apparatus under a substantially turbulent flow and with substantially unaltered solids content. The chemicals charged to the pulp are caused to react so completely with the pulp during its rapid movement through the processing apparatus that they are substantially consumed when the movement is terminated. The pulp is then discharged from the processing apparatus and dried, optionally after further chemical treatment steps. | DE SCRIPT IOgTechnical fieldThe present invention relates to refining of cellulose material, such as chemical pulps, e.g. sulphate pulpsj soda pulps and sulphite pulpsj semi-chemical pulps, chemi-mechanical pulps and mechanical pulps such as groundwood pulps produced at normal pressure or excess pressure, refiner mechanical pulps and thermo-mechanical pulps. The term refining is used here primarily in reference to bleaching and extraction. Background ArtBleaching of chemical, semi-chemical and mechanical pulps with bleaching chemicals such as chlorine, chlorine dioxide, hypochlorite or lignin-preserving chemicals such as peroxy- compounds and dithionite is well-known in cellulose technology and usually takes place by the chemicals being mixed into the pulp, after which the bleaching reaction - generally at a pulp consistency below 2.0 % - is carried out for several hours at temperatures which seldom exceed 85 C. Befining cellulose pulps, with the intention of removing hemi-cellulose and/or extractive substances such as resin, fatty acids and unsaponifiable substan¬ ces, takes place by admixing of alkali such as sodium hydroxide in the pulp, subsequent to which the refining chemicals are allowed to react with the pulp for some hours at temperatures generally below 85 C. However, higher temperatures than 85°C can also be used in refining cellulose pulps, e.g. in hot alkali refining for producing dissolving pulp. It is known from Svensk Papperstidning No. 15 (1977) pages 480 - 482. that in experiments with peroxide bleaching of unbleached sulphate pulp at 110 C in a digester, a very rapid and complete reaction between the peroxide and the pulp has been established, in¬ dicatingi-dat other reaction mechanisns were imrαlyed at hi .temperatures- than at lower temperatures. I spite of. this the authors-have, however, for reasons of economy proposed a two-stage bleaching sequence con¬ sisting of an oxygen stage followed by a peroxide stage at 7QOC 'in~- stead of a single-stage peroxide bleaching at above 100 0 to obtain sufficient brightness increase when blea.chlng sulfate pulp, even if the selectivity will be lower than in single-stage high-temperature peroxide bleaching. The experiments were carriedout wLlh.a -shortest b-Leach- ing time of five minutes and with the pulp in a stationary bed and at a pulp concentration of 30 •The Swedish Patent Specification 341 519 describes a method for simultaneously bleaching and drying mechanical pulp to enable obtaining rapid drying of the pulp while retaining brightness. Ehe finely divided pulp, impregnated with hydrogen peroxide at a consistency of 20 - 50 , is dried in an air stream under normal pressure and with a residence time of 2 seconds to 10 minutes at a temperature of 260 - 538 C to a solids content of 65 - 95 • This method has several disadvantages, however.The consumption of expensive bleaching chemicals and energy will be great, and the content of fibre knots too high. Furthermore, the method does not work in the presence of sulphur compounds in the drying gas, and bleaching with reducing bleachers, e.g. dithionite, cannot be carried out, since these decompose due to the oxygen content of the drying air. Disclosure of inventionThe object of the present invention is to provide a method of refining cellulose pulps by means of bleaching or extraction, which gives the advantage of short processing time in combination with low chemical consumption and low energy consumption, while at the same time the finished product is given good quality characteristics. Accordingly, the present invention relates to a method of refining by bleaching or extraction of cellulose pulps, in which the pulps in a finely divided form at a consistency of10 - 65 are treated with chemicals at a temperature of 10 - 250 and dried, which is characterized in that the finely divided pulp, impregnated with chemicals, at a consistency of 30 - 65 is continuously fed into a processing apparatus which has an excess system pressure of 5 - 400 kPa and an atmosphere substantially consisting of steam with an oxygen content of less than 1 by volume and a temperature of 100 - 150 C, in that the pulp is rapidly moved, without alteration of the fibre characteristics by mechanical working, through the processing apparatus under substantially turbulent flow and substantially unaltered dry content, and in such a way that added chemicals have substantially completely reacted when the conveying through the processing apparatus is terminated, the pulp subsequently being discharged from the processing apparatus and dried after possible further chemical treatment steps.Best Mode of CarryingOut the Invention -in accordance with the invention, the moisture content of the pulp during passage through the processing apparatus should preferably not be altered by more than at most 8 and especially by less than 6 percentage units. It is especially suitable in accordance with the invention that before entering into, the processing apparatus, the pulp is dewatered to a pulp consistency of greater than 30 , preferably 45 or more, to recover the excess of bleaching solution and to carry out the division into finely divided form in a disc refiner. In the case where the chemical refining operation includes bleaching, the desired steam atmosphere is provided by supplying steam, which preferably has an excess pressure of 100 - 200 kPa. JFurthermore, in accordance with the invention, the steam atmosphere shall only contain at most 1 by volume of oxygen for the heat transfer to function in a satisfactory v/ay. It is advantageous, in accordance with the inven- tion, if the steam is separated from the pulp after the latter - has passed through the processing apparatus, the steam being re¬ cycled to the processing apparatus. A suitable temperature for the steam supplied is 100 - 150 C. Pulp and steam must be supplied to the processing apparatus in such a way that a substantially turbulent flow of pulp is obtained. This can be achieved mechanically or pneumatically. A suitable conveying speed for pneumatic conveying is more than 10 m/sec. The temperature in the processing apparatus is kept at 100 - 150 C, preferably at 105 - 120 C, and the excess pressure at 5 - 400 kPa, preferably 50 - 300 kPa. Suitable bleaching chemicals for use in accordance with the invention are chlorine dioxide, hypochlorite, peroxy . compounds, peroxides and dithionite. Especially suitable for use in accordance with the present invention are hypochlorite and lignin-preserving bleaching agents such as peroxides and dithionite. » In bleaching in accordance with the invention it has been found to be particularly advantageous if the pulp, at a low pulp concentration, e.g. 4 %, is first impregnated with complex- ing agents such as ethylenediaminetetraacetic acid (EDTA),OMPI diethylenetriaminepentaacetic acid (JKTPA) etc. before entry into the processing apparatus, the pulp subsequently being dewatered to a concentration of over 10 , suitably 15 - 35 , to remove heavy metals in the best way. Such dewatering can suitably be done in a drum filter, a centrifuge or a press. After possible shredding into centimeter-large pieces, the pulp is subsequently impregnated with a bleaching chemical solution, which furthermore can contain alkali, e.g. NaOΞ, and pH and peroxide stabilizers, e.g. sodium silicate} and protecting agents, e.g. magnesium sulphate. Impregnation can be carried out by spraying the bleach ing solution onto the flakes or by mechanical mixing, e.g. in a mixer. After this, the pulp is further dewatered once again to a high 'consistency, suitably over 30 , preferably 45 - 65 , so that the excess of bleaching chemicals is removed and can be recovered. This dewatering is suitably performed in a press. The dewatered pulp is then to advantage subjected to further disinte¬ gration, e.g. in a disc refiner or a spike roller shredder, by which means it is given flake form to be easily accessible for the temperature increase in the processing apparatus. The process in accordance with the present invention is also very suitable in extracting hemicellulose and extractive substances from cellulose pulp, e.g. for producing dissolving pulp etc. In this case the chemicals are alkali, e.g. sodium hydroxide or magnesium hydroxide. The procedure is here mainly the same as with the use of bleaching chemicals, i.e. the pulp is treated with an alkali solution at an excess pressure of 50 - 300 kPa, preferably 100 - 200 kPa, in a steam atmosphere provided by the supply of steam separated from the pulp after the passage of the pulp through the processing apparatus, with the difference that the pulp is washed after steam separation and before drying, the dissolved-out hemicellulose and extractive substances being separated (extraction).After treating with chemicals in accordance with the invention, the treated pulp, which has a solids content of at least 40 if it has been subjected to bleaching,* or at least 30 if it has been subjected to extraction, can be taken directly to paper manufacturing or other further processing, if such is\JΛ suitable, whereafter it is finally dried. The pulp can also be dried before the paper manufacturing, which is the most usual case in practice. Such drying is especially suitable if carried out as flash drying, i.e. when the pulp is suspended in a turbulent gas stream with a temperature of 1 10 - 500°C. The transfer of heat from the drying medium to the pulp is thereby facilitated. It is especially suitable for the drying medium to consist of superheated steam at an excess pressure of 20 - 400 kPa, in which case very good heat economy can be achieved by using the excess steam thus obtained for other heating purposes, e.g. as heat source in the chemical process in accordance with the invention. A suitable drying apparatus according to this method, a so-called counter-pressure drier, is described in the Swedish Patent Specification 393 855. In this drying apparatus, the pulp is dried in the form of flakes, which flow through vertical excess pressure towers at a rate of 21 m/s. The pulp flakes and steam are given the high speed by means of fans. The conveying or carrier steam is heated indirectly b pressurized steam pipes, the tempera¬ ture of which is kept considerably higher than that of the carrier steam. The carrier steam heats the moist pulp instantanteously, &ich leads to a rapid evaporation of the moisture in the pulp. A dry pulp is obtained by this drying process after 10 - 20 seconds. During the drying operation, the pulp can also be treated with pH-regulating substances, e.g. S0_, which is supplied in gaseous form, or calcium oxide in powder form.After passing through the drying unit, the excess steam is recovered by having the dried pulp pass through a hydrocyclone.The invention is illustrated by the following working examples. Example 1Washed birch pulp produced chemi-mechanic lly by partial delignification with bisulphite and defibration in a disc refiner, and having a brightness of 66 SCAU was mixed in a mixer with hot water and 0.2 diethylenetriaminepentaacetic acid (DTPA), calculated on the dry weight of the pulp, so that the pulp consistency was 4 % and the temperature 62°C. The pulp was dewatered to 35 solids content after 30 minutes. The dewatered pulp was shredded to_OMPI_ centimeter-large pieces and mixed in a mixer with a solution containing 18 g/l hydrogen peroxide, 25 g/l sodium silicate,- 9 g/l sodium hydroxide and 0.2 g/l magnesium sulphate. After the admixing of the bleaching solution, the pulp was dewatered in a press to 50 % pulp consistency for removing the excess of chemical The dewatered pulp contained 3.0 % hydrogen peroxide, 5.0 % sodiu silicate, 1.5 sodium hydroxide and 0.04 magnesium sulphate, calculated on the dry weight of the pulp. The pulp obtained was divided into individual fibres and fibre bundles by treatment in a disc refiner and was thereafter continuously fed via a sluice feeder into a processing apparatus in the form of a modified flas drier, in which the carrier was saturated steam at an excess press of 70 kPa and a temperature of 115°C- The steam, which consisted of saturated excess steam from a counter-pressure drier, was introduced into the flash drier in such a way that a turbulent flow was aehaeved, a fan being used for the further transport of the pulp. The conveying speed of the pulp through the processing apparatus was about 10 m/s, and the pulp passed the unit in 8 seconds. The solids content of the pulp on exiting from the modified flash drier was 45 * Before leaving the apparatus, stea was separated from the pulp in a hydrocyclone, and used for the steaming of the wood material supplied. The chemically processed pulp was ed out via a rotary valve feeder, washed with water and analyzed. The analysis result obtained is shown in Table 1 • The water used for washing only had traces of peroxide. Example 2Example 1 was repeated with the addition that after pass¬ ing through the modified flash drier, the pulp was continuously introduced at substantially constant solids content without wash¬ ing into a drying unit of the counter-pressure type, in which the drying medium was super-heated steam at an excess pressure of 300 kPa and a temperature of 150 C, to dry the pulp. The pipes used for heating the carrier steam were supplied with saturated steam at 160 C, which resulted in that the carrier steam was rapidly super-heated and that a rapid transfer of moisture from the pulp to the carrier steam was obtained. Pulp and steam were thereafter taken to a cyclone for separating steam from the pulp. The solids content of the dried pulp was 91.2 and it had a pH of 7.7. The pulp was analyzed and the results obtained are shown in Table 1. For the sake of comparison, a sample of the impregnated and finely divided pulp used in Example 1 was processed in the counter-pressure drier used in Example 2, with carrier steam at a temperature of 150 C and an excess pressure of 300 kPa, it thus being simultaneously subjected to bleaching and drying while the solids content was changed from 50 to 91.5 • The pulp was analyzed and the analysis results obtained are shown in Table 1 •For still further comparison, a sample of the impregnated and finely divided pulp used in Example 1 was processed in a conventional flash drier described in the above-mentioned Swedish Patent Specification 341 519. The drying air temperature was 450 C and it was heated with the aid of an oil burner. The drying air temperature was 120 C at the end of the drying operation. The pulp was analyzed and the analysis results are shown in Table 1 belowsTreatment Starting Example 1 Example 2 Simultan- Simultah - pulp Bleaching Bleaching eous bleach- eous blea i- followed ing and dry- ing and by drying ing in a drying in a i β>jJQ. CSi-tύfiUJϊ.rc conventional drier flash drierSolids content 50 45.0 91.2 91.5 91.1Brightness according to SCAN % 66.0 85.3 85.5_ 73.0 72.5Brightness gain, % 19.3 19.5 7.0 6.5Fibre bundles number per 100 g pulp 60 250. 280 1050 pH 5.6 8.2 7.7 7.8 6.2Table 1OMPI ^Z£a^ It will be apparent from Table 1 that quite surprisingly it has been found possible in accordance with the invention to bleach chemi-mechanical pulp under an extremely short time to a very high brightness, and thereafter to dry the pulp without intermediate treatment to a solids content of about 91 while maintaining an acceptable number o'f fibre bundles. As will be seen from the two right-hand columns, the bleaching result will. be considerably worse if bleaching and drying are done simultaneously, in which case the poor bleaching result can possibly be explained by the bleaching solution evaporating before it has had time to have any substantial bleaching effect. The brightness gains obtained show that only about one third of the' optimum bleaching ef ect was obtained while simultaneousl bleaching and drying in accordance with the known technique. The method in accordance with the invention was furthermore very economical with energy. Example 5Washed birch pulp was produced chemi-mechanically by delignification with bisulphite and defibration in a disc refiner The pulp had a brightness of 66 SCAN and was treated in the way set forth in Example 1, and with the same batches of chemicals before entering the modified flash drier. In the latter, the saturated carrier steam temperature was kept at 105 C, correspond ing to an excess pressure of 20 kPa. The passage time through the drier was 7 seconds. Before departing from the drier, steam was separated from the pulp in a cyclone, and used for steaming the supplied wood material. The chemically treated pulp was fed out via a rotary valve feeder and taken to a storage tank where it was stored for 15 minutes at a dry content of 47 • The temperatu of the pulp at the end of the residence time was measured and found to be 90 C. An analysis of the pulp at the end of the stor¬ ing time showed a hydrogen peroxide content of 0.1 % with a pulp brightness of 84.9 SCAU. The example shows that in accordance with the invention a milder chemical treatment at a lower temperature can be combined with a short after-treatment, e.g. a residence period in a storage tank, for completing the bleach¬ ing process, and reach a higher brightness value even so. Example 4Example 3 was repeated with the difference that the pulp in the storage tank was diluted to a concentration of 4 with a hot aqueous solution containing sodium dithionite so that the temperature became 76 C and the amount of dithionite charged was 0.4 %t based on. the weight of dry pulp. The residence time in the storage tank was regulated to 10 minutes. An analysis of the pulp processed in this way gave a brightness of 88.3 % SCAN, which is an extremely high brightness for chemi-mechanical pulps, and can be compared to the brightness for fully bleached chemical pulps. Example 5Example 2 was repeated with the difference that gaseous sulphur dioxide was added to the pulp before its entry in the counter-pressure drier, and in an amount corresponding to 0.3 counted on the dry weight of the pulp. The solids content of the pulp after .passing through the drying unit was 91.8 , its brightness 82.2 % SCAN and its pH 7.0. By the addition of sulphur dioxide it is thus possible, in accordance with the invention, to bleach and dry the pulp as well as adjust the pH to a desired level. Exem el 6Example 2 was repeated with the difference that the initial pulp consisted of groundwood pulp from spruce wood, having a brightness of 62 SCAN, and that mixing in a mixer with bleaching solution containing hydrogen peroxide, alkali, pH- stabilizers and protectors was excluded. After treatment in the disc refiner the pulp was taken via the sluice feeder into the modified flash drier, the pulp being sprayed immediately after the sluice feeder with a solution containing sodium dithionite and ethylene-diaminetetraaeetic acid (complexing agent) in an amount such that the pulp contained 0.8 % sodium dithionite and 0.15 of the complexing agent, counted on the dry weight of the pulp. Processing conditions were otherwise the same as in Example 2. The processed pulp had a solids content of 91.9 and a bright¬ ness of 73 SCAKT, which is a very high value in using dithionite as a bleaching agent.OMPI For the sake of comparison, an experiment was made with simultaneous bleaching and drying in a conventional flash drier, in accordance with the Patent Specification 341 519 mentioned above, the conditions being the same as in the corresponding comparative experiment in Example 2, with the difference that mixing with bleaching solution in the mixer was replaced by additing dithionite solution when shredding the pulp, so that the pulp contained 0.8 sodium dithionite and 0.15 % ethylene- diaminetetraaeetic acid calculated on its dry weight. The pulp thus treated had a solids content of 91.5 while its brightness was only 63 SCABT. The results show that bleaching and drying in accordance with the present invention completely surprisingly give a very good bleaching effect, while simultaneosu bleaching and drying in conventional flash driers only give minor bright- ness improvement. A possible explanation may be that the dithio¬ nite decomposes in a conventional flash drier, due to the presence of oxygen in the drying air. With bleaching in a steam atmosphere under excess pressure, in accordance with the inven¬ tion, there is no oxygen present in the carrier steam to an extent such that bleaching is disturbed. In the technical literature, the maximum brightness improvement with dithionite bleaching for a period of 60 minutes and 4 pulp consistency is given to be about 10 - 11 units. The treatment according to the invention resulted in a brightness improvement of 11 units, which thus shows that maximum brightness improvement had been achieved. Example 7Thermo-mechanical pulp produced from 50 % spruce and 50 % aspen, with a brightness of 56.1 SCAIT, was mixed as in Example with 0.2 DTPA and hot water in a mixer so that the pulp consistency was 4 and the temperature 62°C, the pulp then being dewatered to 35 % dry content. The dewatered pulp was mixed in a mixer with a bleaching solution containing 12 g/l hydrogen peroxi 20 g/l sodium silicate, 6 g/l sodium hydroxide and 0.1 g/l magnes sulphate, and was thickened in a press to 50 solids content. Th pulp thus dewatered contained 2.0 % hydrogen peroxide, 4.0 % sodi silicate, 1.0 sodium hydroxide and 0.02 magnesium sulphate, calculated on the dry weight of the pulp. The pulp thus impregnat with bleaching chemicals was taken through a disc refiner and was afterwards ed into a modified flash drier containing a bleaching compartment and a drying compartment with steam separa¬ tion between the compartments and after the drying compartment. The carrier steam temperature in the bleaching compartment was 114 C with an excess pressure of 64 kPa, and it consisted of saturated excess steam, coming partly from the bleaching compart¬ ment and partly from the drying compartment, and introduced via a fan in the bleaching compartment so that a turbulent flow was obtained. The residence time of the pulp in the bleaching compartment was 9 seconds and in the drying compartment 12 seconds, and it was dried to a solids content of 90.5 %, The brightness of the bleached and dried pulp' was 79.2 SCAN, which is a very high brightness for ther o-mechanical pulp. Usual tower bleaching of the pulp would have required a charge of 3 o hydrogen peroxide and a bleaching time of 2 hours. Example 8A sulphite pulp from spruce wood, which was bleached in one step with chlorine dioxide and neutralized with sodium•z. hydroxide had a viscosity of 1150 dm /kg according to SCAN, an extractive content of 0.42 according to SCAN and a brightness of 69 SCAN. The pulp had a solids content of 30 and was mixed with a diluted solution of sodium hypochlorite and sodium hydroxide to 10 pulp consistency and was dewatered to a solids content of 52 %. The dewatered pulp contained 0.7 % sodium hypochlorite, calculated as active chlorine, and 0.5 % sodium hydroxide counted on the dry weight of pulp. The pulp was shredded to flakes in a disc refiner and introduced into a modified flash drier containing a bleaching compartment and a drying compartment. On entering the bleaching compartment, the carrier steam tempera¬ ture was 120 C, corresponding to an excess pressure of 100 kPa. The residence time in the bleaching compartment was 8 seconds and in the drying compartment 12 seconds. The processed pulp had a solids content of 90.1 , a.viscosity of 1105 dm5Λg» an extract content of 0.42 and a brightness of 89.5 » It is apparent from the example that in accordance with the invention it is possible to bleach sulphite pulp in a very short time without notable degradation of the carbohydrates, in comparison with conventional tower bleaching, which would have required a residence time of several hours. Example 9 A semJrbleached pine sulphate pulp with a brightness of•z76 SCAN and a viscosity of 945 dm /kg was mixed with DTPA, hydrogen peroxide, sodium hydroxide and water such that the pulp consistency was 8 %, the suspension then being thickened to a solids content of 45 » The dewatered pulp contained 0.8 hydrogen peroxide, 0.2 % DTPA and 0.6 % sodium hydroxide. The pulp was shredded to flakes in a disc refiner and was introduced into a modified flash drier containing a bleaching compartment and a drying compartment. The carrier steam temperature on entry into the bleaching department was 120 C, corresponding to an excess pressure of 100 kPa. The residence time in the bleaching compartment was 9 seconds and in the drying compartment 12 seconds. The treated pulp had a dry content of 91.3 %t a viscosit of 922 dm /kg and a brightness of 85 SCAN. The viscosity was thus surprisingly high, considering that the brightness was improved by as much as 9 units. The example shows that in accordance with the invention it is possible to bleach sulphate pulp without notable degradation of the carbohydrates in a very short time in comparison with conventional tower bleaching, which would have required a residence time of several hours. Example 10Screened spruce sulphite pulp with a brightness of 62•zSCAET, a viscosity of 1140 dm /kg and an extractive content of 1.88 SCAN was charged with sodium hydroxide and water so that the pulp consistency was 10 and was afterwards thickened to a dry content of 42 $£. The pulp contained 2 % sodium hydroxide. It was introduced into a modified flash drier in which the carrier was saturated steam with a temperature of 115 C, corresponding to an excess pressure of 69 kPa. The residence time in the modified drier was 12 seconds. After separating steam in a cyclone> the pulp was fed out via a rotary valve feeder to a storage tank, where it was diluted with hot water. The solids content of the pulp on exiting from the drier was 39.5 , itsOMPl^ - viscosity 1055 dm /kg and its extractive content was 0.38 SCAN. The example shows that with processing in accordance with the invention it is possible to effectively deresinate sulphite pulp in a very short time. Deresinating conventionally in a tower requires a time of at least one hour. Example 11In this working example, bleaching under excess pressure in a closed processing apparatus, internally provided with a screw conveyor, was tried out. The turbulent flow of the pulp through the processing apparatus was provided mechanically in this ease. The screw conveyor was placed at the bottom of the processing apparatus, which was disposed horizontally in this case, the conveyor conveying the pulp at a rate of about 1 m/s through the apparatus to a pressure cyclone directly connected to the discharge end, this cyclone being in turn provided with a screw eeder for controlling the residence time of the pulp in the cyclone.In a thermo-mechanical pulp mill, spruce pulp with a solids content of 33 was taken out directly from the disc refiner in which the pulp had been defibrated, and was taken to a chemical mixer under the same excess pressure as the disc refiner, which was 150 kPa in this case. The following, calculated in percent by weight of dry pulp, were mixed into the pulp: 3 H20≥, 5 # Na2Si0 , 1.5 % NaOH, 0.02 % MgSO^ • 7 HgOg and 0.2 DTPA. After the bleaching chemicals had been mixed in, the pulp had a dry content of 32 % and a temperature of 110°C. The pulp mixed with bleaching chemicals was then transported by means of a high consistency pump for bleaching in the processing apparatus described above. The total residence time in the apparatus was calculated to about 6 seconds. The pulp was then taken from the apparatus to the pressure cyclone for separating steam, and the pulp separated from steam was allowed to fall down into the screw discharger. The time for passing through the cyclone and the screw discharger was estimated to be about 3 seconds. The pulp coming from the screw discharger had a tempera¬ ture of 96°C, a pulp consistency of 32 and contained 0.06 residual peroxide. After diluting with cold water to 4 :% pulpOMPI - consistency the pH of the pulp suspension thus obtained was measured and found to be 8.1 • The diluted pulp was then dewatered to a pulp concentration of about 30 in a centrifuge and was dried to a solids content of about 92.4 • The brightness of the pulp thus obtained was measured and found to be 74.3 % ISO, which must be regarded as surprisingly high in consideration of the short bleaching time, and the relatively simple bleaching installation which had been used. Example 12 The same bleaching apparatus as in Example 11 was used in this example, with the exception that the bleaching chemicals were not mixed in a special chemical mixer, but were supplied, in the thermo-mechanical pulp mill, to the disc refiner in which the chips were defibrated to pulp. The excess pressure in the disc refiner was 120 kPa on this occasion, and corresponded to a temperature of 123 C. The bleaching chemicals were added at different places along the radius of the grinding discs. 0.15 % DTPA and 3 Ξ O- were thus added close to the centre of the grinding discs, while 1.0 NaOH was added at a point halfway along the radius of the discs, and 3.0 % Na„Si0„ at a point about5 cm from the outer edge of the disc. The chemical charges given relate to percent by weight of dry pulp.The pulp obtained on defibration in the disc refiner- was blown to a pressure cyclone connected to the processing apparatus, which was provided internally with a screw conveyor.During the passage through the pressure cyclone and the processin apparatus, the excess pressure was reduced from 120 kPa o 50 kPa and thereby the temperature was also reduced from 123 C'to 111°C. After a residence time of 4 seconds in the processing apparatus, the pulp was blown to a second cyclone for separating steam from the pulp. After passing through this cyclone, the temperature in the pulp was measured and found to be 95 C, and its content of residual peroxide to 0.14 • The pulp consistency was 36 %. After diluting with cold water to a pulp consistency of 4 , the pH of the pulp suspension was measured and found to be 8.2. The diluted pulp suspension was then dewatered to a pulp consistency of about 30 % in a centrifuge, and dried to a solids content of 91.8 %. SUREOMPI WIPO The brightness of the pulp thus obtained was measured and found to be 74.6 $> ISO.In manufacturing thermo-mechanical pulp it is thus possible to already add the bleaching chemicals in the disc refiner, and in applying the method in accordance with the inven¬ tion to still obtain a surprisingly bright pulp in a short time, and with simple bleaching apparatus.The above examples show by way of conclusion that the process in accordance with the invention, applied to bleaching, enables bleaching of both mechanical and chemical pulp during the transport of the pulp together with steam under excess pressure and possible subsequent drying. Apart from the bleach¬ ing effect, excess steam is also obtained hereby, which can be utilized for different purposes, giving the process good heating economy. The bleaching chemical cost is also low with the method according to the invention. Applied to extraction, the possibility is obtained of carrying out an effective extraction reaction during a very short time, while the pulp is being conveyed by steam at excess pressure. In both types of reaction, the rapid reaction time further results in that the investment cost for apparatus will be low, and the need of buildings for setting up apparatus will be minimum. The use of high concentration in the method in accordance with the invention furthermore results in environmental advantages. | CLAIMS1. A method of refining cellulose pulps by bleach ng or extraction, the pulps in a concentration of 10 - 65 and in a finely divided form being treated with chemicals at a temperature of 10 - 250°C, and dried, characterized in that the finely divided pulp, impregnated with chemicals and at a consistency of 30 - 65 ι is continuously fed into a processing apparatus having an excess system pressure of 5 - 400 kPa and an atmosphere substantially consisting of steam with an oxygen content of less than 1 by volume and a temperature of 100 - 150°Cj in that the pulp is rapidly moved, without alteration of the fibre characteristics by mechanical working, through the processing apparatus under a substantially turbulent flow and with substantially unaltered dry content; and in that charged chemicals are caused to react so completely with the pulp during its rapid movement through the processing apparatus that the chemicals are substantially consumed when the movement, is termina¬ ted, the pulp being then discharged from the processing apparatus and dried after possible further chemical treatment steps.2. A method as claimed in claim 1, characterized in that the dry solids content of the pulp during passage through the processing apparatus is altered by at most 8 percentage units, preferably at most 6 percentage units.3. A method as claimed in claims 1 - 2, characterized in that the pulp, before entering the processing apparatus, is subjected to dewatering to a pulp consistency of over 45 % for removing chemicals, and is transformed into flake form.4. A method as claimed in claim 1 , characterized in that the pulp is bleached with bleaching chemicals at an excess pressure of 100 - 200 kPa, in that the steam atmosphere is provided by supplying steam; and in that steam is removed from the pulp after it has been discharged from the processing appara¬ tus, the steam then being recycled to said apparatus.5. A method as claimed in claim 4j characterized in that the cellulose pulp is a high-yield pulp, and in that the bleach- ing chemical is a peroxide or a dithionite.6. A method as claimed in claims 4 - 5, characterized in that before entry into the processing apparatus the pulp is' UR£ϊJOMPΓ wipc impregnated with a complexing agent, dewatered to a consistency of over 10 , preferably 15 - 35 %, impregnated with bleaching solution, pressed and transformed into flake form.7. A method as claimed in claims 1 - 3» characterized in that the pulp is treated with an alkali solution at an excess pressure of 50 - 300 kPa, preferably 100 - 200 kPa, in that the steam atmosphere is provided by supplying steam, and in that steam is separated from the pulp after the latter has been dis¬ charged from the processing apparatus, said steam being returned to said apparatus, the processed pulp being subsequently washed and dried after possible bleaching.8. A method as claimed in claim 7, characterized in that a sulphite pulp is extracted with sodium hydroxide. .9. A method as claimed in claims 1 - 8, characterized in that the drying is carried out in a flash drier.10. A method as claimed in claim 9, characterized in that the drying in the flash drier is carried out with superheated steam (so-called counter-pressure drying).11. A method as claimed in claim 10, characterized in that excess steam from drying is recycled to the treatment with chemicals.OMPI' W,PO ,κ\ | MODO CHEMETICS AB | LINDAHL J; SVENSSON G |
WO-1979000868-A1 | 1,979,000,868 | WO | A1 | XX | 19,791,101 | 1,979 | 20,090,507 | new | C07D451 | C07D205, A61K31 | C07D317, C07D463 | C07D 317/26, C07D 463/00, M07D 317/26, M07D 463/00, 124HC1B61A+A3, 124HC1B61A+B2+A3 | TRICYCLIC(AZETO-ISOQUINOLINE)B-LACTAMES | A new compound with a nucleus containing a benzo-fused carbocyclic ss-lactame system is disclosed. The compound has antibacterial activity against B. subtilis. | TRICYCLIC (AZETO-ISOQUINOLINE) β-LACTAMS , Research in the β-lactam field has centered mainly on penicillins and cephalosporin compounds, both of which have the β-lactam fused in a bicyclic ring system. Recently, new β-lactam systems which maintain their antibiotic properties have been reported. Examples include nocardicin [J. Amer. Che . Soc, 98, 3023 (1976)], which contains a monocyclic β-lactam nucleus, clavulanic acid (Belgian Patent No. 827,926), which has an όxygen- containing bicyclic β-lactam nucleus, and bicyclic systems related to cephalosporins in which the sulfur atom has been moved to another position, [J. Amer. Chem. Soc. , 99, 2353 (1977)] or has been replaced by oxygen or a ethylene group [J. Med. Chem. , 20, 551 (1977)]. The carbocyclic cephalosporin system noted above is believed to be the closest prior art; however it is also believed not to be material to the patentability of the compounds of this invention. Other similar β-lactams systems have been reported; however, all these systems are also not believed material prior art to the present invention.I have now prepared a novel tricyclic β-lactam system--which-jcontains a fused benzo system; in particular, derivatives of the lα-amino-l,2-dihydro-2-oxo-9bβH-azeto- [2,1-a]isoquinoline-4-carboxylic acid nucleus. DESCRIPTION OF THE INVENTIONThe compounds of this invention have the following chemical formulawherein M is hydrogen, a carboxylic acid protective ester residue, or a pharmaceutically acceptable non-toxic cation. The term a carboxylic acid protective ester group is one which has a clear and definite meaning within the art. Many ester groups are known and used in the art to protect a carboxylic acid group from interfering with chemical reactions in undesired ways. At the appropriate time, the esters are cleaved by standard methods to give the desired free carboxylic acid moiety. Many examples of such ester groups are set forth in the chemical litera¬ ture, including review articles and books such as Protective Groups in Organic Chemistry , McO ie ed., Plenum Press, New York, 1973. Examples of the most common esters include t-butyl, benzyl, nitrobenzyl, methoxybenzyl, benzhydryl, and trichloroethyl. The selection of which ester group to use depends on various factors, including subsequent reaction conditions and desired methods of removal. The selection of the proper ester group is within the ability of persons skilled in the art. Pharmaceutically acceptable non-toxic cations are also well-known in the art. In general, they include alkali metal cations, alkaline earth cations and organic or inorganic ammonium cations. The sodium and potassium salts are particularly advantageous. Again, the selection of useful and proper cations is within the ability of persons skilled in the art. 1 «v»The compounds of this invention are prepared by a totally synthetic route with the monocyclic β-lactam (1) as starting material. Compound 1 is prepared by the sequence of reactions set forth in Scheme I. Conversion of β-lactam 1 into the compounds of this invention is outlined in Scheme II,OMPI7 -tyA - WIPO 2 3DMB =6SCHEME IURE_ OMPI ^NAT COOCH2Ph COOCH2PhSCHEME IIBenzyl alcohol 2 [J. Chem. Soc. (C) , 1818 (1969)] is oxidized by standard oxidizing agents such as Crθ3 to benzaldehyde ^. Condensation of 3^ with 2,4-dimethoxy- benzylamine gives i ine 4, which is reacted directly with phthalimidoacetyl chloride to give monocyclic β- lactam wherein Ft is phthalimido. Treatment of 5 with methylhydrazine gives the amino-β-lactam derivative 6. Acylation of 6 with phenoxyacetyl chloride by standard methods followed by oxidative cleavage of the dimethoxy¬ benzyl group with K2S2O8 gives the monocyclic β-lactam 1. When β-lactam 1 is treated with an ester of glyoxylic acid (where the ester is selected from those protective esters known within the art) in the presence of triethylamine, compound 7 is obtained. The alcohol moiety of 7 is converted to the chloro derivative by treatment with thionyl chloride and pyridine. Reaction of the chloro derivative with triphenyl phosphine gives the ylide 8. Treatment of 8 with a mild acid such as p_-toluensulfonic acid yields the ester compounds of this invention. Cleavage of the ester group by standard methods gives the compounds of the invention where M is hydrogen. The free acids can be converted to the pharmaceutically acceptable salts by standard methods known in the art. The compounds of this invention where M is hydrogen or a cation have antibacterial activity against B. subtilis. They are useful for sterilization of laboratory glassware or for treating infections of B. subtilis in animals. The compounds of this invention where M is a protective ester group are useful as intermediates for the antibacterially active compounds.The following examples are presented to il¬ lustrate general methods of preparing the compounds of this invention to one skilled in the art and are not to be construed as limiting the scope thereof. All tempera¬ tures are given in degrees Centigrade.EXAMPLE 1 2-(2-Dioxolanyl)benzaldehydeA suspension of sodium acetate (6.56 g, 0.08 mol and pyridinium chlorochromate (17.2 g, 0.08 mol) in dry methylene chloride (200 ml) was cooled in an ice bath under a nitrogen atmosphere and treated with a solution of 2f-(2-dioxolanyl)benzyl alcohol (9.6 g, 0.053 mol) in methylene chloride (25 ml) over a 15 minute period. The reaction was stirred at room temperature for 2 hours and diluted with ether (200 ml) . The solid was collected and washed with ether, and the filtrate was washed with 5% aHC03 and brine and dried. The solution was evaporated to give the title aldehyde; 7.8 g (82%).EXAMPLE 2 cis-1-(2,4-Dimethoxybenzyl)-2-[2-(2-dioxolanyl)phenyl]-4- oxo-3-phthalimidoazetidineTo an ice-cold solution of 2,4-dimethoxybenzyl- amine (3.6 g, 21.5 mmol) in methylene chloride (40 ml) was added a solution of aldehyde from Example 1 (5.0 g,22.4 mmol) in methylene chloride (25 ml). The solution was stirred 10 minutes, 4A molecular sieves (9 g) were added, and the reaction was stirred at room temperature for 1.75 hours. IR analysis indicated no amine or' aldehyde groups.The mixture was cooled in ice and triethyla ine (2.61 g, 25.8 mmol) was added, followed by the dropwise addition of phthalimidoacetyl chloride (5.54 g, 24.8 mmol) in methylene chloride (40 ml) over a 15 minute period. The reaction was stirred for 30 minutes and then filtered. The filtrate was washed with 5% NaHC03 and brine, and the organic phase was dried and evaporated to an oil, which on standing with ether and chloroform gave a solid product; 9.3 g. The solid was recrystallized from ethyl acetate; 7.1 g (64%), mp 170-172°.EXAMPLE 3 cis-3-Amino-l-(2,4-dimethoxybenzyl)-2-[2-(2-dioxolanyl)- phenyl]-4-oxoazetidini The product from Example 2 (5.8 g) was dissolved in methylene chloride (40 ml) and filtered to remove a trace of insoluble solids (0.15 g) . The»filtrate was cooled with an ice bath and treated under a nitrogen 1 atmosphere with methylhydrazine (0.85 g, 18.7 mmol). The reaction was stirred 2 days under nitrogen at room temper ture and then filtered to remove a solid, which was washe with a small amount of methylene chloride. The filtrate5 was evaporated in vacuo to give 4.65 g of the title pro¬ duct.EXAMPLE 4 cis-1-(2,4-Dimethoxybenzyl)-2-[2-(2-dioxolanyl)phenyl]-4- 10 oxo-3-phenoxyacetylaminoazetidineThe amino compound from Example 3 (4.22 g,11 mmol) was dissolved in ethyl acetate (60 ml) and cooled in an ice-alcohol bath. Triethylamine (1.67 g,16.5 mmol) was added, followed by the dropwise addition15 of phenoxyacetyl chloride (2.06 g, 12.1 mmol) over a period of 5 minutes. The reaction was stirred for 45 minutes with cooling and then filtered. The filtrate was washed- with 5% NaHCθ3 and brine. The dried filtrate was evaporated to give the title product; 2.0 g. The20 product was recrystallized from ethyl acetate-ether; 1.02 g, mp 137-138°. The solid which was filtered from the reaction solution was stirred with hot ethyl acetate (100 ml) and filtered. The filtrate was treated with ether (200 ml) and cooled to give additional product;253.91 g, mp 138-139°.EXAMPLE 5 cis-2-[2-(2-Dioxolanyl)phenyl]-4-oxo-3-phenoxyacetyl- aminoazetidine 0 The product of Example 4 (1.56 g, 3 mmol) was dissolved in a mixture of acetonitrile (120 ml) and dis¬ tilled water (30 ml) , degassed with argon for 30 minutes, and brought to reflux. A degassed solution of K2S2θs (5.67 g, 21 mmol) and Na2HP0 -7H20 (2.81 g, 10.5 mmol) 5 in distilled water (120 ml) was added in 8 equal portions at 4 minute intervals to the refluxing solution, the reaction being kept at pH >6 by the addition of solid Na2HP04*7H20. The acetonitrile was evaporated and the residue was extracted with ethyl acetate. The extracts were washed with brine, dried, and evaporated to an oil, 2.07 g. The oil was extracted with petroleum ether to remove the dimethoxybenzaldehyde and then was triturated with ethyl acetate-ether. It was cooled in ice and the resulting solid product was collected; 0.54 g (49%), mp 137-138°dec.EXAMPLE 6Benzyl α-Hydroxy-α-fcis-2-[2-(2-dioxolanyl)phenyl]-4-oxo- 3-phenoxyacetylamino-l-azetidinyl]acetate Freshly distilled benzyl glyoxylate (312 mg, 1.9 mmol) and freshly distilled tetrahydrofuran (15 ml) were stirred with 4A molecular sieves for one hour and then cooled in ice. To this solution was added the solid product from Example 5 (437 mg, 1.19 mmol) followed by the dropwise addition of triethylamine (240 mg, 2.37 mmol). The ice bath was removed and the reaction was stirred for 1.5 hours. The solution was filtered and the filtrate was evaporated to dryne'ss. The residue was dissolved in chloroform and chromatographed on a silica gel column with a chloroform-ethyl acetate gradient as eluant to give the title product, 525 mg (83%) .EXAMPLE 7Benzyl 1,2-dihydro-2-oxo-lα-(phenoxyacetylamino)-9bβH- azetό[2,1-ajisoquinoline-4-carboxylate ' The product of Example 6 (309 mg, 0.58 mmol) was dissolved in freshly distilled tetrahydrofuran (20 ml) and cooled to -6°. To the cold solution was added pyridine (68 μl, 0.847 mmol) and thionyl chloride (58 μl, 0.812 mmol), and the reaction was stirred for 2 hours at -6°.. The solid pyridine salt was collected and the filtrate was evaporated to dryness under high vacuum. The chloro product was dissolved in freshly dis¬ tilled tetrahydrofuran (15 ml) and was treated with pyridine (103 μl, 1.28 mmol) and triphenylphosphine (304 mg, 1.16 mmol). The reaction was refluxed 1.5 hours under an argon atmosphere, stirred overnight at room temperature, and then refluxed an additional 4.5 hours. The solution was decanted from a small amount of solid and evaporated to dryness. The oil was dissolved in chloroform:ethyl acetate (1:1) and chromatographed on silica gel (25 g) with chloroform:ethyl acetate (1:1) and then ethyl acetate as eluants to give the ylide product, 280 mg (62%) .The above product (277 mg, 0.357 mmol) was dissolved in 9:5 acetone:water (9 ml) which had been previously degassed with argon. The solution was cooled in an ice bath and treated with p_-toluenesulfonic acid (277 mg, 1.46 mmol). The reaction was stirred at room temperature for 1.75 hours during which time the product precipitated. The solution was cooled in an ice bath and the title product was collected and washed with additiona cold acetone-water solvent; 105 mg (65%-) , mp 136-8°.EXAMPLE 81,2-Dihydro-2-oxo-lα-(phenoxyacetylamino)-9bβH-azeto- [2,1-a]isoquinoline-4-carboxylic acidThe product of Example 7 (55 mg, 0.12 mmol) was dissolved in freshly distilled tetrahydrofuran(24 ml) and hydrogenated at atmospheric pressure for2 hours in the presence of 10% Pd on carbon (55 mg) . The catalyst was removed by filtration and the filtrate was evaporated to dryness. The product was triturated with ether and ethyl acetate; 25 mg, mp 167-168 dec. | I claim :1. A compound of the formula:where M is hydrogen, a carboxylic ac d protective ester residue, or a pharmaceutically acceptable non-toxic cation.2. A compound as claimed in claim 1 where M is hydrogen, t-butyl, benzyl, nitrobenzyl, methoxybenzyl, benzhydryl, trichloroethyl, sodium ion, or potassium ion,3. A compound as claimed in claim 2 where M is hydrogen.4. A compound as claimed in claim 2 where M is sodium ion. 5. A compound as claimed in claim 2 where M is potassium ion.6. A compound of the formula:7. Antibacterial compositions comprising a compound of claim 1 where M is hydrogen or a pharmaceuti¬ cally acceptable non-toxic cation. . .1. A compound of the formula;where M is hydrogen, a carboxylic acid protective ester residue, or a pharmaceutically acceptable non-toxic cation.2. A compound as claimed in claim 1 where M is hydrogen, t-butyl, benzyl, nitrobenzyl, methoxybenzyl, benzhydryl, trichloroethyl, sodium ion, or potassium ion.3. A compound as claimed in claim 2 where M is hydrogen.4. A compound as claimed in claim 2 where M is sodium ion. 5. A compound as claimed in claim 2 where M is potassium ion.6 . Cancelled.7. Antibacterial compositions comprising a compound of claim 1 where M is hydrogen or a pharmaceuti¬ cally acceptable non-toxic cation.IJURO Λr- WI | SMITHKLINE CORP | PERCHONOCK C |
WO-1979000871-A1 | 1,979,000,871 | WO | A1 | XX | 19,791,101 | 1,979 | 20,090,507 | new | A61L15 | null | A61L15 | A61L 15/18, A61L 15/44 | A COMPRESS FOR TREATMENT OF WOUNDS | A compress for treatment of discharging wounds. The compress is soaked in a solution containing sodium chloride and/or zinc salt(s) and is then dried. The dry compress is applied to the wound and is fixed with a bandage. The secretion of the wound is absorbed by the compress, thereby cleaning the wound and preventing crust formation. An antibacterial effect is also obtained. Sodium chloride and the zinc ion effect the wound bottom directly and stimulate the healing of the wound. | A COMPRESS FOR TREATMENT OF WOUNDSBackground of the inventionFor the treatment of chronic and infected peripheric wounds moist sodium chloride compresses are mainlv used at present, i.e. compresses soaked in an isotonic or a hypertonic sodium chloride solution. These moist compresses are placed in the wound and then a common bandage is applied. Sodium chloride solution on wounds prevents crust formations and keeps the wound soft - and pliable, so that joints can be bent. Besides the epithelization of the wound bottom is facilitated and the secretion from the wound is absorbed into the compress. A hypertonic sodium chloride solution also has a cleaning effect on non-vital wound tissue by osmotically bursting poorly vital cells. This solution to some extent also has an antibacterial effect - at least prevents the growth of several types of bacteria.The disadvantages of this treatment are that it re¬ quires several changes a day, that it causes macera¬ tion of the wound edges and that it is difficult to perform at home.The sodium chloride compress however has the great advantage that the patient never becomes sensibilisized by the treatment. On the contrary to this compresses treated with antibiotics , which are used to a certain extent, causes sensibilization in many cases. A new medical dressing Debrisan however has not shown sensi¬ bilization and is told to have better absorbation capacity than moist sodium chloride compresses. The disadvantages of this preparation however are a very high price and that it is difficult to apply, since the active substance is a dry powder, which easily runs out from the wound.In the German patent specification 577.798 a dressing material impregnated with an oxygen delivering com¬ pound, e.g. percarbonates or perborates, is described. Here the purpose however is to effect the secretion from the wound by chemically changing it when it has been absorbed in the dressing, i.e. a quite different effect to that achieved by sodium chloride.In the German patent specification 112.192 is described a sanitory towel impregnated with a solution containing a compound which prevents crust formations of the blood, e.g. sodium chloride is mentioned. This patent is probably based on an important mistake, since it is a well-known fact that menstrual blood normally is fluid and does not coagulate.This is due to that the endometriu in the uterus has a high content of plasminogen activators. These provides a decomposition of the fibrin possibly formed, which keeps the coagulum together. If a disease in the woman would allow coagulum to be formed in the sanitory towel the salt content would not have any greater effect on the hardness of the coagulum.Description of the inventionAccording to the invention a new type of a salt compress is provided, which is prepared by immersing a com¬ press in a solution containing sodium chloride and/or zinc εalt(s), after which the compress is dried. The salt remains in the compress._OMPl The salt (sodium chloride or zinc salt) effects the wound bottom directly, at which sodium chloride is a physiologic stimulator for healing of wounds and the zinc ion effects certain enzymes positively, which are important for the healing of wounds.The compresses, which are somewhat stiff, are care¬ fully pressed against the wound with a spatula and are fixed with a bandage against the moist wound bottom, at which they soften at the same time as secretion from the wound is absorbed by the compress. The wound bottom is in connection herewith cleaned and crust formation is prevented, since the protein in the secre¬ tion, which is a basic substance for crust formation, will go into the compress. An antibacterial effect is also achieved, since the bacteria will follow the secretion into the compress and there be exerted to a strong osmotic effect from the salt in the compress. Since the dry compress has a good osmotic effect the risk for inflammation in and around the wound is decreased. This leads to pain easing.. In other respects the dry salt compress has the same effect on the wound as conventional moist sodium chloride compresses.They however have several advantages compared to moist sodium chloride compresses, by the fact that the wet handling of these and unnecessary manualΛwork for the nursing staff at the handling of salt solutions in bottles are avoided. Moreover moist sodium chloride compresses have to be changed several (3-6) times a day, while 2 changes normally is sufficient for dry salt compresses .Description of practical testsTests have been made in the form of an open studyOMPI on 15 patients with peripheric wounds of different geneses. Five patients had gangrenous wounds owing to arterial insufficience in a foot or the feet. Three patients had decubitus in the gluteal region. Four patients had wounds on an amputation stump. One patient had a chronically infected wound in the hip area on the left side after a collum fracture and operation. One patient had a chronically infected wound oh the left forearm caused by pressure from a plaster bandage. One patient had a wound from a radiation damage.All wounds were discharging and infected and showed at the beginning of the test poor epithelization and granulation formation. The arterial wounds were strongly painfull. In all cases dry wounds with an improved epithelization and granulation formation were achieved within 10 days, a result which proves to be better than the experiences from treatment with moist sodium chloride compresses. In nine cases the treatment with dry sodium chloride compresses were continued during the whole process of healing, i.e. up to 0 days, without any drawbacks being noticed. It was expected that the patients would complain of pain or increased pain when the dry compress was applied to the wound. This was however not the case, but only as an excep¬ tion and during a short time. No maceration of the wound edges did occur.The nursing staff performing the treatment of the wounds of the patients were satisfied with the simplicit of the bandaging of the wounds. The patients were pleased with the dry salt compresses, because they usually involved only two changes a day and because the compresses did not stuck in the wounds and causing pain at the changing. Cultivation of bacteria in seven cases showed a con¬ siderable reduction of the mixed flora of bacteria in the wounds but slight or no effect on staphylo- cocci.As a summary it can be stated that the dry sodium chloride compresses have proved to have an unexpectedly positive effect, i.e. several important advantages and no disadvantages compared to the conventional treatment with moist sodium chloride compresses.The compress is delivered in a sterile packing in the usual way. As was previously mentioned also zinc salts can be used in the compress.-BU EAUOMPI | C L A I MA sterile compress for the treatment of discharging wounds, said compress containing salt/salts in solid condition, c h a r a c t e r i z e d i n, that the salt(s) is/are sodium chloride and/or zinc salt(s), said salts being intended to effect the wound bottom directly and stimulate the healing of the wound and by osmotic forces effect the secretion from the wound being absorbed by the dry compress. | HYLERSTEDT E; MOELNLYCKE AB; NORDQVIST P | HYLERSTEDT E; NORDQVIST P |
WO-1979000872-A1 | 1,979,000,872 | WO | A1 | XX | 19,791,101 | 1,979 | 20,090,507 | new | E04H3 | null | A47C1, E04H3 | A47C 1/126, E04H 3/12B | TELESCOPING SEATING SYSTEMS WITH AUTOMATICALLY FOLDING CHAIRS | In a telescoping seating system having a number of rows (10, 11, 12) which may be moved between an extended or use position and a retracted or storage position, chairs (S, B) or other seating is mounted on stanchions (22) which are pivotally mounted to the rear of the deck (13) in each row. The stanchions are pivoted to an upright position when the system is extended for use and folded to a horizontal position when the system is retracted for storage by means of an actuator mechanism (40, 41) mounted to the forward portion of the next higher row and operative in response to relative movement between adjacent rows. In this manner, the height of the seats is independent of the rise of the system for more comfortable seating. A torsion rod assembly (50, 64, 65, 60) is mounted beneath the seating to counterbalance at least some of the weight of the seating in the storage position. Locking members (27) engage the stanchions in the use position to secure the seating in the raised position. The locking members are released in response to the closing motion between adjacent rows to permit the seating to be folded to the storage position in the space between adjacent decks. | AUTOMATICALLY FOLDING CHAIRSThe present invention relates to telescoping seating systems of the type which may be moved between an extended or use position in which the rows are in stepped or tiered rela¬ tion, and a retracted or storage position in which the rows are aligned vertically.The present invention is particularly directed to a telescoping seating system which is provided with individ¬ ual chairs which may be arranged in groups and which are automatically folded onto the deck when the system is re¬ tracted for storage, and automatically raised for use when the system is extended.In a preferred embodiment for operation in a fully automatic mode, the seating system has a plurality of rows. Each row includes a horizontally extending deck. The rows are adapted for movement between a use position in which said decks are extended in stepped relation and a storage position in which said decks are retracted in generally vertical alignment. A plurality of seating assemblies are provided in each row, each seating assembly includes stanchions pivot¬ ally mounted for movement at the rear of the deck between a raised and a lowered position. The seating assemblies include backs and seats carried by the stanchions. Actuators are mounted on the forward portion of the next higher row and adapted to engage the seating assemblies as the rows are extended relative to one another. The actuators raise the seating assemblies to an upright use position. Locking elements mounted for movement between a use and a storage position lock the seating assemblies in the raised position when a lower row is fully extended relative to the next higher row. The locking elements are constructed and arranged to be unlocked by the relative motion between the rows to permit the forward folding of the seating assemblies as the rows are retracted for storage. Energy storage means in the form of torsion rods are interconnected between the row and the seating assemblies for partially counterbalancing the weight of the seating assemblies in the lowered position. The torsion rod mechanism is mounted beneath the seating on top of and toward the rear of each deck. A cover plate encloses and hides the mechanism from view and this, together with the fact that the mechanism is mounted to the rear of the deck and out of the way, facilitates maintenance and cleaning.It is also considered an important aspect of the present invention, both from the viewpoint of original manu¬ facture as well as for retro-fitting existing systems that all of the apparatus for automatically raising and lowering the chairs be mounted to the upper side of a deck, rather than beneath or behind the deck where it is not only more difficult to install and maintain, but where the possibility of interfering with the deck support and actuating systems is greater.Another advantage of the present invention is that the seating is folded and unfolded only in response to the relative movement between adjacent rows. This is important because special sequencing of the rows is not required in moving the system between the storage position and the use position.The apparatus of the present invention may be used for various types of seating, such as benches; and it may be adapted to incorporate various chair designs. However, it is preferred to use chairs mounted on beams in groups of two to seven.The DrawingFIG. 1 is an upper front perspective view showing the two bottom rows of a telescoping seating system incorpora ting the present invention;FIG. 2 is a fragmentary side view of the system of FIG. 1 showing adjacent rows in the storage and use positions as well as in intermediate positions illustrating the opening and closing sequence;FIG. 3 is a fragmentary front view of the lower por¬ tion of a stanchion in the raised position, for the embodimen of FIG. 1;FIGS. 4 and 5 are left and right side views respec¬ tively of the apparatus of FIG. 3;O Wl . , - of an adjustable latch for the locking member for the embodiment of FIG. 1, taken through the sight line 6-6 of FIG. 4; andFIG. 7 is a fragmentary, close-up, transverse cross sectional view taken through the sight line 7-7 of FIG. 6.Detailed DescriptionReferring first to FIG. 1, three lower rows of a tele¬ scoping seating system having a plurality of rows are shown. These rows are generally designated 10, 11 and 12 respectively. When the system is extended to the use position (see row 11 relative to row 12) , the rows are in stepped or tiered relation. When the system is retracted for storage, the rows are gener¬ ally vertically aligned.Each of the rows is similar in structure. Referring to row 12, it includes a deck generally designated 13 which includes a forwardly extending horizontal platform 15 and a rear riser 16.The nose of the platform 15 is designated by refer¬ ence numeral 17. The rear riser 16 may be a metal beam mounted between two upright posts, one of which is shown at 18 in FIG. 1. Support arms extend outwardly from the posts 18 and from the riser beam 13 to support the platform 15. The posts are mounted on wheel carriages, one of which is shown at 19 in FIG. 1. Additional details of row structure, including the apparatus for supporting a deck while permitting it to be moved between the extended and retracted positions may be found in U.S. Patent 3,667,171, June 6, 1972 or U.S. Patent 4,041,655, August 16, 1977.As seen in FIG. 1, a group of seven chairs generally designated 20 is mounted to the deck 11 as a single group. Different types of seating or different chairs than those shown may likewise be used. In the illustrated embodiment, individual chairs, each having a back B and a seat S are moun¬ ted to a common beam 21.The beam 21 is supported by a number of stanchions-- four stanchions being shown in the illustrated embodiment and designated 22. As will be described presently, the stanchions 22 are pivotally mounted at their lower ends to the platformIFURE-OMPIA WΪPO~ i RNATX portion of the deck 11. Thus, the beam 21 and stanchions 22 are rotated as a unitary structure to the upright position shown for the row 11 when the row 11 is extended relative to the next higher row 12. The sequence for closing is the re¬ verse of that for opening. When a lower row is retracted beneath the next higher row, the beam 21 and stanchions 22 are rotated forwardly so that the stanchions, beam, backs and seats can be stored in the space between adjacent decks. This is illustrated in FIG. 1 by the position of the chairs in the row 10.Referring now to FIG. 2, the stanchion 22 is pivotall mounted on a pin 25 to a housing 26. A locking member 27 is pivotally mounted at 28 to the bottom of the stanchion 22. The heel of the locking member 27 is formed into a first re¬ cess 29 and a second partial recess 29A. This is best illus¬ trated for the locking members associated with the higher rows 11 and 12 since, in these positions, the locking members are in a released or unlocked position. In the locked position, the recess 29 snugly engages a pin 30 which is also secured to the stanchion housing 26. The forward bearing surfaces of both recesses 29 and 29A are ground on radii centered at the axis of pin 28 to insure that the locking member will not be dislodged by an occupant of the seat. At the forward end of the housing 26, there is fixed a stop pin 32, and a set screw 33 which is received in a threaded nut or plate welded to the inner surface of the front of the housing 26 (see FIG. 4).The chair is secured to the beam 21 by means of a mounting bracket generally designated 35 which includes a laterally extending plate 36 having a forward surface 37. There is an open space forward of the plate 37, and it is designated 38. This space is open and clear above the beam 21 so as to receive an inwardly turned hook portion of a latch ing member 40 which is pivotally mounted at 41 to a bracket 42 secured to the nose of the deck of the next higher row.As is known in the art, the forward portion of each deck rests on and is supported by the rear portion of the next lower row. In this embodiment, a cantilever arm 47 for the row 11 extends forwardly of its associated post 18 and rests on a roller 48 mounted to the post 18 for the next lower row 10. This positions the forward portion of the deck in the use position, and it can be seen to be aligned with the -uppermost portion of the locking member 27 of the next lower row (refer¬ ring to the right hand portion of FIG. 2) so as to engage and unlock that member when the two adjacent tows are moved relative to each other to the storage position.A torsion rod 50 is secured to each stanchion 22, and it extends laterally thereof and is fixed to the housing26 associated with the next adjacent stanchion. The detailed structure of the torsion rod and housing, as well as that for the adjustable latch member 30 will be described presently. However, it will be understood that the torsion rod 50 acts as an energy storing means such that when the chair, is lowered, the torsion rod 50 is twisted clockwise (when viewed from the left) , as illustrated in the sequence of positions of the end of the torsion rod 50 in rows 10, 11 and 12 in FIG. 2. Thus, in the storage position, the torsion rod 50 acts to at least partially offset the weight of the chair, the beam 21 and the stanchions 22.Turning now to FIGS. 3-5, the housing 26 includes first and second side plates 52, 53 which are secured together by an upper flange member 54 providing a back 55 and a top 56, and a lower flange member providing a bottom 57 and a front 58. The back wall 55 may be secured to the rear riser of a deck, and the bottom wall 57 may be secured to the platform.As best seen in FIG. 3, the top portion 56 defines a slot 58 to permit the locking member 27 to assume the locked position shown in FIG. 5.The previously described pin 25 and stop member 32 are conventionally mounted to the side plates 52, 53. It will be observed from FIG. 3 that the side plates are spaced apart sufficient to permit both the stanchion 22 and the lock member27 to be placed between them.The right end of the pin 25 extends beyond the side plate 53 (again, best seen in FIG. 3) and a casting 60 is pivotally mounted thereto, held by an E-ring. Referring to FIG. 5, the casting 60 extends downwardly and defines a cradle portion 61 which receives and secures the turned portion of a torsion rod 50A. The torsion rod 50A is used to store energy to raise the stanchion to the right of that shown in FIG. 3. The back of the cradle 60 is flanged and limited in rearward motion by means of a bolt 62 threadedly received in a plate 63 welded to the bottom 57 of the housing 26, and locked by a nut 63A. Turning the bolt 62 permits adjustment of the ten¬ sion in the torsion rod 50A in the storage position.Referring now to FIG. 3, the right end of the torsion rod 50 is turned and placed in an aperture illustrated by the dash line 64 in the stanchion 22; and a bracket 65 welded to the stanchion 22 also acts to secure the right end of each torsion rod. Referring now to FIGS. 6 and 7, the latch 30 includes a hex head bolt 68 which has a splined shaft 69 and a threaded end 69A which receives a nut 70. A smooth sleeve 71 having an eccentric bore 72 is received over the splined portion 69 of the bolt 68, located between the side plates 52, 53 of the housing 26. The splines 69 prevent rotation of the sleeve 71; and the eccentricity of the bore 72 permits adjustment of the location of the latching member relative to the cavity 28 on the locking member 27 simply by rotating the bolt 68. Once the adjustment is made, the nut 70 is tightened on the bolt 68 so that the sleeve 71 is frictionally held by the side plates 52, 53 of the housing 26. This adjustment achieves a snug fit of the locking member and is used to com¬ pensate for any warp (i.e. lateral misalignment) of the stanchions. Set screw 33 is tightened to engage the stanchion 22 and take any play out of the structure in the raised, locked position that may be caused by manufacturing tolerances in the pivotal connections at pins 25, 28 and 30 (see FIG. 4). Such tolerances are desirable for this type of structure in the opening and closing movements of the rows--particularly the higher rows which are not as rigid as the lower rows. The weight of the chairs, frame and occupants take out the vertical play. Thus, the adjustable member 33 is operative, only in the locked or open position of each stanchion to re¬ duce horizontal play that would otherwise by present, and which is even desirable during opening and closing movements._OM pera onReferring back to FIG. 2, when the rows are closed, the actuator element 40 is located in a generally downward position, and extends beneath its associated platform. When the next lower row (referring to row 12) is approximately half open, the actuator member 40 is received in the space 38 with the inwardly turned portion of the actuator 40 beneath the surface 37 of the transverse plate 36. When the actuator member is engaged by the beam 21 (which in this case defines the bottom of the slot 38 and limits the actuator so that the actuator is guided against the rear or lifting surface 37) , it rides forwardly until it engages the surface 37, and there¬ after, in cooperation with the torsion rods, lifts the chairs, beam and stanchions in progressive fashion as the row continues to be extended (see row 11) . The stanchions rotate about the pins 25. As the lower end of the stanchion is moved counter¬ clockwise during opening, the center of gravity of the locking member 27 is moved rearward until it becomes over center rela¬ tive to the axis of its mounting pin 28. As opening motion continues, the locking member eventually falls in a snapping action and engages the sleeve 71 of the latching member 30. This normally occurs as the forward surface of the lower end of the stanchion 22 engages the stop member 32 or play compen¬ sation means 33. However, even if the locking member falls sooner in the motion, the surface 29A will act as a safety stop.In reversing the sequence for closing the rows, it will be observed that the space 38 permits the actuator 40 to ride forwardly during the initial relative motion between two adjacent rows--at least until the nose of the upper row en¬ gages and unlocks the locking member 27. The continued rela¬ tive closing motion forces the locking member clockwise about the pin 28, and in a short distance, the nose then engages the rear of the stanchion 22, (which may be provided with a bear¬ ing member 80) so that the continued closing motion forces the seating forwardly and downwardly for storage between adja¬ cent decks, as best seen at the upper left hand portion of FIG. 2. The forward motion of the latching member is limited by pin 25. Referring back to FIG. 1, cover panels 80 are mounτ ted to the lateral flanges provided by the top wall 56 and forward wall 58 of the housing 26. | Clai s1. In a telescoping seating system having a plu¬ rality of rows, each row including a horizontally extending deck, said rows being adapted for movement between a use posi¬ tion in which said decks are extended in stepped relation and a storage position in which said decks are retracted in generally vertical alignment, the improvement characterized by: a plurality of seating means in each row, each seating means including stanchion means pivotally mounted for movement at the rear of said deck between a raised and a lowered position, said seating means further including back means and seat means carried by said stanchion means; actuator means mounted on the forward portion of the next higher row and adapted to engage said seating means as said rows are extended relative to one another for raising said seating means to an upright use position; locking means mounted for movement between a use and a storage position for locking said seating means in the raised position when a lower row is fully extended rela¬ tive to the next higher row, said locking means being con¬ structed and arranged to be unlocked by the relative motion between said rows to permit the forward folding of said seat¬ ing means as said rows are retracted for storage; and energy storage means interconnected between said row and said seating means for partially counterbalancing the weight of said seating means in the lowered position.2. The apparatus of claim 1 wherein said energy storage means comprises torsion rod means interconnected between the rear portion of the deck of one row and associated frame means mounted on that row.3. The apparatus of claim 1 wherein each of said stanchion means is pivotally mounted at its lower end to said deck, and wherein said locking means comprises a leg pivotally mounted to said deck at a position forward of said pivotal mounting of said stanchion means, said locking leg means in¬ cluding a slot for lockingly engaging said stanchion in the raised position.4. The apparatus of claim 3 wherein said actuator means is adapted to engage said locking leg when said lowerIJΪFREX;OMPI y wipo row and the next higher row are moved to a closed position to unlock said stanchion prior to lowering the same.5. The apparatus of claim 1 wherein each of said seating means further includes an upwardly extending opening receiving the actuator means of the next higher row when said stanchion is in the raised position.6. The apparatus of claim 5 wherein said actuator for said seating means is pivotally mounted to the next higher row and depends therefrom in the storage position; said open¬ ing for receiving said actuator including a first surface for engaging said depending actuator when said lower row is ex¬ tended.7. The apparatus of claim 6 wherein said opening is further defined by a second, bearing surface to which said actuator is guided by said first surface and against which said actuator bears during final placement of said seating means in the use position.8. The apparatus of claim 1 wherein said stanchion means are pivotally mounted to said deck of a lower row at a location above said deck and beneath a horizontal extension of the platform of the next higher row; said locking means being pivotally mounted to said stanchion means beneath its pivotal mounting to its associated deck and extending rear- wardly thereform for engaging a fixed member on said deck in locking engagement when said stanchion is fully raised, said locking means being unlocked by engagement with the next higher row when said two rows move to a closing position relative to each other.9. The apparatus of claim 8 further comprising housing means for enclosing the pivotal mounting of the lower portion of said stanchions and for enclosing the lower portion of said locking means in the use position.10. The apparatus of claim 9 further comprising adjustable means on said housing for bearing against said stanchion in the raised 'position for urging the same rearwardl to minimize horizontal play in the pivotal mountings of said stanchion to said deck and said locking member to said stan¬ chion.O 11. The apparatus of claim 10 wherein said fixed member of said locking means comprises a splined bolt; a sleeve eccentrically mounted on said bolt; and bracket means for securing said bolt to said platform to be engaged by said recess of said locking element in the operable position, whereby snug engagement between said recess and said sleeve may be obtained by rotating said bolt about its axis.12. The apparatus of claim 1 wherein said actuator means comprises a link pivotally mounted to the forward end of a higher row and engaging frame means carried by the next lower row section for urging the same to the raised position when the lower row is extended for use.13. The apparatus of claim 12 further comprising adjustable means operative only in the fully raised position of said stanchions for compensating for horizontal play in the mountings of said stanchions and said locking members .OΛ'.PI . wipo ,* | AMERICAN SEATING CO | HARTMAN A |
WO-1979000877-A1 | 1,979,000,877 | WO | A1 | XX | 19,791,101 | 1,979 | 20,090,507 | new | G10D13 | null | G10D13 | G10D 13/08 | MUSICAL INSTRUMENT WITH SPRING BARS AND MANUAL ROTARY ACTUATORS | A musical instrument employing several musically tuned spring bars (2) which are played independently at the option of the user by manually turning rotary actuators (3). Each rotary actuator comprises three parts: a turning wheel (4); a separate portion (5) bearing protusions (19) to engage, flex and release the corresponding musical bar (2) as the user rotates the turning wheel (4) a part of its full rotation; and a part (6) acting with a suitable means such as a leaf type spring (7) serving to brake the actuator each time a bar (2) is struck until the user again rotates the turning wheel (4). The instrument is enclosed in a resonant housing (8) having openings (18) through which a part of each turning wheel (4) extends for access to the player. | DESCRIPTION TitleMUSICAL INSTRUMENT WITH SPRING BARS AND MANUAL ROTARY ACTUATORS Technical Field The invention relates to musical instruments, and in partic¬ ular to those of small size in which the musical tones result from the mechanical vibrating of spring bars fixed at one end. Background ArtThe instrument of the present invention employs small spring musical bars similar to those which have been used widely for over a century in music boxes that automatically play predetermined melodies. Such automatic devices, however, do not serve as real musical instru¬ ments whereby the user creates the musical effect by playing notes ac¬ cording to his own choice of tones, intervals, etc. Some instruments have been invented that employ spring musical bars played at the user's option, such as those disclosed in U.S. Patents Nos. 123,969; 579,031; and 2,788,698, in which the in¬ struments are played by means of a keyboard as in a piano.The instrument of the present invention has certain advan- tages over the prior art because the individual musical bars are played at the user's option by corresponding individual rotary actuators, as disclosed below. Disclosure of the InventionThe general structure of the instrument is that of a base carrying spring bars of various musical tones, rotary actuators with braking means, and a resonant housing.The music producing bars of this instrument are similar to those used in automatic music boxes, and they may be fixed to the in¬ strument's base either singly or in groups, being attached to the base at one extremity and vibrating freely at the other. The bars have varied tonal qualities and are played selectively at the option of the user by corresponding separate rotary actuators. The bars are of dif¬ ferent length, width and thickness according to the musical effect desired. They may have weights to further modify their tone, and they may have dampers to stop their vibration before they are restruck to prevent the noise that occurs when a striker pin touches a bar while it is in vibration.OMPI y* ^ The bars vibrate when the user turns the corresponding ro¬ tary actuators which are mounted on an axle for free separate rota¬ tion. One part of each rotary actuator is conveniently shaped for manual rotation by the user, and another part of each rotary actuator is formed with protrusions that engage, flex, and release the corres¬ ponding bar to vibrate musically when the actuator is turned by the user.Each actuator is biased by a suitable means to a position freeing the bar from the striking protrusions so that the musical vi- bration may continue freely until diminished to zero or reactuated.The instrument is ordinarily enclosed in a resonant housing with one or more openings through which a portion of the rotary actu¬ ators extends for manipulation by the user.A major object of this invention is to provide a soft toned musical instrument of exceptional convenience for persons of nearly every age, physical condition and economic means. To this end, the invention has several advantages over the prior art.First of all, the rotary actuator system allows the instru¬ ment to be much smaller than instruments with other types of actuators such as keyboards. As a result, the instrument is more portable and can be left more conveniently in any number of places.Secondly, the mechanism is considerably less complex than other instruments, with fewer parts to be manufactured and assembled. This simplicity, together with its smallness, allows the instrument to be manufactured quite inexpensively and thus be accessible to a greater number of people.In spite of its small size, the instrument is quite durable since it has no particularly fragile parts. As a result the instru¬ ment can safely be carried about, for example in one's pocket, or be used by children, with little likelihood of damage.Another advantage of this invention is that it is quite free from undesirable operational sounds. The rotary actuators allow for continuous movement in either direction, thereby avoiding the noise likely to occur with other types of actuators that must return back to starting position after each actuation. In addition, while vari¬ ous braking means are possible with this invention, the one described in the best mode and shown in the drawings is entirely noiseless and is possible only with rotary actuators of this kind.O PI^RNAΥλ Since the invention is intended to be a true musical in¬ strument, allowing the user the satisfaction of personal creativity in composing sound combinations or melodies, it is obvious that auto- matic music boxes, which may be as small and portable as this instru- went, are not comparable to this invention because they only allow the playing of predetermined melodies.The instrument of this invention may be made with any num¬ ber of musical notes, but it can satisfy the greatest number of people when it has only a limited group of notes, for example four notes that complement each other as in a basic chord. In this way, the instru¬ ment always gives pleasing results, even when played at random by persons with no musical training. At the same time, four pleasantly related notes can be arranged into a great number of interesting mel¬ odies and thus allow the user a wide range of personal creativity according to his talents. Figures in the DrawingsFigure 1 is a top plan view of the instrument with the housing partially broken away.Figure 2 is a side elevation on the line 2—2 of Figure 1. Figure 3 is a perspective view of the instrument shown inFigures 1 and 2 with the housing partially broken away.Figure 4 is a top plan view showing another version of the same instrument, with the housing partially broken away.Figure 5 is a side elevation on the line 5—5 of Figure 4. Best Mode for Carrying Out the InventionThe drawings illustrate the best mode contemplated for carrying out the invention, with Figures 1, 2 and 3 showing one ver¬ sion of the best mode, and Figures 4 and 5 showing a slightly differ¬ ent arrangement of the same elements. Both versions show four bars and actuators, but any number of bars and corresponding actuators may be used.The instrument has a base (l) which serves as the struc¬ tural support of the other components, namel s musically tuned steel spring bars (2) of different tones, rotary actuators (3) with one portion serving as a turning wheel (4), another portion serving as a striking wheel (5)» and another portion (6) held by a spring (7) serving as a braking unit, and the entire instrument is contained in a resonant housing (8). The musical bars (2) are of selective length and thickness to provide their given distinctive pitch when they are vibrated.In Figures 1, 2 and 3 the bars are mounted in pairs, but they may also be mounted individually or in other groupings such as the comb (9) arrangement of Figures 4 and 5* The bars (2) are mounted at one end by screws (lO) on a raised portion of the base (ll), with the other end extending freely from the mounting.In the drawings only one bar (2) corresponds to each actu¬ ator (3). Other forms of the instrument may have more than one bar for each actuator, for example, to obtain the so called mandolin effect occuring when several bars of the same tone are struck almost simul¬ taneously, or to obtain a richer tone effect by allowing some adjacent bars of the same tone to vibrate in sympathy with the struck bars.The manually operated rotary actuators (3) are mounted for free rotation upon a shaft (12) spaced from the free ends of the bars (2) and supported by upstanding brackets (13). The shaft (12) may be fitted tightly into a deep groove (14) in the supporting brackets (13) as in Figures 1, 2 and 3, or it may extend through the brackets (13) and be held by a suitable head (15) at one end and pin (16) at the other end, as in Figures 4 and 5.The rotary actuators (3) are spaced along the shaft (12) so that one actuator is in position to operate each musical bar (2) or group of bars. In order to provide suitable spacing between the actu¬ ators (3) and to prevent each actuator from contacting the adjacent actuators and possibly causing them to rotate, suitable spacer wash¬ ers (17) may be disposed on the shaft (12).The turning wheel (4) portion of the actuator (3) extends partially through an opening (18) in the housing (8) so as to be ac¬ cessible for turning by the user. The peripheral edge of the wheel (4) may have ridges to afford good finger grip.The striker portion (5) of the actuator (3) has a plurality of radially extending striker protrusions (19) adapted to engage, flex and release the corresponding bar (2) when the actuator (3) is rotated. In the drawings, each actuator (3) has four such protrusions (19) in the striker portion (5) spaced 90° from each other. Other forms of the instrument may have fewer or more protrusions per actuator.Partial rotation of the actuator (3) by the user causes a protrusion (19) to engage and flex the free end of its corresponding bar (2) and then release it so that it springs back and vibrates at its characteristic pitch. After each such flexing and vibrating of the corresponding bar (2) the actuator (3) is retained out of engage¬ ment with the bar (2) by the braking system (6,7) The braking portion (6) of the actuator is preferably of polygonal contour having the same number of sides as there are pro¬ trusions (l9). Thus, in the present embodiment the braking portion(6) is square in transverse section.A leaf spring (7) extends from the base (l) to which it is fixed by suitable means. In Figures 1, 2 and 3 the spring (7) is fitted tightly into a groove (20) of a lower section of the plat¬ form (ll) supporting the musical bars. In Figures 4 and 5 the spring(7) is fitted into a small upstanding bracket (21) on the floor of the base (l). The spring is tensioned to press radially against the outer surface of the braking portion (β) of the actuator and to ride thereon as the actuator (3) is rotated by its turning wheel (4).The spring (7) thus tends to retain the actuator (3) nor¬ mally in a resting position when the spring (7) engages a flat side of the braking portion (6). As the actuator (3) is rotated, the spring (7) flexes to ride over a corner of the braking portion (6) and upon passing dead center of the corner the spring (7) will urge the actuator (3) to proceed to the next successive flat surface con¬ tact with the spring (7) thereby assisting in the rapid release of the flexed bar (2). * The user in moving the turning wheel (4) to impart vibration to the corresponding bar (2) can feel the resistance in the initial movement and then the assistance in the later movement. For this pur¬ pose each protrusion (l9) should be located circumferentially of the striking portion (5) of the actuator at about the same radius position of a corner of the braking portion (6) of the actuator so that the spring (7) will be first past dead center of a corner when the protru-' sion (19) releases the bar (2) and so that when the spring (7) engages a flat side of the braking portion (6) it will retain the actuator (3) in a position where the bar (2) is free to vibrate out of contact with a protrusion (19). The relationship may vary depending upon the angu¬ lar location of the spring (7).The illustrated base (l) and housing (8) are simple in form, but they may have any convenient shape or additional features such as openings for screws for fastening to other objects, or openings for attaching a wristband, etc.The housing (8) and base (l), as well as other parts of the instrument may be decorated as desired. The housing (8) is preferably constructed to serve as a res¬ onant sounding board and/or resonant air chamber.The illustrated housing (8) has no bottom part but fits tightly on top of the base (l). Other forms of the housing (8) may have a bottom piece so as to enclose all sides of the instrument. Exploitation in IndustryThe instrument of this invention can be made of a variety of metals, plastics and wood, preferably by die casting and/or injection molding of the actuators, base and housing, and by stamping of the musical bars and springs. Industrial exploitation is feasible for the following reasonsBecause the parts are very few and small, the instrument can be manufactured quite inexpensively.It is a small and simple instrument, but at the same time durable and of fine musical quality, with appeal for people of all ages and conditions.Besides being a source of musical enjoyment, the instrument is an effective means of relieving nervous tension because it engages the user in a relaxing form of mental and physical activity.In addition tά providing musical pleasure and an outlet for nervous tension, the instrument can be used as a simple communication device.whereby musical codes can be played to convey messages, for example by sick persons unable to speak, or by persons using radio communication. Musical codes can also be used very well to identify persons being paged over loudspeakers, as in a hospital. Because of its small size, the instrument can easily be held in the palm of one's hand, carried about, and left anyplace. It is also suitable for incorporating into other objects, for example pen holders for desks, ashtrays, etc. It can be made miniature enough to wear on a wristband or as a pendant or other form of jewelry. | CLAIMS Various modes of carrying out the invention are contemplated as being within the scope of the following claims. I claim: 1. A manually operable musical instrument having a base (l) and a plurality of musical bars (2) fixed at one end of each to the base and adapted to produce individual generally different musical tones when vibrated, characterized in that said musical bars are vi¬ brated individually and selectively at the option of the user by means of a plurality of manually operable rotary actuators (3) mounted on the base for free separate rotation, each actuator having a first portion (4) destined for contact by the user to manually rotate the same and a second portion (5) generally integral with said first portion to rotate therewith and disposed adjacent to the end of a corresponding bar (2), said second portion (5) having a plurality of circumferentially spaced protrusions (19) positioned so as to flex and release the end of the corresponding bar upon a partial rotation of the actuator thus causing the bar (2) to vibrate upon release from contact, said second portion(5) being formed so that its said protrusions are not touched by the user during said manual rotation, and there being means retaining said pro¬ trusions out of engagement with the corresponding bar (2) except during a part of the rotation of said actuator.2. The instrument of Claim 1 and a housing (8) for said in¬ strument having at least one opening (18) therein through which the irst named portion (4) of each of said corresponding rotary actua¬ tors (3) is exposed for manual operation.3* The instrument of Claim 1 in which said last named means comprises a resilient biasing means normally urging each said rotary actuator rotationally to a position out of engagement with the cor- responding bar.4. The instrument of Claim 1 in which said last named means comprises a leaf o wire spring disposed generally tangentially to each corresponding actuator and pressing thereagainst.5. The instrument of Claim 4 in which the peripheral portion of said actuator contacted by said spring is generally polygonal and said spring presses radially thereagainst whereby engagement by said spring with a lat side of said portion of the actuator tends to re¬ tain said actuator against rotation. 6. The instrument of Claim 1 in which there is only one musical bar per actuator.7. The instrument of Claim 1 in which there is more than one bar of the same tone per actuator. 8. The instrument of Claim 7 in which only one bar is struck by its actuator while the other bar or bars are of such character that they vibrate in sympathy with the struck bar.9. The instrument of Claim 7 in which the several same toned bars corresponding to any actuator are struck and vibrated one a ter the other in rapid succession during one partial rotation of the actu¬ ator before said last named means operates to retain the protrusions out of engagement with the bars.10. The instrument of Claim 1 in which there are two or more bars of different tones per actuator. 11. The instrument of Claim 1 with dampening devices fixed in any manner so as to stop residual vibrations in any bar before it is replayed.O PI | PANEVSKA M | PANEVSKA M |
WO-1979000879-A1 | 1,979,000,879 | WO | A1 | EN | 19,791,101 | 1,979 | 20,090,507 | new | A01M23 | null | A01M23 | A01M 23/24 | A TRAP,PREFERABLY FOR MICE,RATS AND MINK | A trap, preferably for mice, rats, voles and mink. It consists of two substantially rectangular plates (1, 2) of a resilient material, connected to each other along a hinge (3) at one of their short sides, a shorter plate (1) being provided with a first tongue (5) projecting from a short side (4) opposite to the hinge (3) and substantially in the plane of the plate (1), the other long plate (2) being provided at its end remote from the hinge (3) with a second tongue (8) bent under said plate (1), and with a slit (7) in the folding zone (6), the first tongue (5) being disposed for glidably passing through said slit, said bent tongue (8) tapering towards a first short, rectangular lip (9) bent up towards the shorter plate (1) and disposed such that when the long plate (2) is given a resilient and concave curvature in relation to the shorter plate (1), it passes in through an opening (10) made in the short plate (1) and is enabled to remain there by means of bait (12) placed between the first lip (9) and a second lip (11) upstanding from an edge remote from the hinge (3). | A trap, preferably for mice, rats and mink.The present invention relates to a trap, which is distinguished for great effectiveness and that it can easily be produced in large series to an extremely low price. The trap in accordance with the •invention has been given the configuration and characterizing features apparent from the accompanying patent claims.The invention is illustrated by the accompanying drawing, on which Fig. 1 is a perspective view of a trap in accordance with the invention, in a set condition,Fig. 2 is a perspective view of the same trap in an unset condition,Fig. 3 is a side view of the same trap in a set con- dition,Fig. is a plan view from below of the same trap in a set condition,Fig. 5 is a side view of the same trap in an unset condition, and Fig. 6 is a plan view from below of the same trap in an unset condition.Two substantially rectangular plates 1,2 of different lengths are disposed with the longer above the shorter one, and are attached to each other by means of a hinge • 3 along one of their short sides. The shorter 1 of these two plates 1,2 is provided with a tongue 5 pro¬ jecting from its short side remote from the hinge 3, the tongue being bent away from the longer plate•2 such that it forms an angle of 150°-170°, preferably l6θ°, to the shorter plate 1. The long sides of the shorter plate 1 are provided with flanges 14 directed towards the long plate 2. At its free end, the long plate 2 is provided with a tongue 8, bent down under the shorter plate 1 and tapering towards a short, rectangular lip 9. In the folding zone, the long plate 2 is provided with a slit 7 in which the tongue 5 of the shorter plate 1 is • glidably accommodated. The long sides of the long plate 2 are suitably provided with teeth 10 directed towards the shorter plate 1. The tongue 8 of the lon plate 2 is bent in under the shorter plate 1 such th when the long plate 2 is given a concave, arcuate sha in relation to the shorter plate 1, with the tongue o the shorter plate 1 substantially wholly thrust out through the slit 7 , said tongue 8 'will- lie substanti¬ ally parallel to the underside of the shorter plate 1 The lip of the tongue 8 is bent in towards the sho ter plate 1 such that' it forms an angle of 85°-110° t the tongue 8 and such that it will pass in through a rectangular opening 10 made in the shorter plate 1, when the long plate 2 is given the concave, arcuate shape in relation to the shorter plate 1. From the si of this opening 10 nearest to the hinge 3, there is a second lip 11 bent up at an angle of 25 -45° to the shorter plate 1, and of a length such that its free e is situated at a distance of at least one fifth of th whole length of the previously-mentioned lip 9 from i free end and so close to the lip 9 that bait 12, plac* *! between the two lips 9,11, is pressed against the oth lip 11, thus preventing the bait 12 from gliding out the opening 10. When a animal, attracted by the bait 12, thrusts i head towards the bait 12 and pulls-it away, the lip 1 glides out of the opening 10, the long plate 2 straig out and, guided by the tongue 5, comes down with grea impact over the neck of the animal and presses the fo against the flange 14 of the shorter plate 1. It has found advantageous to form the shorter plate 1 wider the long plate 2 such that this plate can pass betwee the flanges 14 of the shorter plate 1 when the long p straightens out so that the flanges 14 act as shearin edges. It has further been found advantageous to make flanges so high that they attain the same height as t upper edge of the bait 12, and to provide them with aOM4 At, V-shaped notch opposite the bait 12, this notch ha¬ ving a greatest width such that it corresponds to that of the necket of the animal. The edges of the notch will then be pressed with great force against the jugular vein of the animal and, if the blow has not already led to its death, stop the supply of blood to its brain which after a few seconds results in un- conciousness and death.OMPI . A, W1PO ,Λ» | Claims1. A trap, preferably for mice, rats, voles and mink, characterized in that it consists of two sub¬ stantially rectangular plates (1,2) of a resilient material, connected to each other along a hinge (3) at one of their short sides, the shorter plate (1) being provided with a first tongue (5) projecting from a short side (4) opposite to the hinge (3) and substantially in the plane of the plate (1), the other long plate (2) being provided at its end remot from the hinge (3) with a second tongue (8) bent und said plate (1), and with a slit (7) in the folding zone (6), the first tongue (5) being disposed for gl dably passing through said slit, said bent tongue (8 tapering towards a first short, rectangular lip (9) bent up towards the shorter plate (1) and disposed such that when the long plate (2) is given a resilie and concave curvature in relation to the shorter pla (1), it passes in through an opening (10) made in th short plate (1) and is enabled to remain there by me of bait (12) placed between .the first lip (9) and a second lip (11) upstanding from the edge (4) remote rom the hinge (3).2. A trap as claimed in claim 1, characterized in that the long plate (2) is longer than the shorter plate such that in a set condition it forms an arc w a height great enough for an intended animal to put head under it and remove the bait (12).3. A trap as claimed in claim 1, characterized in the long plate (2) is provided with teeth (13) along long edges and facing towards the shorter plate (1).4. A trap as claimed in claim 1, characterized in the shorter plate (1) is provided.with flanges (14) its long sides and facing towards the long plate (2)5. A trap as claimed in claim 1, characterized in the tongue (5) of the shorter plate (1) is slightly away from the long plate (2).6. A trap as claimed in claim 5, characterized in that the tongue (5) forms an angle of 150°-170° to the plate (1). 7. A trap as claimed in claim 6, characterized in that the tongue [ 5 ) forms an angle of 160 to the plate (1).8. A trap as claimed in claim 1, characterized in that the first lip (9) forms an angle of 85°-110° to the second bent tongue (8).9. A trap as claimed in claim 1, characterized in that the second lip (11) forms an angle of 25°-45° to the shorter plate (1).10. A trap as claimed in claim 9, characterized in that the second lip (11) is disposed to lie against a bait (12) placed between, the two lips (9,lD> in the set state of the trap, and at a distance from the free end of the first lip (9) corresponding to at least one fifth of the total length of the first lip (9).IJUREATJ*-OMPI . A. W1PO Λ*v | RYDBERG S | RYDBERG S |
WO-1979000893-A1 | 1,979,000,893 | WO | A1 | EN | 19,791,115 | 1,979 | 20,090,507 | new | A45C11 | null | A45C11, A63B49 | A45C 11/00, A63B 49/18 | RACQUET DISPLAY CASE | A racquet display case (12) for carrying, displaying and storing a racquet of predetermined overall length, the racquet having a handle of a predetermined cross sectional area and a head of a predetermined thickness and span. The case (12) has a rigid frame defining a center opening (60), the preferred embodiment of the rigid frame includes a generally parallel upper (20) and lower (22) nan of length substantially equal to but slightly greater than that of the overall length of the racquet, and a first (16) and second (18) generally parallel end run extending between the upper (20) and lower (22) runs. The upper (20) and lower (22) runs are spaced from one another a distance substantially equal to but slightly greater than the span of the head end of the racquet. The frame (12) includes means for holding the racquet in confining relation to the center opening (60). Compartment structure (300) with an access opening are included on the frame and extend along the racquet handle. | SUMMARY OF INVENTIONRACQUET DISPLAY CASEIn the past, there have been numerous types of receptacles, some of which have been especially designed for carrying racquets. Many of these have been in the form of a racquet head pocket into which the head of a racquet is positioned and clamped or captivated with the handle extending from it. Others have been of the suitcase type, i.e., two hingedly connected mating half cases or half receptacles which open along a hinge line like a clam to gain common access to a receptacle interior separated by septums into a main area to receive a racquet and other sub- sidiary areas clustered about the main area to receive tennis balls or other paraphernalia. This invention is of an improved racquet carrying display and stor¬ age frame or case which is not composed of hingedly connected parts or of a pocket into which the head of the racquet is adapted to be thrust, but, rather, is in the form of a ring sized to bound the outline of the main plane of the racquet head and within which ring the racquet is adapted to be protectively held and displayed and which device is further provided with separate, independent, parallel, elongate compart¬ ment structure aligned on opposite sides of the handle of the racquet and bounded by the ring, and wherein the ring and compartment structure are character¬ ized by a common main plane of symmetry which is, generally speaking, common to a racquet when protec¬ tively housed and displayed within the frame.The shape of the minimum amount of space which is ordinarily occupied by a racquet is, generally speaking, clumsy because the racquet is usually rounded at one end and includes a central, elongate handle or stem extending from the head. In short, a racquet stored separately without a receptacle for it cannot readily be aligned vertically or horizontally, and, most often, it is stored with its longitudinal centerline at a tilt angle. The concept of the present invention is the provision of a racquet carrying case of minimum size which provides a gener¬ ally horizontally aligned protective shield and wherein the racquet is displayed in a horizontal attitude for carrying it or storing it. The carrying case utilizes spaces on opposite sides of the handle of the racquet and between the racquet handle and the ring to provide auxiliary compartment structure connected to the ring or frame. Generally, the invention is of a relatively thin racquet case which is not substantially longer than the overall length of a racquet and not substantially wider than the netted end of the tennis racquet and not substan- tially thicker than the racquet handle except for the auxiliary comaprtments so that minimum space is required to protectively house a racquet and in which the racquet is displayed. The device is adapted to receive two racquets in parallel, side-by-side rela¬ tion on opposite sides of a common plane of symmetry in an alternative embodiment described hereinafter.Technical Field:This invention relates to a relatively thin racquet carrying and racquet display structure or case which includes a frame loop which is of optimum size in that it makes maximum use of space within which a racquet is to be protectively housed and displayed when not in use and which peripherally bounds three separate zones, a first main zone where¬ in a racquet is protectively located and secured and ■ a pair of elongate auxiliary compartment zones, one on each side of the racquet handle and generally parallel to it and which compartment zones are each provided with compartment structure; and the compart¬ ment structure first main zone and frame are all characterized by a common plane of symmetry.OMPI Background Art:In the past there have been numerous types of racquet cases. For example, U.S. Letters Patent 298,125 shows a case for lawn tennis implements which comprises a single compartment where everything is housed together in contrast to the instant invention where there are there independent and compactly arranged compartments which are arranged in spaced relation with respect to one another by a circum¬ scribing frame or skeletal ring. U.S. Letters Patent 1,027,786 is for a racquet case and press wherein a single compartment system for a tennis racquet is provided without regard to the provision of space for balls and other tennis equipment; and, moreover, this prior art device is for a racquet case with a built-in press. U.S. Letters Patent 1,541,895 is of a container for a tennis racquet; however, the utilization of space and the compact arrangement of the compartments is not as set forth and claimed in this invention. The travel kit and game of U.S. Letters Patent 3,990,573 is of an executive travel kit utilizing a single enclosure system primarily intended for a golf putting arrangement and briefcase. Also, U.S. Letters Patent 4,023,800 is of a pair of side members hingedly connected together and not of an independent' compart- ment system compactly arrnaged in accordance with the geometrical configuration as is more fully set forth hereinafter.An additional U.S. patent in the art is No. 3,963,103 which provides structure to jacket the head of a racquet only with the handle extending from the racquet head jacketing structure and not protectively housed within a frame in a displayed condition. There is also a French patent, 1,565,476, which is of a suitcase type structure, i.e., opens like an oyster shell about a hinge, to provide common access to a plurality of open' compartment structure defined by septums and a racquet press.It will be seen that the instant invention differs from that of the prior art in that it provides a frame loop or frame ring defining a main plane of symmetry and within which the racquet is adapted to be secured generally symmetrically with respect to the plane of symmetry so as to be protectively housed within the ring which includes means to connect to the periphery of the racquet and to the ring wherein the racquet handle extends along a line longitudi¬ nally generally coincident with the longitudinal centerline of the ring, and wherein separate, inde- pendent, elongate compartment structure is provided, one on each side of the handle and within the frame boundary; and wherein the compartment structures are symmetrical with respect to the plane of symmetry through the frame and racquet so that no hinges are required to gain access to the racquet reducing the number of parts required and protectively housing the racquet within the frame so that it is adapted to be displayed while in a protected condition.Objects of the Invention:It is an object of this invention to provide a carrying and display case for a racquet or other equipment, such as tennis balls, which is of an optimized geometric configuration, the main dimen- sions of which are dictated by the outline of the racquet. In other words, a relatively thin racquet case in the form of a frame ring is provided which is of an overall length, overall height, and overall thickness which is dictated by the dimensions of a standard racquet in that a) the overall case length is slightly larger than the overall length of a standard racquet, b) the overall case height is slightly larger than the span across the face of the head of the racquet; and c) the case thickness is slightly larger than that of the racquet handle. On the case longitudinally extending pouches or compart¬ ment structures are provided on opposite sides of the handle zone and between the handle zone and the frameOMP • W1P ring. These are somewhat larger than the handle thickness projecting outwardly slightly but in sym¬ metrical relation with respect to a longitudinally extending center plane through the case. Structure is also provided on the frame ring to hold the rac- quet protectively within the ring.It is another object of this invention to provide a racquet case characterized by an outer ring defin¬ ing the thin case frame and wherein the ring is spanned by the faces of the racquet and wherein a first elongate upper compartment and a second elong¬ ate lower compartment are provided on opposite sides of the zone of the case which receives the racquet handle.Generally speaking, it will be apparent from the following description that it is an overall object of this invention to provide an improved, inexpensive and convenient to use racquet carrying case which may be utilized for carrying not only the racquet, but associated equipment, such as balls and for storing the same in a compact condition in a realtively small compartment and closets when not in use and in which the racquet is adapted to be displayed as will be appreciated by those familiar with the decorative designs of relatively expensive tennis racquets. In accordance with these and other objects which will become apparent hereinafter, the instant inven¬ tion will now be described with reference to the accompanying drawings in which: Brief Description of the Drawings: Figure 1 is a side elevation view of the instant invention;Figure 2 is a top plan view of the device shown in Figure 1;Figure 3 is a view in cross section taken on the plane indicated by the line 3-3 of Figure 1;Figure 4 is a veiw in cross section taken along the plane indicated by the line 4-4 of Figure 1 and looking in the direction of the arrows; and_OMPI_ y Figure 5 is a view similar to that shown in Figure 4 and illustrating an alternative embodiment of the instant invention wherein two racquets are housed in the carrying case.Detailed Description of the Preferred Embodiment:Referring to the drawings wherein like reference characters designate like or corresponding parts throughout the several views, and referring parti¬ cularly to Figure 1, there is shown a racquet carry- ing and display frame or case generally designated by the numeral 12. It includes a frame ring of inter¬ connected or interjoined runs, an end run 16, an opposite end run 18, and an upper run 20 and a lower run 22. In the embodiment illustrated, see Figure 4, these runs are shown as being hollow or tubular with outer, inner and side surfaces 25, 26, 27 and 28; however, the same may be solid. Additionally, as shown, a peripheral decorative band 29 may be pro¬ vided which also serves to maintain mating ring run parts together along a line of abutment and of junc¬ ture 31; however, any type of run structure may be utilized in defining the frame ring. Generally speaking, in the preferred embodiment, the skeletal ring or frame construction utilized is of rigid plastic material and is provided with a pair of support feet generally designated by the numerals 32 and 33. In Figure 4 it is seen that the supports diverge defining two outwardly-extending feet por¬ tions 34 and 36 to provide stability. In the embodi- ment shown, a slim line design is illustrated; the upper run side surfaces diverge downwardly with respect to one another as do the side surfaces of the lower run 22. Alternatively, the cross-sectional area of the runs of the ring may be of common size. In any event, it is seen that a carrying and display case or ring is provided, and the overall length of the carrying case, i.e, the distance between the frame end runs is slightly greater than the overallf Oi length of the racquet, but not sufficiently great so as to permit tilting of the racquet from the position shown in the drawings to an askew position. Further, the distance between the upper and lower runs is slightly greater than the overall span across the head end of a racquet but no substantially greater. There is thus defined a case or frame interior which may be considered as having a main plane of symmetry which is common with respect to the runs of the frame and generally coincident wiht the main center plane of a racquet when positioned therein as shown in Figure 1 and which plane may be considered to be represented by the line designated by the numeral 31 in Figure 3. It will also be recognized that there is a longitudinally-extending centerline of the racquet shown in Figure 1 which is generally coin¬ cident with a longitudinally-extending centerline through the frame extending through the end runs and is generally designated by the numeral 41 in Figure 3.. It may be considered that, above this line 41 there is a zone, which is designated by the letter A, adjacent the upper run and the end run 16; and a lower zone, designated by the letter B, which is adjacent the lower run 22 and the end run 16, the zones A and B being on opposite sides of the longi¬ tudinally-extending centerline 41 of the frame. Extending from the frame there is a septum with opposite main outer faces which preferably is of rigid plastic material having opposite outer faces 54 and 56. Septum as used herein means a wall generally and a dividing wall particularly with respect to the outer runs and the cutout. This may be considered to be a skin joining the runs of the frame; and it may be composed of two spaced parallel sheet pieces or it may be a single rigid sheet spanning the frame. In any event, the septum defines a cutout generally designated by the numeral 60 which includes a first portion 62 sized to receive the head end of a racquet and a second portion 64 which is elongate and extends^ 'zύ 'a tA ijOMPI'A* WlPO from the first potion toward the first end run 16 of the frame and which is sized to receive the handle of the racquet. Holding means are provided on the frame to hold and orient a racquet generally as shown in Figure 1 and designated by the numeral 70 in this cutout. The holding means in the embodiment shown include the septum extending from the frame and clamp means, such as that designated by the numerals 80, 82, 84 and 86, which extend from the septum slightly into the coutout gripping at their extending or terminal ends, a jacket generally designated by the numeral 90 which is sized to receive the head end of a racquet and includes an access opening 92 which may have a zipper closure 94 which can be opened by movement of the operator ring 96. It is thus seen that a person using the racquet may open the zippered opening, insert the racquet and the racquet will be held in the position shown in Figure 1 with the stem of the handle 101, which is often highly decorative, being displayed. Alter- natively, although not shown, the clamps might engage the side surface of the racquet head without the use of the jacketing means 90 for full display of the racquet.The frame is provided with a carry handle 103 on pivot means 105 and 107 connected to the upper run 20; the handle can be rotated into the down and out-of-the-way position shown in Figure 1, that is, in the recessed portion 109 of the top run 20.Referring to the zone A, a compartment means generally designated by the numeral 204 is provided which, it is seen, includes an upper surface 206, a lower surface 208 and side surfaces 210 and 212 bounding a zone or chamber 214 sized to receive a tennis ball or group of tennis balls. Additionally, a hinge is provided as at 222 for pivotal movement of the side surface 212 which comprises a door, and there is a keeper means 240 provided on the upper run20 with snap means 246 for snapping engagement with^BUk f _ O ^ i the side surface 212 to hold it in the position shown in Figure 3 for convenient access. Similarly, lower compartment means designated by the numeral 300 are provided in the zone designated by the numeral B and the structure will not be there redescribed for purposes of brevity with the excpetion of noting that the compartment means, either the one in zone A or zone B, or both, may be separate units suitably fixed as by adhesive means or other means to the frame or the septum which extends from the frame. As shown in Figure 5, the device is adapted to have two jackets 90 and 91 in close, side-by-side relation adapting the case for carrying two racquets simultaneously and displaying the same conveniently, if desired. While the structure shown in the drawings is shown in a preferred embodiment, it is recognized that departures may be made therefrom within the scope of the overall concept of utilizing an open sided frame to protectively ring a racquet, which frame has a geometrical configuration that, as seen in side elevation circumscribes the tennis racquet by an upper and lower line which are parallel and end lines and wherein the zones on the opposite sides of the handle of a racquet held and displayed in the frame are utilized as compartments for balls or other play-related items and there is thus defined a three compartment unit, each of which compartment may be opened as desired by use of the zipper or other type fastener means and the racquet and tennis equipment are adapted to be easily transported and conveniently utilized. | ClaimsWhat is claimed is:1. A racquet case for carrying, displaying and storing a racquet of a predetermined overall length,5 the racquet having a handle of a predetermined cross sectional area and a head end of a predetermined thickness and span, said case comprising: a rigid frame defining a center opening, the rigid frame including an upper and lower run in-]_0 spaced parallel relation and of a length substan¬ tially equal to but slightly greater than that of the overall length of the racquet, and said frame includ¬ ing a first and second end run in spaced parallel relation with respect to one another and extending15 between said upper and lower runs, and said upper and lower runs being spaced from one another a distance substantially equal to, but slightly greater than the span of the head end of the racquet, and each of said runs having an outer and an inner20 surface and spaced side surfaces extending from the outer surface and said side surfaces of each run being equispaced from one another defining a medial main plane of symmetry of said frame, means for holding the racquet in confining25 relation to the center opening extending from the frame to hold the racquet between the runs with the main plane of the racquet oriented generally coin¬ cident with the plane of symmetry, with the handle generally parallel to the upper and lower runs, and30 the head end adjacent the second end run, and compartment means including access means for opening and closing said compartment means carried by the frame and extending along the racquet handle.35 2. The device as set forth in claim 1 wherein means for holding the racquet in confining relation to the center opening comprise:OiWPi -li¬ the runs defining a cutout of a predetermined size generally in the shape similar to, but slightly larger than, a racquet to. be carried and displayed in the frame, said cutout having a first portion closely adjacent the upper, lower and second runs, the first portion being sized to receive the head of the rac¬ quet and the cutout having a second elongate portion extending from the first end run to the second end portion sized to receive the racquet handle.3. The device as set forth in claim 2 wherein the holding means includes means on the inner surface of the runs for engaging the racquet and holding the racquet in confining relation to the center opening.4. The device as set forth in claim 3 wherein said holding means comprises the runs defining the cutout such that the outer inner and spaced side surfaces form a cutout of a predetermined size and shape which engages the racquet head and handle and holds the racquet in confining relation to the center opening.5. The device as set forth in claim 3 compri¬ sing rigid plastic sheet form material bounding said cutout.6. The device as set forth in claim 3 wherein said holding means includes a jacket sized to receive the head end of the racquet and access means for inserting the head end into the jacket means.7. The device as set forth in claim 6 wherein zipper means are provided for opening and closing the access means of said jacket.8. The device as set forth in claim 3 wherein support means including diverging feet are provided on the lower run and extending outwardly with respect to the side surfaces of said lower run. 9. The device as set forth in claim 3 wherein said holding means is arranged to hold a first and second racquet in closely adjacent, parallel, commonly- oriented positions with respect to said medial main plane of symmetry of said frame. 10. The device as set forth in claim 3 wherein said compartment means comprise a first and second compartment, said first compartment being an elongate compartment adjacent said upper run and said second compartment is adjacent said lower run and said second compartment is sized to receive a plurality of tennis balls therein, said compartment means being symmetrical with respect to said plane of symmetry of said frame.11. A frame for use in carrying and displaying a racquet of predetermined size and shape and being of a predetermined maximum thickness, said frame comprising: a top surface and a bottom surface spaced from one another and end surfaces interconnecting the top and bottom surfaces, the end surfaces being spaced from one another a distance substantially equal to the overall length of the racquet, a main septum spanning the top, bottom and end surfaces of the frame, the main septum defines a central cutout zone between the top, bottom and end surfaces, the cutout zone being sized and configured to nestle the racquet bounded by the top, bottom and end surfaces with the handle oriented parallel to the bottom surface, means for releasably engaging the tennis racquet and holding the tennis racquet in the cutout, the means carried on the main septum adjacent the cutout, compartment means carried on the main septum between the top, bottom and end surfaces including a first and second compartment, each of said compart¬ ments being of a width greater than the top, bottom and end surfaces and being symmetrical with respect to a common plane and said top, bottom and end sur¬ faces being symmetrical with said plane, and each compartment including access means, and said top, bottom and end surfaces protectively housing said racquet.12. The device as set forth in claim 11 wherein said septum means comprises rigid plastic material extending from said top, bottom and end surfaces.13. The device as set forth in claim 11 wherein band means are provided about said top, bottom and end surfaces.14. The device as set forth in claim 11 wherein said top surface includes a recess intermediate said end surfaces and handle means are provided in spanning relation of said recess and pivot means are provided mounting said handle means to said frame.15. The device as set forth in claim 11 wherein said means carried on the septum means to releasably engage the tennis racquet comprise a jacket sized to receive the head end of the racquet and access means for insertion of the racquet into said jacket means and closure means for closing said access means. | INTENGAN F | INTENGAN F |
WO-1979000900-A1 | 1,979,000,900 | WO | A1 | XX | 19,791,115 | 1,979 | 20,090,507 | new | H01J37 | null | H01J37, H01L21 | H01J 37/317B, T01J 237/304H4R, Y01N 4/00 | LOW-DENSITY PATTERN IN A PHOTORESIST | By modifying the raster scanning mode of operation of an electron beam exposure system, it is practicable to directly define low density features (100-102) in a relatively insensitive positive photoresist (10) that exhibits high resolution and good processing characteristics. As a result, it is feasible to utilize such a system as an adjunct in what is otherwise a photolithographic fabrication process to define certain critical features of a micro-miniature device. | A LOW-DENSITY PATTERN IN A PHOTORESISTTechnical FieldThis invention relates to the fabrication of semiconductor devices and circuits and, more particularly, to a microlithographic process that includes both photo- beam and electron beam lithographic steps. Background of the InventionIt is known to utilize direct electron lithography and photolithography during respectively different steps of a process for fabricating a microminiature integrated device. In such a process, an electron beam exposure system is advantageously employed to define some of the more critical features of the device. The other features are defined photolithographically.For the electron lithographic step(s) of such a hybrid process, highly sensitive electron resists are available. By utilizing these resists, it is economical in some cases to expose even large areas of a resist-coated wafer with an electron beam system. But, in practice, such resists are typically characterized by (1) relatively poor resolution of developed patterns in thick films, (2) relatively poor tolerance to many dry etching processes of practical importance and (3) the disadvantage that the substitution of electron resists for photoresists in a photolithographic fabrication sequence requires modification of a number of the standard photolithographic processing steps other than the exposure step itself. For these reasons in particular, proposals to utilize an electron beam system to complement a photolithographic device fabrication process have not heretofore usually appeared attractive.Moreover, in such a hybrid fabrication process, it appeared not to be feasible to expose a relatively insensitive photoresist (rather than a sensitive electron resist) with a high-speed electron beam system of the raster scanning type. Summary of the InventionIn accordance with a basic aspect of the principles of the present invention, applicants recognized that, by uniquely modifying the raster scanning mode of operation of an electron beam exposure system, it is practicable to directly define low-density features in a relatively insensitive positive photoresist that exhibits high resolution and good processing characteristics. As a result, it is feasible to utilize such an electron beam exposure system as an adjunct in what is otherwise a photolithographic fabrication process to define certain critical features of a microminiature device.In particular, applicants' invention is a new method of operating a raster-scan-mode-of-operation electron beam lithographic system to irradiate a photoresist-coated workpiece that is supported on a continuously moving table. The method comprises the step of generating deflection signals that compensate for both table motion and the regular raster scan deflection signals of the system to cause the electron beam to dwell only on each of a plurality of selected portions of a low-density pattern for a time that is substantially greater than the time during which each portion would be exposed during regular raster scanning of the surface of the workpiece.In one specific embodiment of applicants' invention, an electrostatic deflector is added to a conventional electron beam exposure system of the raster scanning type. During selected intervals of time, the beam is unblanked and the added deflector is controlled to exactly compensate for the raster scanning signals generated by the standard electromagnetic deflection unit of the exposure system. In that way, the electron beam is in effect held stationary with respect to each of selected portions of a photoresist-coated workpiece for a sufficiently long time to achieve a specified degree of chemical action to result in the desired pattern being formed upon subsequent development. In another specific embodiment, the aforenoted electrostatic deflector is not included in the electron column of the exposure system. In that case, the raster scanning signals provided by the standard electromagnetic deflection unit are modified to provide a resultant set of signals tnat are equivalent to the composite signals achieved by generating both electromagnetic and compensating electrostatic deflection signals.In some embodiments of the present invention, it is advantageous to provide a variable-spot-size capability for the electron exposure system. In that way, the sizes of the selected photoresist portions being irradiated can be selectively controlled. This may be achieved, for example, by providing in the electron column two spaced- apart apertures with a deflection unit therebetween. In such a system, it is feasible to rapidly deflect.the image of-the first electron-beam-illuminated aperture thereby to alter the portion of the second aperture that is illuminated by the beam. Subsequently, the beam propagated through the second aperture is demagmfied to form a variable-size writing spot on the surface of a resist- coateά workpiece.Other ways of controlling the writing spot size are practicable. For example, the strength of one of the electromagnetic lenses included in the column may be controllably varied to form a larger or smaller image. In that case, another electromagnetic lens downstream of the varied one is correspondingly adjusted to form a focussed image of the variable-spot-size beam on the surface of the workpiece.Brief Description of the DrawingA complete understanding of the present invention and of the above and other features thereof may be gained from a consideration of the following detailed description presented hereinbelow in connection with the accompanying drawing, in which:FIG. 1 is a diagrammatic representation of a specific illustrative electron beam exposure system made in accordance with the. principles of the present invention;FIG. 2 is a simplified layout map of a portion of a photoresist-coated semiconductor wafer showing three contact window regions to be irradiated; FIG. 3 shows the manner in which the regular y- άirection raster scanning deflection signals are compensated for at those positions where irradiation of the photoresist layer is to occur; andFIG. 4 illustrates the way in which the x deflections of the exposure system are controlled during successive y-direction scans. Detailed DescriptionFIG. 1 depicts a specific illustrative lithographic apparatus for controllably moving a variable- size electron spot to any designated position on -the top surface of a photoresist layer 10 supported on a substrate 12. In turn, the substrate 12 is mounted on a conventional x-y-movable table 16.The electron beam apparatus of FIG. 1 may be considered to comprise two main constituents. One is the column itself and the other is equipment 14 connected to the column for controlling the operation of various elements therein. The column is characterized by highly accurate high-speed deflection and blanking capabilities generally similar to those exhibited by the columns described in ϋ. S. patent 3,801,792, issued April 2, 1974 to L. H. Lin and in ϋ. S. patent 3,900,737, issued August 19, 1975 to R. J. Collier and D. R. Herriott. In addition, the particular column depicted in FIG. 1 is further characterized by a variable-spot-size scanning capability.The other main constituent of the FIG. 1 apparatus comprises control equipment 14. Illustratively, the equipment 14 is of the general type described in the aforecited Collier-Herriott patent. The equipment 14 supplies electrical signals to the described column to systematically control deflecting, scanning and blanking of the electron beam. Moreover, the equipment 14 suppliesOM 7 control signals to the x-y table 16 to mechanically move the work surface 10 during the electron beam scanning operation, in a manner now well known in the art.The specific illustrative electron column of 5 FIG. 1 includes a conventional electron source 18. For example, the source 18 comprises a standard lanthanum hexaboride electron emitter. In the immediate downstream vicinity of the source 18, the trajectories of electrons emanating from the source 18 go through a so-called10 crossover or source image point 20 which, for example, is about 50 micrometers in diameter. Thereafter the electron paths successively diverge and converge as the electrons travel downstream along longitudinal axis 22 toward the work surface 10.15 Illustratively, the electron column of FIG. 1 includes standard coils 24 by means of which the electron . trajectories emanating from the crossover point 20 may be exactly centered with respect to the longitudinal axis 22. Thereafter the electron beam is directed at a mask plate 26 0 which contains a precisely formed aperture 28 therethrough. The beam is designed to uniformly illuminate the full extent of the opening or aperture 28 in the plate 26 and to appear on the immediate downstream side of the plate 26 with a cross-sectional area that corresponds exactly to the-~- ~ configuration of the aperture 28.By way of example only, the mask plate 26 ofFIG. 1 is shown mounted on and forming an integral unit with an electromagnetic field lens 30. Inclusion of the lens 30 in the FIG. 1 column is not always necessary. And, even when included, the lens 30 may if desired be separate and distinct from the plate 26. If included, the lens 30 is not usually designed to magnify or demagnify the cross- sectional configuration of the electron beam on the downstream side of the plate 26. But, in combination with35 a next subsequent downstream lens, to be described later below, the lens 30 serves to maximize the transmission of electrons along the depicted column and to selectively control the locations of successive crossover points on the axis 22.The cross-sectional configuration of the electron beam that passes through the mask plate 26 of FIG. 1 is determined by the geometry of the aperture 28. In turn, this beam configuration propagates through a conventional electromagnetic lens 36 (for example, an annular coil with iron pole pieces) which forms an image of the aforedescribed aperture on a second mask plate 40. The plate 40 contains a precisely formed aperture 42 and, illustratively, is mounted on and forms an integral unit with electromagnetic field lens 44.A predetermined quiescent registration of the image of the aperture in the mask plate 26 on the plate 40 of FIG. 1 is assured by, for example, including registration coils 46 in the depicted column.The location of the image of the electron-beam- illuminated aperture 26 on the second mask plate 40 of FIG. 1 is selectively controlled in a high-speed way during the time in which the electron beam is being scanned over the work surface 10. This is done by means of deflectors 48 positioned, for example, as shown in FIG. 1 to move the beam in the x and/or y_ directions. Advantageously, the deflectors 48 comprise two pairs of orthogonally disposed electrostatic deflection plates. Electromagnetic deflection coils may be used in place of the electrostatic plates, but this usually leads to some loss in deflection speed and accuracy. Whether electrostatic or electromagnetic deflection is employed, the deflectors 48 may also be utilized to achieve registration of the image of the aperture in the plate 26 on the second mask plate 40. This is done by applying a steady-state centering signal to the deflectors 48. In that case the separate registration coils 46 may, of course, be omitted from the column. T e cross-sectional area of the electron beam transmitted through the apertured plate 40 of the electron column of FIG. 1 is subsequently demagnified. This is done by means of three conventional electromagnetic lenses 64,^ '4* 7 66 and 68 positioned downstream of the plate 40. In one specific illustrative embodiment of the principles of the present invention, these lenses are designed to achieve an overall demagnification of the beam propagated therethrough by a factor of 400. More particularly, these lenses are selected to demagnify the aforementioned cross-sectional area of the beam transmitted by the mask plate 40 and to image a reduced counterpart thereof on the work surface 10. For an overall demagnification of 400, and for a specific illustrative case in which the cross section of the beam immediately downstream of the plate 42 measures 200-by- 800 micrometers, the electron spot imaged on the surface 10 will quiescently be a rectangle 0.5 micrometers wide and 2.0 micrometers high. The other elements included in the column ofFIG. 1 are conventional in nature. Except for one deflector unit, these elements may, for example, be identical to the corresponding parts included in the columns described in the aforecited patents and application. These elements include a beam-limiting apertured plate 70, electrostatic beam blanking plates 72 and 74, an apertured blanking stop plate 76 and electromagnetic deflection coils 78 through 81.If the beam blanking plates 72 and 74 of FIG. 1 are activated, the electron beam propagating along the axis 22 is deflected to impinge upon a nonapertured portion of the plate 76. In that way the electron beam is blocked during prescribed intervals of time from appearing at the surface 10. If the beam is not so blocked, it is selectively deflected by the coils 78 through 81 to appear at any desired position in a specified subarea of the work surface 10. Access to other subareas of the surface 10 is gained by mechanically moving the surface by means, for example, of a computer-controlled micromanipulator, as is known in the art.In addition, the column of FIG. 1 includes deflectors 82. The purpose of these deflectors* will be described later below. The column shown in FIG. 1 is controlled by equipment 14 to operate in a so-called raster-scan-mode- of-operation. This mode, which is described in the aforecited Collier-Herriott patent involves successively scanning the beam on the work surface 10 along parallel equally spaced-apart scan lines. Illustratively, each such scan line may be considered to comprise multiple equally spaced-apart address positions. At each address position during traversal of a scan line, the electron beam is blanked or not in the manner described above.Additionally, the area of the beam that impinges upon the work surface 10 at each address position is selectively controlled.As the variable-size electron spot is deflected along a row of the scan field, the spot is intensity modulated by the beam blanking plates 72 and 74 at, for example, a 20 megahertz rate. This modulation rate corresponds with a single-address exposure time of 50 nanoseconds, which is compatible with the sensitivities of available sensitive electron resist materials.The aforedescribed raster-scan-mode-of-operation constitutes an advantageous mode that in practice is the basis for high-precision high-speed operation of. an electron beam exposure system. Systems embodying this advantageous mode are in use in industry for fabricating microminiature semiconductor devices and circuits.As stated earlier above, it is known to utilize direct electron lithographic techniques in a hybrid device fabrication process to define some of the more critical features of the device, thereby to achieve, for example, increased packing density as well as improved speed and power characteristics. But, for the reasons stated earlier above, the use of sensitive electron resists for the electron lithographic step(s) of such a hybrid process often is not attractive. Moreover, it appeared not to be feasible to expose a relatively insensitive photoresist (rather than a sensitive electron resist) with a high-speed electron beam system of the aforedescribed raster scanningOMPI . V> 1PO type.In accordance with a basic aspect of the principles of the present invention, applicants recognized that, by modifying the raster scanning mode of operation of an electron beam exposure system, it is practicable to directly define low-density features in a relatively insensitive positive photoresist that exhibits high resolution and good processing characteristics. As a result, it is feasible to utilize such an electron beam exposure system as an adjunct in what is otherwise a photolithographic fabrication process to define certain crtical features of a microminiature device.In particular, applicants recognized that certain low-density patterns whose constituent elements are more or less uniformly distributed over each chip area of a wafer could be exposed in a relatively insensitive photoresist without reducing the overall speed of operation of a raster scanning electron beam exposure system. To do this, it was found necessary to alter the standard raster scanning format in a unique way, which will be described in detail later below.More specifically, applicants have determined that a number of available photoresists can be satisfactorily exposed in currently available electron beam lithographic systems of the raster scanning type. Such a system of, for example, the Collier-Herriott type exhibits a beam current density of about 160 nanoamperes per square micrometer at an anode potential of 10 kilovolts. For such a current density, applicants recognized that the dwell time of the electron beam on each photoresist element to be exposed would have to be increased by about 20 to 100 times over the exposure time for each element achieved in standard raster scanning. In practice, this means that if the throughput of a standard raster scanning machine is not to be significantly reduced, only about 1 out of2ϋ-to-100 standard address positions on the workpiece can be exposed. The area exposed, however, can be considerably higher than l-to-5 percent of the total areaI yy ια. because the standard beam diameter (e.g., 0.5 micrometers) of the basic Collier- Herriott system can be expanded (for example to 2.0 micrometers) by utilizing a variable-spot-size column while maintaining approximately the same current density in the larger exposed element.For purposes of a specific illustrative example herein, it will be assumed that a raster scanning electron beam machine is modified to irradiate a low-density set of regularly spaced-apart regions of a positive photoresist layer. In particular, it will be assumed that the regions to be irradiated are definitive of contact window openings in a microminiature device. Further, it will be assumed that each such opening is to be, for example, a square one micrometer on a side. (Square or rectangular spots are formed by the variable-spot-size column shown in FIG. 1.) Three such square contact window openings 100 through 102 are represented in the layout map of FIG. 2. Because of layout rules prescribed for this particular map, there are no other openings with centers in the dashed-line 6-micrometer-on-a-side squares. Continuous movement of the table 16 (FIG. 1) occurs in the x direction indicated in FIG. 2. Scanning of the electron beam takes place in the y_ direction.As described in the aforecited Collier-Herriott patent, correction signals are applied to the deflection coils 78 through 81 (FIG. 1) to compensate for motion of the table 16. In that way a skewed scan is avoided. The scanning beam is thereby controlled to write at successive locations along a y-parallel line. in accordance with a basic aspect of applicants' invention, signals are also generated to exactly compensate for the regular raster scan deflection signals provided by the coils 78 through 81 of FIG. 1. In one particular embodiment, these compensating signals are provided by the electrostatic deflection unit 82. The particular manner in which this is done along one y_ scan is represented in FIG. 3.In FIG. 3 the straight line that extends be'tween points 1U4 and 105 indicates the deflection that would be imparted to the electron beam by the electromagnetic deflection coils 78 through 81 alone. Such deflection would cause one y-direction scan in the standard raster 5 scanning format. (It is assumed that spaced-apart openings 100 and 102 are centered along this particular scan line.) In accordance with this invention, compensating deflection signals are provided by the unit 82 to cause the beam to in effect dwell at two regions along 0 the depicted scan line. These regions constitute the openings 100 and 102. Significantly, the centers of the regions to be irradiated are not limited to the relatively coarse address structure normally employed in a standard raster scanning system to insure economical throughput.1-5 The compensating signals generated by the deflection unit 82 of FIG. 1 are shown in FIG. 3 as dashed lines. The resultant of the compensating signal represented by the line between points 106 and 107 and the regular deflection signal represented by the line between 0 points 106 and 108 is the line between points 106 and 110. This resulting signal maintains the temporarily unblanked beam stationary centered at y_ position No. 0 for approximately 0.6 microseconds, which is typically not sufficiently long to adequately expose available positive ? ~\ photoresist materials. During that period, a region corresponding to the contact window opening 100 (FIG. 2) is partially irradiated.The electron beam is then blanked again while the resulting deflection signal follows the path from point 110 0 to point 108 to point 112. At point 112, the beam is unblanked again. The resulting deflection signal for the next 0.6 microseconds is represented by the line between points 112 and 114. During that interval the beam is in effect maintained stationary centered at y_ position No. 835 to partially expose a region corresponding to the contact window opening 102.In the particular compensated manner specified above, it is apparent that the scanning beam is controlled to dwell on two defined photoresist regions for a period that is approximately twelve times longer than would be the case if the standard raster scanning mode were not modified. But, for the particular relatively insensitive 5 high-resolution positive photoresists to be specified later below, this dwell period is still not long enough to insure adequate exposure of the photoresist material. (However, in some cases of practical interest wherein more sensitive materials are employed, such dwelling along a single y-scan10 line may be sufficient to provide adequate irradiation of one or more regions therealong. But emphasis herein will be directed to the case wherein still additional irradiation of the region(s) is required.)Hence, in accordance with another aspect of the15 principles of the present invention, the standard raster scanning mode is further modified during subsequent y_ scans to enable additional irradiation of the partially exposed regions. The unique manner in which this is done is illustrated in FIG. 4.20 i FIG. 4, y-direction scan line 116 occurring at x position 0 corresponds to the particular nonlinear y_ scan described above and depicted in FIG. 3. Ordinarily, the next or second y-direction scan line to be described would commence at x position 0.5 and extend parallel to the£ J line 116. But, in accordance with another aspect of the principles of this invention, the path of this second scan line is selectively modified. As shown in FIG. 4, the second y-direction scan line commences at x position 0.5 and initially extends parallel to line 116 for the extent30 of path segment 118. Then, at a _ position corresponding to the upper edge of the dashed-line square 109 (FIG. 2) , an x-direction deflection signal is generated to cause the beam to move to a position centered about point 120 in the FIG. 4 depiction. This point represents the center of the opening 100. Illustratively, this x-direction deflection signal is supplied by the aforespecified deflection unit 82. (As noted above, the point 120 is not limited to being coincident with one of the points defining the relatively coarse address structure of a standard raster scanning system. High-accuracy placement of the point 120 and other center points is thereby possible.)An x-direction deflection signal of the type described above is maintained for the entire interval during which the region 100 is,to be irradiated. During this interval, the beam is unblanked and compensating deflection signals of the type described above in connection with FIG. 3 are also generated in the exposure system. As a result, the beam dwells on the region 100 for an additional 0.6 microseconds.In acco'rdance with one specific illustrative mode of operation encompassed within the principles of the present invention, the standard raster scanning mode is resumed whenever the beam extends outside one of the dashed-line squares represented in FIG. 2. Thus, as shown in FIG. 4, the scanning beam is subsequently blanked and moved rapidly from the position centered about the point 120 to point 122. The point 122 corresponds to the lower left-hand corner point 103- (FIG. 2) of the dashed- line square 109. At that point, the aforespecified compensating x-direction deflection signal is removed. In turn this causes the beam path to follow line segments 123 and 124. It is apparent that the segment 124 represents a portion of the unmodified γ_ scan in a standard raster scanning electron beam exposure system. Subsequently, at point 126, the upper edge of the lower left-hand dashed- line square 127 is encountered. In response thereto, the scanning system is controlled to generate another compensating x-direction deflection signal, which causes the beam to traverse line segment 128. At point 130, which corresponds to the center of region 102 (FIG. 2) , the beam is again unblanked and, while the compensating x-direction deflection signal is maintained constant, compensating y- direction signals of the type shown in FIG. 3 are generated. .As a result, the irradiating electron beam is controlled to dwell again on the region 102.Subsequent __ scans starting from successive spaced-apart x_ positions are represented in FIG. 4. For such scans that fall within one of the dashed-line squares of FIG. 2, the magnitudes of the compensating x-direction deflection signals must be progressively increased, as is apparent from the FIG. 4 depiction. In that manner, by also unblanking the beam and generating compensating y- direction deflection signals in the manner described above, further irradiation of the regions 100 through 103 takes place. In accordance with the specific illustrative depiction of FIG. 4, it is evident that each of the regions 100 and 102, for example, is successively irradiated during each of thirteen 0.6-microsecond-long separate dwell intervals. The cumulative effect of these exposures is to achieve substantially complete exposure of the positive photoresist material in the regions definitive of the aforespecified contact window openings.From FIG. 4, it is seen that normal raster scanning occurs at x positions 6.5, 7, and 7.5. These scans occur in the space between the upper two dashed-line squares of FIG. 2. Of course, if three further dwell intervals were needed to additionally irradiate the regions 100 and 102, even these standard scans could be modified in the way specified above to achieve additional exposure of the photoresist. Although emphasis hereinabove has been directed to a variable-spot-size electron column having a separate compensating deflection unit 82, it is advantageous in some cases of practical interest to modify the column in various ways that fall within the scope of the principles of the present invention. For example, an electron beam exposure system of the type described in the Collier-Herriott patent includes a high-speed high-performance set of electromagnetic deflection coils corresponding to the coils 78 through 81 shown in FIG. 1. In such a system, it is feasible to omit the electrostatic deflection unit 82 and instead to apply composite signals to the coils 78 through 81. In turn, the composite signals generate beam- deflecting signals. These composite signals are in effect the resultant of the above-described table-motion- correcting signals, compensating y-direction signals and compensating x-direction signals.Moreover, the aforementioned variable-spot-size capability may be achieved in alternative ways. Thus, for example, the apertured mask plates 26 and 40 and the deflection unit 48 may be removed from the particular illustrative column represented in FIG. 1. In that case, a variable-spot-size round beam can be realized by 0 selectively decreasing or increasing the strength of, for example, electromagnetic lens 36 and, correspondingly, refocussing lenses 64, 66 and 68 to respectively form a smaller or larger focussed image on the surface of the photoresist layer 10. For simple round features, each 5variable-size image will be characterized by substantially the same current density. (If it is desired to vary the size of a rectangular rather than a round beam, a single beam-defining apertured plate may be included in the FIG. 1 column.) o A number of high-resolution photoresists suitable for inclusion in the herein-described electron beam exposure process are known. One such suitable material is poly(styrene-sulfone) which is a copolymer of sulfur dioxide and styrene. This material exhibits a sensitivity 5of 4-to-8 x 10~5 coulombs per square centimeter at10 kilovolts, is resistant to dry etching processes such as plasma etching and is capable of one-micrometer resolution. This material is described in Journal of the Electrochemical Society, Volume 122, No. 10, page 1370, Qθctober 1975.Other suitable positive photoresists for use in the herein-described process include Shipley AZ-1350J (commercially available from Shipley Co. Inc., Newton, Mass.), Hunt HPR-104 (commercially available from 5Philip A. Hunt Chemical Corp., Palisades Park, N.J.) and GAF PR-102 (commercially available from GAF Corp., Binghampton, N.Y.). Counterparts of the aforespecified Shipley and Hunt formulations are described in U. S. patent 3,201,239, and a counterpart of the aforespecified GAF formulation is described in ϋ. S. patent 3,637,384. These and other known photoresist materials make it feasible to operate a raster scanning electron beam exposure system in the unique manner described herein without substantially affecting the overall speed of operation of the system.Finally, it is to be understood that the above- described arrangements and procedures are only illustrative of the principles of the present invention. In accordance with those principles, numerous modifications and alternatives may be. evised by those skilled in the art without departing from the spirit and scope of the invention. Thus, for example, although emphasis hereinabove has been primarily directed to exposing a resist as a basic step in the process of producing a pattern, it is apparent that the principles of the present invention are also applicable to modifying other types of raster scanning electron beam machines such as those adapted, for example, for micromachining applications or for altering the properties of a semiconductor memory. The dwelling strategy described herein is also applicable to these other types of machines to provide new and advantageous operating modes therefor even if a resist layer is not involved.In addition, in some cases of practical importance applicants have determined that it is advantageous to employ both photo-beam and electron beam techniques in the same resist layer. Thus, for a pattern requiring a combination of small critical features and relatively large less critical features, the small features can be exposed by electron beam lithographic steps of the type specified above and the large features can be exposed by standard photolithographic steps. In subsequent steps, the entire layer, including both photo-beam-defined and electron-beam-defined features, is processed as an entity.'BUK__OM 1P ftK | Cl ai ms1. A method of operating a raster-scan electron beam lithographic system to irradiate a workpiece ( 10. 12) with an electron beam, providing relative movement between the electron beam and the workpiece in an x- direction at a first predetermined rate and in an orthogonal y-direction at a second predetermined rate, CHARACTERIZED BY the step of generating compensating deflection signals to compensate for both the x- and y-direction movement to cause the electron beam to dwell on each of a plurality of selected portions of the workpiece for a time that is significantly greater than the time during which each portion would be exposed during normal raster scanning of the surface of the workpiece at said first and second predetermined rates,2. The method of claim 1 CHARACTERIZED IN THAT the workpiece is coated with a resist film which is relatively insensitive to the electron beam when scanned at said predetermined rates, but is sensitive to the beam when exposed for longer time periods, the beam is blanked during scanning of a majority of the workpiece surface and is unblanked at select points along a particular y- direction scan, said points defining the center of said plurality of selected portions of the workpiece.3.....A method as in claim 2 further CHARACTERIZED BY generating compensating x-direction deflection signals during subsequent y-direction scan intervals to cause the beam to dwell on said specified regions along said particular y-direction scan line during periods of said subsequent intervals.4. A method as in claim 3 CHARACTERIZED IN THAT the step of generating compensating x-direction deflection signals further comprises the step of maintaining the magnitude of said compensating x-direction signal constant during a prescribed period of each different one of said subsequent y-direction scan intervals but progressively increasing said magnitude for respective successive ones of said intervals.5. A method as in claim 4 CHARACTERIZED IN THAT said resist coating constitutes a positive photoresist material characterized by high-resolution and ease of processing. | WESTERN ELECTRIC CO; WESTERN ELECTRIC CO INC | ALLES D; MAC RAE A; PEASE R |
WO-1979000903-A1 | 1,979,000,903 | WO | A1 | XX | 19,791,115 | 1,979 | 20,090,507 | new | C08G59 | null | C08G59 | C08G 59/40B2D, C08G 59/56 | EPOXY SURFACER CEMENTS CURED WITH POLYAMINE-KETIMINE MIXTURES | Room temperature curable epoxy compositions and method are disclosed. The compositions comprise resinous epoxide; a mixed amine-ketimine curing agent comprising a cyclic polyamine having at least two epoxide-reactive, aliphatic amino functional groups, a portion of the amino functional groups in the mixed curing agent being in ketimine form the remainder being in the free amine form; and water in at least about the stoichiometric proportion for hydrolyzing the ketimine groups to the free amine form. The compositions may also comprise inorganic filler such as finely divided silica and sand. The ingredients of the composition are mixed to form a sprayable composition. The working life, or pot life, of the composition can be controlled without excessively affecting the working viscosity or sprayability of the composition by varying the ratio of free amine to ketimine groups in the mixed curing agent and varying the proportion of water in the composition to maintain at least the stoichiometric proportion for hydrolyzing the ketimine groups. | EPOXY SURFACER CEMENTS CURED WITH POLYAMINE KETIMINE MIXTURES.-BackgroundThe present invention relates to room temperature curable epoxy coatings, particularly to room temperature curable epoxy compositions for forming thick protective cement coatings on substrates such as steel and concrete. Resinous epoxid'es are reacted with primary and secondary amines to provide such materials as adhesives, films, cements, floor toppings, highway surfacings, impregnated products such as fiberglass reinforced epox laminates and the like. Epoxy cement compositions are widely used as protective surfacers on concrete and steel substrates such as walls, ceilings, and floors, reactors, storage tanks, etc. which are exposed to corrosive chemicals. Such surfacer cements usually include inorganic fillers such as finely divided silica and graded silica sand, and are applied in thick coatings of from about 1 to 15 millimeters in thickness.Room temperature cured chemically resistant epoxy compos¬ itions are described in U.S. Patent 3,794,609 to Metil, assigned to the assignee of the present application. The disclosure of the Metil patent is incorporated herein by this reference. The patent describes epoxy compositions comprising resinous epoxide, a polyfunctional organic solid amine effective alone as a high temperature curing agent for resinous epoxide, and a solvent for the curing agent which modifies the action of the curing agent to provide room temperature curing. Exemplary amine curing agents are aromatic amines such as metaphenylene diamine, p,p*-methylene dianiline, p,p'-diaminodiphenyl oxi and other cyclic amino substituted compounds. Such compositions have a reasonable pot or working life, for exa 2 1/2 to 3 1/2 hours, and a reasonable setting time, for example, 8 to 48 hours. Such compositions cure by chemical reaction rather than by release of solvent and hence can be used in a very thick coatings.U.S. Patents 3,291,775 to Holm, the disclosure of which is incorporated herein by this reference, describes room temperature curing epoxide compositions comprising resinous epoxide and ketimine curing agents. The ketimine curing agents are reaction products of polyamine curing agents and ketones or aldehydes. Such compositions are stable in the absence of moisture but when exposed to moisture, for example, when coated on a substrate exposed to moist air, the compositions absorb moisture. The ketimine groups of the curing agents react with the absorbe moisutre to form free amine groups, which then react with the epoxide groups to cure the composition. The described compositions are not desirable as cement surfacer compositi because they depend for cure upon absorption of moisture from the atmosphere. Thin films on the order of 0.05 to 0.5 millimeter thick will cure at a reasonable rate by absorption of moisture from the atmosphere. However, such compositions would cure much too slowly, if at all, when applied in thick coatings such as films from about 1 to 15 millimeters in thickness. Moreover, the use of ketimine curing agents alone may not, depending upon the content of inorganic filler, if any, in the composition, provide a composition having sufficient body during its working life for application in thick, sag-free coatings to sub¬ stantially vertical surfaces. The patent also discloses that in addition to ketimines, accelerators such as water and aliphatic polyamines in minor amounts up to about 3% based on the polyamine curing agent may be employed.Other ketimine curing agents for epoxy resins are described in U.S. Patents 3,386,953, 3,432,574, 3,442,856, 3,401,146 and 3,397,178. U.S. Patent 3,337,606 to Floyd describes epoxy compositions containing long chain aliphatic curing agents having a ketimine group and a nitrile group, and states that water may be included in such compositions to accelerate cure. Example IX of the patent shows water used in stoichiometric proportion to the ketamine group. However, although the curing agents described in the Floyd patent are said to give tough, flexible epoxy coatings, they are not desirable for preparing epoxy cement surfacer compositions that must have high resistance and attack by solvents and corrosive chemicals and high- echanical strength when applied in thick coatings. Summary of the InventionA room temperature epoxy coating composition of the present invention comprises a resinous epoxide, a mixed amine-ketimine curing agent comprising a cyclic polyamine having at least two epoxide-reactive aliphatic amino functional groups, a portion of said aliphatic amino functional groups in said mixed amine-ketimine curing agent being in ketimine group form, the remainder being in free amine form; and water in at least about the stoichiometric proportion for hydrolyzing said ketimine groups to free primary amine form. Preferably, the water is present in minor excess between about 0.8 and about 2 times the stoichiometric proportion. The compositions preferably further comprise an inorganic filler such as finely divided silica or a filler such as finely divided silica or a graded silica sand in amounts of between about 1 and about 30 parts by weight per part by weight of resinous epoxide. A method for using such compositions comprises forming a mixture of a resinous spoxide, a mixed amine-ketimine curing agent,-BUREΛi/ OMPI water and inorganic filler, applying such mixture in a layer between about 1 and about 15 millimeters thick to a substrate; and allowing said layer to harden. In another embodiment, the working life of such a composition is con¬ trolled without undesirably affecting the working viscosity by varying the proportion of free amine to ketimine in the mixed curing agent and varying the proportion of water in the composition to maintain at least about the stoichiometric ratio.OM Detailed Description of the InventionHardenable epoxy compositions of the present invention comprise resinous epoxide, a mixed amine-ketimine curing agent, and water in at least about the stoichiometric proportion for hydrolyzing the ketimine. Any resinous epoxide known in the art which can be cured to a solid state by reaction with organic amines may be used in practice of the present invention. Such resins are described in U.S. Patents 3,291,775, 3,386,953, 3,442,856, 3,401,146, and 3,397,178, the disclosures of which are incorporated herein by this reference. Useful resinous epoxides are also described in U.S. Patent 3,794,609, and include aliphatic, cycloaliphatic, and aromatic resinous epoxides. Useful resinous epoxides include the reaction products of polyhydric phenols with polyfunctional halohydrins. Typical polyhydric phenols useful in the preparation of such resins include resorcinol and various bispheonols resulting from the condensation of phenol with aldehydes and ketones such as formaldahyde, acetaldahyde, acetone, methyl ethyl ketone, and the like. A typical epoxy resin of this type includes the reaction products- of epichloro- hydrin and 2,2-bis(p-hydroxyphenyl) propane (Bisphenol A). /Typically, the molecules of the resin have two terminal epoxide groups linked by from 1 to about 10 Bisphenol A units. Another group of epoxy resins are those which are the reaction product of epichlorohydrin and bis (p-hydroxy- phenol)sulfone. Another group of epoxy compounds which may be employed are the glycidyl esters of polymeric fat acids, which are obtained by reacting the polymeric fatty acids with poly¬ functional halohydrins such as epichlorohydrin. Such glycidyl ester resinous epoxides have been commercially available. The polymeric fat acids are prepared by the polymerization of unsaturated fatty acids such as soybean, - UREAIΓOMPI -» WIP0 , linseed, tung, corn, and safflower oils to provide a mixture of dibasic and higher polymeric fat acids.Other types of epoxy resins which may be used in the present invention include the polyglycidyl ethers of tetraphenols which have two hydroxy aryl groups at each end of an aliphatic chain. These are obtained by reacting tetraphenols with polyfunctional halohydrins such as epichlorohydrin. The tetraphenols used in preparing the polyglycdyl ethers are known compounds obtained by con- densing the appropriate dialdehyde with the desired phenol. Still ariother group of resinous epoxides are the epoxidized novalac resins which are obtained by reaction of ephichlorohydrin with the well known novolac resins. The novolac resins are produced by condensation of a phenol with an aldahyde in the presence of an acid catalyst and then condensing the resulting resin with epichlorohydrin in the presence of an alkali metal hydroxide. Typical tetraphenols include tetrakis (hydroxyphenyl) alkanes such as 1,1,2,2-tetrakis(hydroxyphenyl) ethane, 1,1,4,4-tetrakis (hydroxyphenyl) butane, and the like.Epoxy resins that are useful in this invention also include epoxidized olefins such as spoxidized polybutadiene and epoxidized cyclohexenes, and the diglycidyl ethers of polyalkylene glycols, the preparation of which are described in U.S. Patent 2,923,696, which is incorporated herein by reference.Epoxy resins having a high content of aromatic groups are preferred for resistance to chemical attack.In general, the resinous epoxides have more than one epoxide group per molecule, preferably two terminal epoxide groups per molecule. In addition, the resinous epoxides typically have epoxy equivalent weights, that is, the number of grams of resinous epoxide per gram equivalent of epoxide group, of between about 140 and 2,000. The epoxy equivalent weight of the resinous epoxide is also-BU EOMP defined as the mean molecular weight of the resin divided by the mean number of epoxy radicals per molecule. Resinous epoxides having an epoxy equivalent weights of less than about 140 or more thaii about 2,000 may also be used in the practice of this invention.The mixed amine-ketimine curing agents useful in practice of this invention are based upon cyclic polyamines having at least two aliphatic amino groups that are reactive with epoxide groups of a resinous epoxide, at least one of the amino groups being a primary amino group. By aliphatic amino group as the term is used herein, is meant an amino group in which the nitrogen neither is a member of an aromatic ring system nor is bonded directly to a carbon that is a member of an aromatic ring. By this definition, the amino group of aminobenzene is aromatic , whereas the amino group of aminomethylbenzene is aliphatic . Preferably, the nitrogen of each aliphatic amino group is a member of a ring or is bonded to a ring carbon directly or through a one or two carbon divalent radical. These polyamines may be alicyclic (cycloaliphatic) , heterocyclic, and aromatic, and may be saturated or unsaturated and monocyclic, poly- cyclic, or fused polycyclic. They may also be substituted with various substituents such as ester groups, urethane groups, hydroxyl groups, thio groups, ether groups, halogens, and the like. These cyclic polyamines fall into three broad categories:1) aromatic compounds having at least two aminoalkyl sub'stituents, such as 1,3-bis (amino ethyl) benzene, also called m-xylylene diamine, and 1,4-bis (2-aminoethyl) benzene; 2) cycloaliphatic compounds including heterocyclic compounds, having at least two amino or aminoalkyl sub¬ stituents, such as 1,3-bis (aminomethyl) cyclohexane, 1,3-diaminocyclohexane, 3,5,5-trimethyl-3- (aminomethyl)- cyclohexylamine, also called isophorone diamine, N,N'-bis- (2-aminoethyl) piperazine,4,4*-methylene di(cyclohexylamine) , 1,8-diamino-p-menthane, and a poly ethylene polycyclohexyl- amine represented by the structural formula and which can be prepared by condensing aniline with formaldehyde and then by hydrogenating the resulting condensate; and3) heterocyclic compounds in which the nitrogen of a reactive amino group is part of the ring, such as N-(2-aminoethyl) piperazine, in which one ring nitrogen is a secondary amine and hence reactive with epoxides. The preferred polyamine curing agents provide re¬ latively rigid, short cross-links in epoxy compositions, giving hard, dense cured compositions that are resistant to solvents, chemical attack, and discoloration and have excellent mechanical strength and durability. The mixed amine-ketimine curing agent of the present invention comprises a cyclic polyamine as described above or a mixture of such cyclic polyamines. In the mixed amine-ketimine curing agent, a portion of the amino functional groups of the cyclic polyamine are in ketimine form and the remainder of the amino functional groups are in free amine form before the components of the epoxy compositions of the present invention are mixed and allowed to react. The amino functional groups in ketimine form and in free amine form may be distributed in a variety of ways among the molecules of cyclic polyamine that con¬ stitute the mixed amine-ketimine curing agent. Thus, some molecules of the cyclic polyamine may have both amino groups in ketimine form; some may have one amino group in ketimine form and one- amino group in free amine form; and some may have both amino groups in free amine form. Since only primary amines can be converted to ketimine form, a cyclic polyamine having only one primary amino functional group and one secondary amino functional group can have only one of its amino groups in ketimine form. When mixtures of cyclic polyamines are used, one type of polyamine may be largely in ketimine form while another type is largely in free amine form. The mole ratio of ketimine groups to free amine groups in the mixed amine-ketimine curing agent as a whole is more important than the distribution of such groups among the molecules constituting the curing agent.The mixed amine-ketimine curing agent may be prepared from the described cyclic polyamines in at least two ways. In one approach a portion of the cyclic polyamine is re- acted with a ketone as described below to convert substantial¬ ly all or a great proportion of the primary amino groups of the cyclic polyamine to the ketimine form. The resulting cyclic ketimino compound is then mixed with unreacted cyclic polyamine in a proportion that provides the desired ratio of ketimine groups to free amine groups. In another approach, cyclic polyamine is reacted to a predetermined extent with a ketone to produce directly a mixture of reaction products having the desired ratio of ketimine groups to free amine groups. The mixed reaction product thus obtained is employed as the mixed amine-ketimine curing agent in accordance with practice of this invention.When a cyclic polyamine having two primary amino groups such as m-xylylene diamine, is reacted with a ketone, the reaction product may comprise a mixture of unreacted poly- amine, monoketimine, and diketimine products. Such a mixed product may have the desired ratio of ketimine groups to free amine groups, or it may be blended with unreacted amino compound to produce a mixed amine-ketimine curing agent having the desired ratio. Such mixtures are included in the meaning of the term mixed amine-ketimine curing agent as the term is used herein.If desired, the mixed amine-ketimine curing agent may be a single compound in which substantially all of the molecules of the compound have at least one ketimine group and at least one free amihe group. Such a compound may be made by partially reacting a diamino compound, for example, m-xylylene diamine, with a ketone and purifying the result¬ ing mixture of products to obtain a pure product having one amino group and one ketimino group per molecule. Such a compound is also included within the meaning of the term mixed amine-ketimine curing agent as the term is used herein.Cyclic polyamines useful in practice of this invention have at least one primary aliphatic amino functional group. To form the mixed amine-ketimine curing agent, at least a portion of the primary amine groups of the cyclic polyamine are reacted with a ketone to convert the primary amine groups to the ketimine form. The ketimine forming reaction is well known and is described for example in the above mentioned U.S. Patents 3,386,953, 3,442,856, 3,401,146, 3,397,178, 3,432,574, and 3,291,775. See particularly U.S. Patent 3,291,775 which describes the reaction of m-xylylene diamine with methyl isobutyl ketone to produce N,N-di (4-methyl-2-pentylidene) m-xylylene diamine. Ketones useful in the preparation of ketimines for use in practice of the present invention include dialkyl, diaryl, and alkylaryl ketones having a total of 3 to about 13 carbons. Specific examples include acetone, methyl ethyl ketone, methyl n-butyl ketone, methyl isobutyl ketone methyl isoamyl ketone, methyl amyl ketone, ethyl isoamyl ketone ethyl amyl ketone, acetophenone, and benzophenons. Preferred are methyl isobutyl ketone and methyl isoamyl ketone.Mixed amine-ketimine curing agents for use in practice of this invention comprise cyclic polyamines having amino groups in ketimine form and amino groups in free amin form.. Amino groups in ketimine form are included within the term amino functional groups as the term is used herein. At least about one mole percent of the amino functional groups in the mixed amine-ketimine curing agent are in ketimine group form. For example, from about 10 to 90 mole percent of the epoxide reactive amino functional groups may be in ketimine form. Preferably, from about 25 to 75 mole percent of the amino functional groups are in the ketimine form. The proportion of free amine to ketimine may be varied to provide a composition having a working life in the range of from about 1 to 8 hours, desirably at least about 2 hours for sprayable compositions.The use of a mixed amine-ketamine curing agent has a number of benefits. The free aliphatic amino functional groups react quickly with the resinous epoxide when the composition is mixed to provide a sprayable composition that has sufficient body for application to substantially vertical surfaces in thick layers, such as layers of from about 1 to 15 millimeters or more in thickness. The amino functional groups in ketimine form do not participate in the curing reactions until they are hydrolyzed to the free amine form by the water included in the composition. Thus the amino functional groups in ketimine form have a delayed curing action which gives the composition adequate working life. By varying the proportion of ketimine groups to free amine groups in the mixed amine ketimine curing agent, compositions having the desired body and working life for a particular application may readily be formulated. To provide complete cure of thick coatings, compositions of the present invention include water in at least about the stoichiometric proportion for hydrolyzing ketimine groups in the mixed amine-ketimine curing agent to the free amine form, that is, at least about 0.8 mole of water per mole of ketimine group present. It is preferable to employ-BUREAU0 P1 more than the stoichiometric amount of water to assure a more rapid and complete cure. Quantities of water in exce of the stoichiometric proportion, for example, between about 1 and 2 times the stoichiometric proportion, may be used. The incorporation of at least about the stoichiomet proportion of water provides compositions which cure independently of atmospheric moisture. Such compositions cure uniformly even when applied in thick coatings and thu achieve mechanical strength in depth more quickly than compositions which cure from the exposed surface inwardly by absorption of moisture from the air.During the curing process the water hydrolyzes the ketimine groups in the curing agent to produce free amine groups and the ketone from which the ketimine groups were formed. The ketone thus liberated may in part evaporate from the cured coating and in part remain within the cured coating. The presence of such ketone in the cured composi does not appear to deleteriously affect the solvent resis¬ tance, the chemical resistance, or the mechanical strength of the cured composition.Preferably, compositions of the present invention als include an inorganic filler, for example, graded silica sand, finely divided silica such as fumed ilica or pre¬ cipitated silica, and barium sulfate. The fillers contrib to the body or working consistency of the composition duri its working life, lower the cost of the composition, provi a non-slip surface,.and improve the strength of the cured composition. Finely divided silica filler may be included in amounts of from about 1 to 5 parts per part of resinous epoxide. Inorganic filler such as sand may be included in amounts from about 1 to about 30 parts per part of resinous epoxide. Pigments or colorants may also be incluCompositions of the present invention preferably also include accelerators such as phenol, aliphatic.polyamines, mercaptans, acids, and the like. The solvents disclosedjUR0M ' W1P in U.S. Patents 3,794,609 may also be included. Such solvents include ethers such as butyl glycidyl ether, cresyl glycidyl ether, and allyl glycidyl ether; alcohols such as isopropyl alcohol, benzyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, and furfuryl alcohol polymers; and low viscosity organic solvents containing epoxy groups such as styrene oxide, propolene oxide, and epichlorohydrin in minor amounts of up to about 1 part per ten parts of resinous epoxide. Organic solvents such as methyl isobutyl ketone, acetone, and petroleum hydrocarbons may also be included in minor amounts.The following example illustrates a composition of the present invention:EXAMPLE I The following composition includes three components, a liquid resin component, a curing agent component, and a filler component. Before the composition is mixed for use, the components are kept in separate containers. If desired, the filler component may be mixed with the liquid resin component or with the curing agent component for storage. Resin ComponentAraldite 6004 Epoxy Resin 94.4 gramsWater 2.1 gramsCuring Agent Component m-Xylylene diamine (MXDA) 8.0 gramsKetimined MXDA and methyl isobutyl ketone 17.7 gramsPowder ComponentGround Silica 70.0 gramsSupplied by Ciba Geigy, epoxide equivalent = 175, viscosity 4000 eps. The three components were combined and stirred by hand for one minute. In this composition, the mole ratio of water to kitimine groups is about 1.1 to 1. The following properties were determined for the mixture upon mixing and curing at about 73°F.Pot Life: 1 1/2 hoursSet Hard: 9 1/2 - 11 hoursCompressive Strength (after 7 day cure) : 8802 psEXAMPLE II1 2. £Epαn 828 Epoxy Resin 100.0 grams 100.0 grams 100.0 gKetimine of 1,3-Bis (aminαnethyl) cyclohexane and methyl n-butyl ketone 40.7 1,3-Bis (aminomethyl) cyclohexane 18.9 18.9 Methyl n-butyl ketone 26.8 Furfuryl alcohol 26.8 Water 5.0 Epoxy resin supplied by Shell Chemical, epoxide equivalent 195, viscosity = 16,000 cpsThe ingredients of each formulation were stirred together to form a uniform mixture and the gel time of each was determined. A B - CGel time, 73°F 3 hours 1 1/2-2 hrs. 1/4 h A comparison of the gel time of Formulrtion A, which contai only a ketimine curing agent, with the gel times of Formula tion B and C, which contain the corresponding free amine curing agent, shows that a wide vatiation in gel time can be achieved by varying the proportion of ketimine and free amine in the curing agent./-BUO , EXAMPLE III Resin ComponentAraldite 6004 70.5 gramsCarbon black pigment, paste 2.9 IIAsbestos (a thickener) 2.1 IIWater 2.3 IICuring Agent Component m-Xylylene Diamine (MXDA) 4.6 Ketimine of MXDA and methyl isobutyl ketone 23.5 Powder ComponentGraded Sand 380 The components were mixed and allowed to stand at about 73°F. The mole ratio of water to ketimine groups is 0.82 to 1,Pot Life: 1.1/2 hours A similar composition was prepared in which all of the MXDA was in free amine form. The pot life was 20 minutes. When all of the MXDA was in ketimine form, the pot life was 5 - 8 hours.In formulating a composition of this invention for a particular use, it is preferable to adjust the ratio of free amine to ketimine to provide a pot life that is sufficient but not excessive, so that the time required for hard setting will not be unduly prolonged. EXAMPLE IVThe following composition includes amixed curing agent having a free polyamine and a ketimine of a different polyamine.Resin ComponentAraldite 6004 70.5 gramsWater 2.3Curing Agent Component m-Xylylene Diamine 4.6Ketimine of 1,3-Bis (aminomethyl) cyclohexane and methyl isobutyl ketone 24.0Powder ComponentGraded silica sand 380.0The composition was mixed and allowed to cure at about 73°F. Pot Life: 1 3/4 hoursSet Hard: approximately 16 hoursCompressive Strength (after 7 day cure) : 7825The present invention has been described with referenc to particular details and embodiments thereof. These particulars are intended to illustrate rather than to limit the invention, the scope of which is defined in the followin claims:O | WHAT IS CLAIMED IS:1. A room temperature hardening epoxy cement composition comprising:(1) a resinous epoxide; (2) a mixed amine-ketimine curing agent comprising a cyclic polyamine having at least two aliphatic amino functional groups reactive with the resinous epoxide, a portion of said aliphatic amino functional groups in said mixed amine-ketimine curing agent being in ketimine group form; and(3) water in at least about the stoiciometric proportion for hydrolyzing said ketimine groups to free primary amine form.2. The composition of claim 1 in which said ketimine groups are the reaction product of primary amine functional groups of said cyclic amino compound and a dialkyl ketone, a diaryl ketone, or an alkyl aryl ketone having three to thirteen carbon atoms.3. The composition of claim 1 further comprising between about 5 and about 30 parts by weight per part by weight of epoxide of inorganic filler.4. A composition of claim 1 in whcih the cyclic polyamine is an aromatic compound having at least two epoxide reactive aminoalkyl substituents. polyamine is 1,3-bis(aminomethyl) benzene.6. The composition of claim 1 in which the cyclic polyamine is a cycloaliphatic compound having at least two epoxide-reactive amino or aminoalkyl substituents.7. The composition of claim 5 in which the cyclic polyamine is 1,3-bis(aminomethyl) cyclohexane.8. The composition of claim 6 in which the cyclic polyamine is p,p*-methylene di(cyclohexylamine) .9. The composition of claim 6 in which the cyclic polyamine is 1,3-diaminocyclohexane.10* The composition of claim 11 in which the cyclic polyamine is N-(2-aminoethyl)piperazine.11- The composition of claim 6 in which the cyclic polyamine is 3,5,5-trimethyl-3- (amino methyl)cyclohexylami12. The composition of claim 6 in which the cyclic polyamine is 1,8-diamino-p-menthane.13. The composition of claim 1 in which the cyclic polyamine compound is a heterocyclic compound in which the nitrogen of an epoxide reactive amino functional group is part of the ring. 14. The composition of claim 11 in which the cyclic polyamine is N- (2-aminoethyl)piperazine.15. The composition of claim 2 in which the ketone is methyl isobutyl ketone.16. The composition of claim 2 in which the ketone is methyl isoamyl ketone.17. The composition of claim 1 in which between about 10 and about 90 mole percent of said aliphatic amino functional group in said mixed amine-ketimine curing agent are in ketimine form.18. A method of forming a protective epoxy cement surface on a substrate which comprises : forming a mixture of (a) a resinous epoxide;(b) a mixed amine-ketimine curing agent comprising a cyclic polyamine having at least two aliphatic amino 0 functional groups reactive with the resinous epoxide, a portion of said aliphatic amino functional groups in said mixed amine-ketimine curing agent being in ketimine group form;(c) water in at least about the stoichiometric 5 amount for hydrolyzing said ketimine groups to free amine form; and(d) between about 5 and about 30 parts by weight per part by weight of epoxide of inorganic filler; applying said mixture in a layer between about Q 1 and about 15 millimeters thick to said substrate; and allowing said layer to harden. . e me o o c a m compr s ng e s eps o forming said mixture and allowing said mixture to react partially to produce a sprayable cement composition havin sufficient body for forming a sag-free layer between abou 1 and about 15 millimeters thick on a substantially verti surface, and applying said sprayable composition to said substrate.20. The method of claim 18 in which the cyclic polya is an aromatic compound having at least two epoxide-react aminoalkyl substituents.21. The method of claim 18 in which the cyclic polya is a cycloaliphatic compound having at least two epoxide- reactive amino or aminoalkyl substituents.22. The method of claim 18 in which the cyclic polya is a heterocyclic compound in which the nitrogen of an epoxide-reactive amino functional group is a member of the ring.23. The method of claim 18 comprising the step of controlling the ratio of amino functional groups in ketim form to amino functional groups in free amine form for regulating the working life of the mixture.-BO0 | AMERON INC | BRINDELL G; FRACCICA R |
WO-1979000912-A1 | 1,979,000,912 | WO | A1 | XX | 19,791,115 | 1,979 | 20,090,507 | new | G11C11 | null | G06F13, G11C5, G11C7, G11C11 | G06F 13/42C3S, G11C 5/00, G11C 5/06M | MEMORY DEVICE HAVING A MINIMUM NUMBER OF PINS | A circuit for reducing the number of external pins or terminals on a memory device includes a counter circuit which periodically causes the signal on a first external pin to be provided to the power terminal of an internal power supply within the memory device and, at the same time, causes the ground level signal on a second external pin to be provided to the ground terminal of the internal power supply. At other times during the receipt of signals on the two external pins, the signal on the first pin provides both memory select and clocking functions and the signal on the second pin provides memory mode select, address, and data input and output functions. | MEMORY DEVICE HAVING A MINIMUM NUMBER OF PINSBackground of the InventionThe present invention is directed to a circuit for minimizing the number of external pins or terminals on a memory device. More particularly, the present invention is directed to a memory device wherein the external power and ground pin functions are merged with other pin or- terminal functions.Pin reduction for purposes of increasing the number of memory devices that can be assembled in a given area allocated to computer memory is the subject of co-pending ϋ. S. application Serial No. 812,290, entitled A Minimum Pin Memory Device , now ϋ. S. Patent No. , and co-pending ϋ. S. application Serial No. , entitled Memory Device Having A Reduced Number of Pins , bearing Assignee's Docket No. 2659, now U. S. Patent No. , which applications are both assigned to the same assignee as the present application. In the aforementioned -application SerialNo. 812,290, pin reduction is accomplished by merging the functions provided by signals on various pins. A first terminal provides both a clocking and a memory select function. A second terminal is bi-directional and provides memory mqde selection, address and data input and output functions.Further pin reduction is provided for in the second of the abovementioned applications, namely U. S. application Serial No. . In such appli- cation, a circuit is provided in a memory device for receiving signals applied to two external pins. A threshold detector in the circuit detects the differ¬ ence in voltage level of the signals; when such difference reaches a predetermined level, the signals are applied to the power and ground terminals of an internal power supply within the memory device. Thus, the need for external power and ground terminals in a memory device is eliminated.The subject matter of the present application provides an alternative approach to further pin reduction and the elimination of external power and ground terminals in a memory device.Summary of the InventionIn the present invention, pin reduction in a memory device is accomplished by merging the power and ground terminals with external terminals providing other functions.In accordance with the present invention, a memory device includes two external pins which provide clocking, memory select, mode select, address, data in or data out functions, such as in a merged form.The signal at one pin goes periodically to an operating voltage level and the signal at the other pin goes periodically to ground level. Signal processing means, such as rectification circuitry, are connected to the two external pins and provide a relatively constant power signal and ground level signal to the terminals of an internal power supply within the memory device.In the disclosed embodiment, one external pin receives a coded clocking signal which provides both memory selection and synchronization of the memory device. A second external pin receives signals representing memory mode selection, address, data input and data output. Counter circuit means are provided for counting the cycles or pulses of the clocking signal received on the first external pin and when a predetermined number of pulses have been received, such counter operates switch means which connect the first external pin to the power terminal of the internal power supply and which connect the second external terminal, then at a ground or reference voltage level, to the ground or reference terminal ofO the internal power supply.A memory device in accordance with the present invention can thus be seen to have as few as two external pins, with one pin receiving a signal which provides synchronization, memory selection and power functions. The second external pin receives signals providing memory mode selection, address, data input, data output and ground functions.It is therefore one object of the present invention to provide a memory device having a minimum number of external pins or terminals.It is a further object of the present invention to provide a memory device without external power and ground terminals. It is another object of the present invention to use a clocking signal for providing a power signal to a memory device and to use a second signal having other functions for providing a ground signal to such device. Still a further object of the present invention is to provide a memory device having as few as two external- pins, with such pins providing power and ground, as well as memory device selection, memory mode selection, memory address and data input and output functions.These and other objects of the present invention will become more apparent when taken in conjunction with the following description and the attached drawings.Brief Description of the DrawingsFig. 1 is a perspective view of a memory device in integrated circuit structure form and made in accordance with the present invention;Figs. 2A and 2B are, taken collectively, a circuit block diagram of the memory device shown in Fig. 1;• Figs. 3A and 3B are waveforms illustrating the operation of the circuit of Figs. 2A and 2B.Description of the Preferred EmbodimentIn Fig. 1, a memory device 10, in monolithic integrated circuit form, has two external pins or terminals, labelled CQ and FQ. The memory device includes a memory element, such as a charge coupled device (CCD) and, as will be more fully described later, the CQ and FQ pins provide all the necessary external inputs and outputs to the memory device 10 and the memory element therein.Referring now to Figs. 2A and 2B, the memory device 10 is illustrated in block diagram form. The CQ pin is selectively connected by way of a field effect transistor 12 and a coupling capacitor 14 to a clock generator circuit 16 and a decoder circuit 18. The CQ pin is also selectively connected to the power input terminal V of an internal power supply 20 by way of a field effect transistor 24 and a diode 26. The FQ pin is selectively connected to the ground input terminal GND of the internal power supply 20 by way of a field effect transistor 30. The FQ terminal is also selectively connected, by way of a field effect transistor 32 and a coupling capacitor 34, to the output of a NAND gate 60 and to the inputs of various data receiving components within the memory device; more specifically, to the D Input of a D-type flip-flop 36, to the D input of an address shift register 38, and to the DATA IN terminal of a memory element 40, which, as mentioned earlier, may be a CCD or some other type of memory element. A capacitor 42 is connected across the leads to the power terminal V and the ground terminal GND of the internal power supply 20.The transistors 12, 24, 30 and 32 are periodically activated by circuitry that includes an initialization circuit 50 and a counter circuit 52. The initialization circuit 50 has its input connectedA to the C~ terminal and is connected at its output to the RESET input of the counter circuit 52. The other input D of the counter circuit 52 is connected directly to the Cn terminal. The initialization circuit 50 delivers, upon receipt of a widened clock pulse on pin CQ, at the beginning of operation of the memory device, a signal to the RESET input of the counter 52 so that the counter may begin to count the clock pulses at the CQ terminal and also cause an initial voltage to be provided across the power terminal V and the ground terminal GND of the internal power supply 20. Circuits which sense a change in pulse width are well-known in the art and could comprise generally a delay network and a flip-flop. Such a circuit could also be used in the previously mentioned decoder circuit 18 although, for. reasons which will become apparent later, initialization circuit 50 should sense only a pulse width change wider than the pulse width change sensed by decoder circuit 18. A circuit of the type which could be used in decoder circuit 18 and initialization circuit 50 is described in greater detail, for example, in the aforementioned U. S. application Serial No. 812,290. The counter circuit 52 is also a circuit well-known to those skilled in the art. It is initialized or reset by a signal at its RESET input, and counts the positive pulses received at its D input. It provides an' enabling signal at its output each time a predetermined number of pulses at its D input are counted, and also when the circuit is initialized by a signal at the RESET input.The output of the counter circuit 52 is connected to the gates G of the field effect trans- istors 24 and 30 and to the input of an inverter 56. The output of the inverter 56 is connected to the gates G of the field effect transistors 12 and 32. Incidentally, it should be noted that the internal power supply 20 provides the necessary operating voltages VQ through V and a ground level signal GND to various active circuit components within the memory device 10, including the initialization circuit 50, the counter circuit 52, and the inverter 56.Those portions of the memory device in Figs. 2K and 2B which are shown enclosed by broken lines 70 are essentially the circuit structure shown and described in the previously mentioned application Serial No. 812,290. Accordingly, reference can be had to such application for a more detailed description of the individual components and the operation of the circuit within the broken lines 70. It can be noted that the circuit within lines 70 has four inputs which carry signals labeled CLOCK, POWER, GROUND AND FUNCTION, and in the present memory device 10 these, four signals originate from the signals applied at the two pins CQ and F« . As will be described in greater detail below, the signals applied to the CQ and FQ pins are processed or rectified by the circuitry which is located outside the broken lines 70 to provide the POWER and GROUND signals delivered to the circuit within the lines 70. In addition, the CLOCK signal is delivered to the clock generator 16 and the decoder circuit 18 from the CQ pin. The FUNCTION signal is delivered to the flip-flop 36, address shift register 38 and memory element 40 from the FQ pin. it should be noted that the CLOCK signal delivered to the clock generator 16 and the decoder circuit 18 is a merged function signal in that it is coded to provide a memory selection signal as well as providing a clocking or synchronizing signal. The FUNCTION signal present on the FQ terminal and delivered to the flip-flop 36, address shift register 38 and memory element 40 is also a merged function signal in that it provides-, by appropriate coding techniques OMPI< W1PO and in conjunction with the CLOCK signal, mode selection, memory address, data input and data output functions.To illustrate the above, reference can be had to Figs. 3A and 3B, which show waveforms representing the signals applied to the CQ and FQ pins. Turning first to Fig. 3A, the depicted waveforms illustrate a recirculation mode, that is, a condition where the memory device 10 has not been selected to receive or provide data, and the data within the memory element 40 is being recirculated within the memory element 40 as it is held ready for use. In this condition, substantially periodic and uniformly spaced clock pulses are received on the CQ pin and are carried to the clock generator circuit 16 which provides the necessary clocking signals, designated 0 through 0 . to the memory element 40 for proper recirculation of the data, and to the other components within the memory device 10 requiring a clock signal.It should be noted that when the memory device 10 is first used, it is necessary that a long initialization pulse first be received at pin CQ, such pulse being shown in Fig. 3A. During this initialization period, the initialization circuit is caused to generate a signal which, when received by the counter 52, in turn causes the counter 52 to generate an enabling signal to activate the transistors 24 and 30. The positive voltage at the pin CQ and the ground level signal then at the FQ pin are applied to the* capacitor 42 and to the input terminals of the power supply 20. This period of initialization is long enough to fully charge the capacitor 42 such that a relatively constant voltage continues across the V and GND terminals of the power supply after initialization until voltages are again applied (in a periodic fashion) to the V and GND terminals, as will be described.The receipt of the initialization pulse and the resulting signal at the output of the initialization circuit also resets the counter 52 in the memory device 10. After initialization, the counter 52 counts the positive pulses (and cycles) of the signal received at the CQ pin and after receipt of the proper number of pulses, an enabling signal appears at the output of the counter 52 and causes the transistor24 and 30 to become conductive. During the period that the transistors 24 and 30 are conductive, generally identified in Figs. 3A and 3B as the power cycle , the positive pulse at CQ is applied to the V terminal of the internal power supply and the signal at the FQ' terminal, which is at ground level, is applied to the ground terminal of the internal power supply 20. After the first power cycle, the counter circuit 52 again counts the pulses received at CQ , and after the proper number is received, the transistors 24 and 30 are again made conductive. Because of the periodic receipt of positive pulses at the power terminal V and ground level signals at the ground terminal GND, the capacitor 42 maintains a substantially constant voltage across the terminals. Although in the waveforms illustrated in Figs. 3A and 3B a power cycle occurs every third pulse at pin CQ, the actual frequency of the power cycles may be different, depending on what is required to maintain the desired voltage across the terminals of the power supply.At times other than the power cycle, the inverter 56 causes the transistors 12 and 32 to be conductive, and the pulses received at the CQ pin are provided by way of the capacitor 14 to the clock generator 16 and decoder circuit 18. The signals at the FQ pin are provided by way of the capacitor 34 to the flip-flop 36, address shift register 38 and memory element 40. However, since the memory device is in a recirculation mode, the signal levels at the FQ pin are, as illustrated by shading, in a DON'T CARE condition.Incidentally, the coupling capacitors 14 - JREO PI A, W1P0 and 34 are provided to eliminate direct current voltages which might be present on the CQ and FQ pins and which might thereby be transmitted to the circuit components within the memory device. These capacitors are necessary since the ground terminal GND of the internal power supply only periodically receives a ground level signal and the ground signal provided at the output of the internal power supply 20 may otherwise float with respect to true ground at times when the ground level signal is not applied at the ground input terminal GND of the power supply.Referring now to Fig. 3B, there is illustra-. ted the condition when the memory device 10 and its memory element 40 have been selected for either reading or writing data, preceded by the recirculation mode. The memory element is selected by decreasing the width of the positive clock pulse applied at the CQ pin. Since data is written or read at a much higher frequency than the frequency at which it is shifted during the recirculation mode, the frequency of the positive clock pulses also increases in Fig. 3B. It should be noted that although the clock frequency of Fig. 3B is illustrated graphically as increasing to twice the clock frequency of Fig. 3A, the frequency in the read or write mode may be a much higher multiple of the recirculation mode frequency. In the illustrated memory device, the external data line to the FQ pin is assumed to be common with the external data line to other memory devices, and so data pulses will be present on the FQ even during the recirculation mode, such data pulses having the same frequency as the clock frequency in the read or write mode. In order to assure that the positive clock pulse during each power cycle of the recirculation mode will occur when the FQ is at ground level, as determined by each power cycle of the read or write mode, it is preferable that the clock frequency ofFig. 3B become a multiple of the clock frequency Fig. 3A. However, if the external data line to the FQ pin is not common to other memory devices, the clock frequencies of Figs. 3A and 3B may be independent of one another. It should also be noted that the decoder circuit 18 is only sensitive to the change in clock pulse width for memory selection, and not to the greater change in clock pulse width occurring at initialization. In a pulse width sensing circuit 0 having a delay network and flip-flop described earlier, the initialization circuit could be accomplished by increasing the delay in the delay network, over that in the decoder circuit.Referring still to Fig. 3B, the positive 5 clock pulse at CQ narrows during the period identified as Memory & Mode Select and the decoder circuit 18 senses the change in pulse width and provides a memory select (MS) signal (logic level 1 ) to the memory element 40, to one input of a NAND gate 60, to 0 the CK ENB terminal of the flip-flop 36, to the CKENB 1 terminal of the address shift register 38, and to the D and SET inputs of a shift register or counter 62.During the Memory & Mode Select period 5 the FQ pin is either at a 0 logic level or at a 1 logic level, to indicate the memory mode selection, i.e., whether the memory element 40 is selected for reading ( 0 logic level) or for writing ( 1 logic level). The mode select signal at the FQ pin during ϋ the Memory & Mode Select period is applied to the D input of the flip-flop 36 where, with the memory select (MS) signal generated by the decoder circuit 18 and delivered to the CK ENB (clock enable) terminal of flip-flop 36, the mode select signal (either a 0 5 or a 1 level) is latched into the flip-flop 36 when a clock pulse is.received at the CK (clock) terminal and appears at its Q output.After the MS signal is also received at the SET and D inputs of the shift register 62, the shift register 62 begins to count to a preset number corresponding to the number of bits A_ through A (Fig. 3B) serially received on the FQ pin and representing the address location which is to be selected in the memory element 40. When the proper number of bits has been counted by the shift register 62, an enabling signal (logic level 0 ) from the Qn output of the shift register 62 is applied to the CK ENB 2 terminal of the address shift register 38 and to one input of an OR gate 64. At such time the OR gate 64 passes the mode select signal from the Q output of flip-flop 36 to the R/W MODE input of the memory element 40 and the pertinent address data bits (AQ through A ) which have been received at the D input of the address shift register 38 are presented to the address inputs 0 through N of the memory element 40.If data bits (DQ through D ) on the FQ pin are to be written into the memory element, such data is presented in serial form to the DATA IN terminal of the memory element 40. If data is to be read from the memory element, the data bits (DQ through D ) in the memory element at the address specified by the address inputs 0 through N are presented in serial form at the DATA OUT terminal of memory element 40 and carried to the FQ pin by way of the NAND gate 60..Although the operation of the circuit components within the broken lines 70 has been described briefly, a more detailed discussion can be obtained, as mentioned earlier, by reference to the aforementioned application Serial No. 812,290.From the above, it can be seen that a memory device in integrated circuit form that includes a memory element can be provided having only two external pins or terminals. The signals provided at the two external pins are coded to provide synchronizing, memory selection, mode selection, memory address, data input and data output functions, and the signals-BU REA7J OMPI . μ yr_m w *viιpι-oυ • κ*y_•,<m RNAΥ\0 are rectified to provide the necessary power and ground signals to the internal power supply within the integrated circuit structure. It should be understood, of course, that signal coding techniques other' than those described above could be used for providing the memory select, mode select, memory address, and data input and data output functions, as long as the signals can be rectified to develop a sufficient voltage difference for providing the power and ground signals.Although a specific embodiment of the invention has been shown in detail, it will be understood by those skilled in the art that changes may be made therein without departing from the spirit and scope of the invention. | AMENDED CLAIMS(received by the International Bureau on 3 September 1979 (03.09.79))1. (cancelled)2. (cancelled)3. (cancelled)4. (cancelled)5. (cancelled)6. (cancelled)7. (cancelled)8. (cancelled)9. (cancelled)10. ( cancelled ) 11,, ( cancelled ) 1-2 ( cancelled )13. (cancelled)14. (cancelled)15. (cancelled)16. (cancelled)17. memory device requiring a power supply voltage and a reference level supply voltage, including a memory element and first and second access terminals adapted to receive respective first and second operation- al signals for said memory device, characterized by sig¬ nal processing means adapted to receive said first and second operational signals and to process said first and second operational signals to provide said power and reference level supply voltages.18. A memory device according to claim 17, characterized in that said signal processing means in¬ cludes enabling means adapted to provide an enabling signal, and switching means (24, 30) responsive to said enabling signal to couple said first and second access terminals (CQ, FQ) to a power supply device (20) included in said memory device (10) and adapted to provide supply voltages and reference level voltages for utilization in said memory device (10). 19. A memory device according to claim 18, characterized in that said power supply device (2) in¬ cludes first and second input terminals coupled to said switching means (24, 30) and having capacitive means (42) coupled thereacross.20. A memory device according to claim 19, characterized in that said switching means includes first and second transistors. (24, 30) coupled to said first and second access terminals (Cnu, Fnu) respectiv*ely.2-1. A memory device according to claim 20, characteriz-fet? in that said first operational signal in¬ cludes periodic 'Clock pulses and said second signal in¬ cludes memory address, data input and data output signal components^22. A memory device according to claim 21, characterized by decoding means (18) coupled to said first access terminal (Cfl) and adapted to provide a mem¬ ory select signal for said memory element (40) in re- sponse to a change in a characteristic of said periodic clock pulses.23. A memory device according to claim 22, characterized in that said signal processing means in¬ cludes counting means (52) adapted to count said clock pulses and to provide said enabling signal whenever a predetermined number of said clock pulses have been counted.24. A memory device according to claim 23, characterized in that said switching means includes a third transistor (12) coupled between said first access terminal (CQ) and an internal clock generator circuit (16) included in said memory device (10), and a fourth transistor (32) coupled between said second access ter-- UREΛOJfiPlW1PO J. ftNATlO 24. ( concluded ) minal (Ffl) and internal data receiving means included in said memory device (10), said third and fourth transis¬ tors (12, 32) having control electrodes adapted to be supplied with the complement of said enabling signal.25. A memory device according to claim 24, characterized in that said signal processing means in¬ cludes an initialization circuit (50) coupled to said first access terminal (CQ) and to said counting means (52) and adapted to cause said counting means to provide said enabling signal in response to an initiating signal applied to said first access terminal (Cn).26. A memory device according to claim 24 or claim 25, tfi^facterized in that said signal processing means iήel ά es- an inverter (56) having an input arranged to receive, said enabling signal and an output coupled to said control electrodes of said third and fourth trans¬ istors (12, 32).27. A memory device according to any one of the preceding claims, characterized i-n that said memory device is in the form of an integrated circuit structure.28. A method for eliminating the external power and ground terminals on a memory device, including the steps providing a first operational signal on a first access terminal having periodic pulses; and providing a second operational signal on a second access terminal which periodically is at a ground level, characterized by the step of processing said first and second opera¬ tional signals to provide a power and a ground level signal for said memory device (10).29. A method according to claim 28, charac¬ terized in that said step of providing a first signal 29 . ( concluded ) includes alternating said first signal between a power level voltage and a ground level voltage and in that said step of providing a second signal includes providing said second signal at its ground voltage level when said first signal is at its power voltage level.30. A method according to claim 29, charac¬ terized in that said step of processing includes the step of counting the number of pulses received at said first access terminal and after a predetermined number of pulses have been received, generating an enabling sig¬ nal for causing said first and second access terminals (C_, F_) to be connected to power and ground input ter¬ minals of an internal power supply device (20) within said memory device (10). | NCR CO; NCR CORP | LAUFFER D; WARD W |
WO-1979000913-A1 | 1,979,000,913 | WO | A1 | EN | 19,791,115 | 1,979 | 20,090,507 | new | A61B5 | null | G10L11, G10L15 | G10L 11/04, G10L 11/04+IDT, S10L 700/013 | SPEECH ANALYSER | A speech analyser is provided for determining the emotional state of a person by analysing pitch or frequency perturbations in the speech pattern. The analyser determines null points or flat spots in a FM demodulated speech signal and it produces an output indicative of the nulls. The output can be analysed by the operator of the device to determine the emotional state of the person whose speech pattern is being monitored. | -1-SPEECH ANALYSER BACKGROUND OF T-HE INVENTIONField of the InventionThis invention is related to an apparatus for analysing an individual's speech and more particularly, to an apparatus for analysing pitch perturbations to determine the individual emotional state such as stress, depression, anxiety, fear, happiness, etc., which can be indicative of subjective attitudes, character, mental state, physical state, gross behavioral patterns, veracity, etc. In this regard, the apparatus has com¬ mercial applications as a criminal investigative tool, a medical and/or psychiatric diagnostic aid, a public opinion polling aid, etc.Description of the Prior Art One type of technique for speech analysis to determine emotional stress is disclosed in Bell, Jr. , et al, U.S. Patent 3,971,034. In the technique disclosed in this patent a speech signal is processed to produce an FM demodulated speech signal. This FM demodulated signal is recorded on a chart recorder and then is manually analysed by an operator. This technique has several disadvantages. First, the output is not a real time analysis of the speech signal. Another disadvantage is that the operator must be very highly trained in order to perform a manual analysis of the FM demodulated speech signal and the analysis is a very time consuming endeavor. Still another disadvantage of the technique disclosed in Bell Jr. , et al is that it operates on the fundamental frequencies of the vocal cords and, in the Bell Jr. , et al^ technique tedious re-recording and special time expan¬ sion of the voice signal are required. In practice, all these factors result in an unnecessarily low sensitivity to the parameter of interest, specifically stress. Another technique for voice analysing to determine emotional states is disclosed in Fuller, U.S. Patents 3,855,416, 3,855,417 and 3,855,418. The technique disclosed in the Fuller patents analyses amplitude char¬ acteristics of a speech signal and operates on distortion products of the fundamental frequency commonly called vibrato and on proportional relationships between various harmonic overtone or higher order formant frequencies. Although this technique appears to operate in real time, in practice, each voice sample must be cali¬ brated or normalized against each individual for reliable results. Analysis is also limited to the occurrence of stress, and other characteristics of an individual's emotional state cannot be detected.SUMMARY OF THE INVENTION The present invention is directed to an appara- tus for analysing a person's speech to determine their emotional state. The analyser operates on the real time frequency or pitch components within the first formant band of human speech. In analysing the speech, the appa¬ ratus analyses certain value occurrence patterns in terms of differential first formant pitch, rate of change of pitch, duration and time distribution patterns. These factors relate in a complex but very fundamental way to both transient and long term emotional states.Human speech is initiated by two basic sound generating mechanisms. The vocal cords; thin stretchedO Pl ϊ^tf AT membranes under muscle control, oscillate when expelled air from the lungs passes through them. They produce a characteristic buzz sound at a fundamental frequency between 80Hz and 240 Hz. This frequency is varied over a moderate range by both conscious and unconscious muscle contraction and relaxation. The wave form of the funda¬ mental buzz contains many harmonics, some of which excite resonance in various fixed and variable cavities associated with the vocal tract. The second basic sound generated during speech is a psuedo-random noise having a fairly broad and uniform frequency distribution.. It is caused by turbulence as expelled air moves through the vocal tract and is called a hiss sound. It is modu¬ lated, for the most part, by tongue movements and also excites the fixed and variable cavities. It is this complex mixture of buzz and hiss sounds, shaped and articulated by the resonant cavities, which produces speech.In an energy distribution analysis of speech sounds, it will be found that the energy falls into distinct frequency bands called formants. There are three significant formants. The system described here utilizes the first formant band which extends from the fundamental buzz frequency to approximately 1000 Hz. This band has not only the highest energy content but reflects a high degree of frequency modulation as a function of various vocal tract and facial muscle tension variations.In effect, by analysing certain first formant frequency distribution patterns, a qualitative measure of speech-related muscle tension variations and interactions is performed. Since these muscles are predominantly biased and articulated through secondary unconscious processes which are in turn influenced by emotional state, a relative measure of emotional activity can be determined independent of a person's awareness of lack of awareness of that state. Research also bears out a general supposition that since the mechanisms of speech are exceedingly complex and largely autonomous, very few people are able to consciously project a fictitious emotional state. In fact, an attempt to do so usually generates its own unique psychological stress finger¬ print in the voice pattern.Because of the characteristics of the first formant speech sounds, the present invention analyses an FM demodulated first formant speech signal and produces an output indicative of nulls thereof.The frequency or number of nulls or flat spots in the FM demodulated signal, the length of the nulls and the ratio of the total time that nulls exist during a word period to the overall time of the word period are all indicative of the emotional state of the individual. By looking at the output of the device, the user can see or feel the occurrence of the nulls and thus can determine by observing the output the number or frequency of nulls, the length of the nulls and the ratio of the total time nulls exist during a word period to the length of the word period, the emotional state of the individual. In the present invention, the first formant frequency band of a speech signal is FM demodulated and the FM demodulated signal is applied to a word detector circuit which detects the presence of an FM demodulated signal. The FM demodulated signal is also applied to a null detector means which detects the nulls in the FM demodulated signal and produces an output indicative thereof. An output circuit is coupled to the word detec¬ tor and to the null detector. The output circuit is enabled by the word detector when the word detector detects the presence of an FM demodulated signal, and the output circuit produces an output indicative of the_ O•• , ~WΪP -NA presence or non-presence of a null in the FM demodulated signal. The output of the output circuit is displayed in a manner in which it can be perceived by a user so that the user is provided with an indication of the existence of nulls in the FM demodulated signal.The user of the device thus monitors the nulls and can thereby determine the emotional state of the indi¬ vidual whose speech is being analysed.It is an object of the present invention to provide a method and apparatus for analysing an individual's speech pattern to determine his or her emotional state. It is another object of the present invention to provide a method and apparatus for analysing an indivi¬ dual's speech to determine the individual's emotional state in real time.It is still another object of the present inven¬ tion to analyse an individual's speech to determine the individual's emotional state by analysing frequency or pitch perturbations of the individual's speech. It is still a further object of the present in¬ vention to analyse an FM demodulated first formant speech signal to monitor the occurrence of nulls therein.It is still another object of the present in¬ vention to provide a small portable speech analyser for analysing an individual's speech pattern to determine their emotional state.BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a block diagram of the system of the present invention. Figures 2A-2K illustrate the electrical signals produced by the system shown in Figure 1.Figure 3 illustrates an alternative embodiment of the output of the present invention.Figure 4 illustrates still another alternative embodiment of the output of the present invention.O PI_ DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTReferring to Figs. 1 and 2A-2K, speech, for the purposes of convenience, is introduced into the speech analyser by means of a built-in microphone 2. The low level signal from the microphone 2 shown in Fig. 2A is amplified by the preamplifier 4 which also removes the low frequency components of the signal by means of a high pass filter section. The amplified speech signal is then passed through the low pass filter 6 which removes the high frequency components above the first formant band. The resultant signal, illustrated in Fig. 2B represents the frequency components to be found in the first formant band of speech, the first formant band being 250 Hz - 800 Hz. The signal from low pass filter 6 is then passed through the zero axis limiter circuit 8 which removes all amplitude variations and produces a uniform square wave output illustrated in Fig. 2C which contains only the period or instantaneous frequency component of the first formant speech signal. This signal is then applied to the pulse generator circuit 10 which produces an out¬ put pulse of constant amplitude and width, hence con¬ stant energy, upon each positive going transition of the input signal. The output of pulse generator circuit 10 is illustrated in Fig. 2D. The pulse signal in Fig. 2D is integrated by the low pass filter circuit 12 whose output is shown in Fig. 2E. The D.C. level or amplitude of the output of the filter as shown in Fig. 2E thus represents theinstantaneous frequency of the first formant speech signal. The output of the low pass filter 12 will thus vary as a function of the frequency modulation of the first formant speech signal by various vocal cord and other vocal tract muscle systems. The overall combination of the zero axis limiter 8, the pulse generator 10, and the low pass filter 12 comprise a con- ventional FM demodulator designed to operate over the first formant speech frequency band. The FM demodulated output signal from the low pass filter 12 is applied to word detector circuit 14 which is a voltage comparator with a referencevoltage set to a level representative of a first formant frequency of 250 Hz. When this reference level is exceeded by the FM demodulated signal, the comparator output switches from OFF to ON as illustrated in Fig. 2F.The FM demodulated signal from the low pass filter 12 is also applied to differentiator circuit 16 which produces an output signal proportional to the in¬ stantaneous rate of change of frequency of the first for¬ mant speech signal. The output of differentiator 16, which is shown in Fig. 2G, corresponds to the degree of frequency modulation of the first formant speech signal. The signal from differentiator 16 is applied to a full wave rectifier circuit 18. This circuit passes the positive portion of the signal unchanged. The nega¬ tive portion is inverted and added to the positive portion. The composite signal is then applied to pulse stretching circuit 19 which comprises a parallel circuit of a resis¬ tor and capacitor in series with a diode. The pulse stretching circuit 19 provides a fast rise, slow delay function which eliminates false null information as the differentiated signal passes through zero. The out- put of null detector 18 is illustrated in Fig. 2H.The output signal of the pulse stretching circuit 19 is applied to comparator circuit 20 which comprises a three level voltage comparator gated ON or OFF by the output of word detector circuit 14. Thus, when speech is present, the comparator circuit 20 evaluates, in terms of amplitude level, the output of the pulse stretching circuit 19. Reference levels of the comparator circuit 20 are set so that when normal levels of frequency modulation are present in the first formant speech signal an output as shown in Fig. 21 is produced and an appropriate visual indicator, such as a green BUREAUOMR [^ W1PO &?NATlO'§ LED 22 is turned ON. When there is only a small amount of frequency modulation present, such as under mild stress conditions, an output such as shown in Fig. 2J is produced and the comparator circuit 20 turns on the yellow LED 24. When there is a full null, such as pro¬ duced by more intense stress conditions, an output such as shown in Fig. 2K is produced and the comparator circuit turns on the red LED 26.Referring to Fig. 3, comparator circuit 20 can have an output coupled to a tactile device 28 for produc¬ ing a tactile output so that the user can place the de¬ vice close to his body and sense the occurrence of nulls through a physical stimulation to his body rather than through a visual display. In this embodiment the user can maintain eye contact with the individual whose speech is being analysed which could in turn reduce the anxiety of the individual whose speech is being analysed, which is caused by the user constantly looking to the speech analyser. In the embodiment shown in Fig. 4 the word detector 14 and the pulse stretching circuit 19 are con¬ nected to a voltage meter circuit 30 which is substituted for the comparator circuit 20. The meter circuit 30 is turned on when word detector 14 is ON and meter 32 pro- vides an indication of the voltage output of pulse stretching circuit 19.Since the pitch or frequency null perturbations contained within the first formant speech signal define, by their pattern of occurrence, certain emotional states of the individual whose speech is being analysed, a visual integration and interpretation of the displayed output provides adequate information to the user of the instru¬ ment for making certain decisions with regard to the emotional state, in real time, of the person speaking. The speech analyser of the present invention can be constructed using integrated circuits and therefore can be constructed in a very small size which allows it to be portable and capable of being carried in one's pocket, for example.The present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The presently dis¬ closed 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 the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore, to be embraced therein.1ΪUREA_ OMPI m IPO , N T\ | CLAIMS :1. A speech analyser for determining the emotional state of a person, said analyser comprising:(a) FM demodulator means for detecting a person's speech and producing an FM demodulated signal therefrom;(b) word detector means coupled to the output of said FM demodulator means for detecting the presence of an FM demodulated signal;(c) null detector means coupled to the output of said FM demodulator means for detecting nulls in the FM demodulated signal and for producing an output indica¬ tive thereof;(d) output means coupled to said word detector means and said null detector means, wherein said output means is enabled by said word detector means whensaid word detector means detects the presence of an FM demodulated signal and wherein said output means produces an output indicative of the presence or non-presence of a null in the FM demodulated signal.2. A speech analyser as set forth in Claim 1 wherein said null detector means comprises:(a) a differentiator means for differentiating the FM demodulated signal;(b) a full wave rectifier means, for rectifying the FM demodulated signal; and(c) pulse stretching circuit means for elimina¬ ting the detection of a null when the differentiated FM demodulated signal passes through zero.3. A speech analyser as set forth in Claim 1 wherein said output means comprises:(a) comparator means for detecting the level of the output of the null detector means and comparingOM W,P•li¬the level with predetermined voltage levels wherein when said level is below a first predetermined level a null exists and when said level is above a second predetermined level a null does not exist; and(b) display means for displaying the output of said comparator means.4. A speech analyser as set forth in Claim 3 wherein said display means comprises at least two lights one of said lights being turned on when the output of the comparator means is indicative of a null and the other light being turned on when the output of the comparator means is indicative of the non-existence of a null.5. A speech analyser as set forth in Claim 4 wherein said display means further includes a third light said third light being turned on when the level of the output of the level detector means is indicative of a transition between the existence and non-existence of a null.6. A speech analyser as set forth in Claim 1 wherein said output means is a voltage meter means.7. A speech analyser as set forth in Claim 3 wherein said display means is a tactile display.8. A speech analyser as set forth in Claim 1 wherein said FM demodulator means includes filter means for passing signals in the range of 250 Hz to 800 Hz.9. A speech analyser for analysing an FM demodulated speech signal said analyser comprising:(a) word detector means for detecting the presence of an FM demodulated signal; (b) null detector means for detecting nulls in the FM demodulated signal and for producing an output indicative thereof; and(c) output means coupled to said word detector means and said null detector means, wherein said output means is enabled by said word detector means when said word detector means detects the presence of an FM demodulated signal and wherein said output means produces an output indicative of the presence or non-presence of a null in the FM demodulated signal.10. A speech analyser as set forth in Claim 9 wherein said null detector means comprises:(a) a differentiator means for differentiating the FM demodulated signal;(b) a full wave rectifier means, for rectifying the FM demodulated signal; and(c) pulse stretching circuit means for elimina¬ ting the detection of a null when the differentiated FM demodulated signal passes through zero.11. A speech analyser as set forth in Claim 9 wherein said display means comprises at least two lights one of said lights being turned on when the output of the comparator means is indicative of a null and the other light being turned on when the output of the comparator means is indicative of the non-existence of a null.12. A speech analyser as set forth in Claim 9 wherein said display means comprises at least two lights one of said lights being turned on when the output of the comparator means is indicative of a null and the other light being turned on when the output of the comparator means is indicative of the non-existence of a null. 13. A speech analyser as set forth in Claim 9 wherein said display means further includes a third light said third light being turned on when the level of the output of the level detector means is indicative of a transition between the existence and non-existence of a null.14. A speech analyser as set forth in Claim 9 wherein said display means is a meter.15. A speech analyser as set forth in Claim 9 wherein said display means is a tactile display.ΪT- REAOMPII m WIPO £ NAΎ\ | WILLIAMSON J | WILLIAMSON J |
WO-1979000915-A1 | 1,979,000,915 | WO | A1 | EN | 19,791,115 | 1,979 | 20,090,507 | new | B66C23 | B66C23 | B66C23 | B66C 23/10, B66C 23/82 | A LOW-PROFILE CRANE WITHOUT TOPPING TOWER | A hoisting line (9) extends from a winch (8), over a second pulley (12) at the head end (3) of the jib (1) of a crane, around a movable pulley (14) and over a third pulley (13) at the head end (3) of the jib (1) to a depending load hook (18). The movable pulley (14) is supported by a topping line (7) which extends over a first pulley (11) at the tail end (2) of the jib (1), around a fifth pulley (15) fixedly mounted on the base (4) of the crane and is attached to the first pulley (11). Loading in the hoisting line (9) is therefore transferred to the topping line (7) extending between the first and fifth pulleys (11 and 15) and topping of the jib (1) about an axis (5) between the tail and head ends (2 and 3) is effected by a light-weight piston-cylinder assembly (6). | A Low-Profile Crane without Topping TowerTECHNICAL FIELD OF THE INVENTION The invention relates to a crane in which topping is eff¬ ected by coupling the topping rigging to the hoisting rig- ging in such a way that no topping tower or mast is requi¬ red, to provide a compact, low-profile crane.BACKGROUND ART In conventional deck crane construction, the topping rig¬ ging extends from a topping tower or mast to the head end of the jib and is controlled independently of the hoisting rigging by means of a topping winch. However, in some applications, for example on hoard ships,- the necessary weight and overall height of a crane provided with a top¬ ping tower or mast has disadvantages and so alternative means, such as a fluid-operated piston-cylinder assembly must he provided to effect topping of the jih. However, this necessitates the use of a very heavy-duty piston- cylinder assembly and the jib and its mounting must be constructed with corresponding robustness. This not only increases the cost of the crane, but substantially reduces any saving in weight achieved by the omission of the top¬ ping tower or mast.»DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a crane which does not require a topping tower or mast for the topping rigging but which is substantially lighter and more economical to construct than known cranes pro¬ vided with fluid-operated, piston-cylinder assemblies for topping the jib.According to the invention, there is provided a crane comprising a jib having a tail end and a head end; first pulley means mounted on the tail end of the jib, secondOMPI and third pulley means mounted on the head end of the jib, and fourth pulley means reciprocable between the first pulley means at the tail end of the jib and the second and third pulley means at the head end of the jib; mounting means for supporting the jib for pivotal move¬ ment about a horizontal axis extending transversely of the jib; a double-acting, piston-cylinder assembly ext¬ ending between the jib and the mounting means for pivot¬ ing the jib about the horizontal axis; fifth pulley means fixedly mounted on the mounting means below the first pulley means at the tail end of the jib; at least one topping line extending around the first and fifth pulley means and having opposite ends respectively connected to the fourth pulley means and to one of the first and fifth pulley means; a hoisting winch; and a hoisting line ext¬ ending from the hoisting winch to the second pulley means, around the second and fourth pulley means, from the fourth pulley means to the third pulley means and around the third pulley means to depend from the head end of the jib. Preferably, the first, second, third and fourth pulley means are supported so that the or each topping line acts on the fourth pulley along an axis which is disposed above the horizontal pivotal axis of the jib.In a crane such as this, where the hoisting rigging is coupled to the topping rigging by means of the fourth pulley means, the turning moment exerted on the jib by a load suspended from the depending end of the hoisting line is counteracted by the moment exerted by the topp¬ ing rigging extending between the first and fifth pulley means. It is therefore possible to effect topping by means of a relatively light-duty piston-cylinder assembly. Thus, when it is required to lift a load, the hoisting winch subjects the hoisting line to tension and this ten¬ sion is transferred into the topping rigging by means of the fourth pulley means coupling the hoisting and topping riggings. The fourth pulley means therefore tend to move towards the head end of the jib so that the topping rigg¬ ing tends to pull the first pulley means down to the fixed fifth pulley means, thus tending to raise the jib. In this case, it is often necessary to use the piston-cylin¬ der assembly to prevent the jib from topping until the hoisting line has been sufficiently shortened. Thereafter, topping of the jib can be effected merely by releasing the piston-cylinder assembly or by applying a very small lift- ing force by means of the piston-cylinder assembly.Similar considerations apply when lowering a load and so has been found that effective topping control can be effected with a relatively light-duty piston-cylinder assembly. Moreover, as a result of the coupling bf the hoisting and topping riggings, substantially level luff¬ ing may also be achieved.Clearly, to maintain static equiblibrium when a load is supported from the head end of the jib, the mounting means must be prevented from tilting and, for this purpose, it is convenient to use a counter-weight which is supported on the mounting means on the opposite side of the hori¬ zontal pivotal axis of the jib to the load. However, the components of the crane may be constructed so that this counter-weight is not excessive and the total weight of the crane is less than an equivalent crane provided with a topping tower or mast.To increase the loading transmitted from the hoisting line to the topping rigging, the second and fourth pulley means may each be provided with a plurality of pulleys so that there is a two or more part purchase between these two pulley means. However, even where the second and fourth pulley means are each only provided with one pulley, the loading transmitted from the hoisting line to the topping rigging is twice the weight of the load.OMPI - -Where a plurality of topping lines are used, it is possible to ensure that the loading on each such topping line does not exceed the loading on the hoisting line by ensuring that the number of topping lines equals the number of lengths of the hoisting line extending from the fourth pulley means to the second and third pulley means. In this case, the third and fifth pulley means must also each contain the pulleys for each of the topping lines.To. ensure that the crane operates in a predictable manner, particularly where more than one topping line is employed, the fourth pulley means may be mounted for movement along guide means which extend along a rectilinear axis between the first pulley means at the tail end of the jib and the second and third pulley means at the head end of the jib.To avoid jack-knifing, or uncontrolled lifting of the jib, as a result of tensile loading on the hoisting line, the first pulley means and the fifth pulley means may be dis¬ posed at different distances from the horizontal pivotal axis so that the axis of the first pulley means is movable into an end position alongside the fifth pulley means on a radial plane containing the horizontal pivotal axis and the axis of the fifth pulley means. In this situation the topping line extending between corresponding pulleys in the first and fifth pulley means are substantially aligned with the radial plane and so, as the first pulley means move into this position, the turning moment imposed on the jib by each said topping line progressively decreases to zero. In fact, elevation of the jib beyond this inclina¬ tion results in the imposition of a restoring force in each said topping line which urges the jib to pivot in the opposite direction.BRIEF DESCRIPTION OF THE DRAWINGS Two embodiments of the invention are hereinafter described,O P /,, IP by way of example, with reference to the accompanying drawings, in which:-Figure 1 is a schematic view of a preferred embodiment of the invention, showing a jib and its mounting means in phantom outline;Figure 2 is a view of the hoisting and topping riggings of the crane shown in Figure 1;Figure 3 is a schematic view of the hoisting and topping riggings of an alternative form of crane; andFigure h is a schematic view of the riggings shown in Figure 3, when the crane is topped.BEST MODES FOR CARRYING OUT THE INVENTION The crane shown in Figure i has a jib i formed of two triangular frames 16 which are held together by cross braces 17 so as to converge towards the head end 3 of the jib 1. First pulley means in the form of two pulleys 11 are mounted at the tail end 2 of the jib 1, adjacent one of the apices of each of the triangular frames 16. Second and third pulleys 12 and 13 are mounted at the head end 3 of the jib i, adjacent another of the apices of each of the triangular frames 16. A hoisting line 9 extends from a hoisting winch 8 supported on a mounting platform k and is trained around the second pulley 12, around a fourth pulley Ik , between the tail and head ends 2 and 3 of the jib 1, and over the third pulley 13 to a depending load hook 18. The mounting platform k also supports a shaft 5 which in turn supports the jib 1 for pivotal movement about a horizontal axis extending transversely of the jib 1 and coinciding with the third of the apices of each of the triangular frames 16. The mounting platform 4 also supports fifth pulley means, in the form of twoO PIΛ,,. WIPO , pulleys 15 which are arranged below the pulleys 11 of the first pulley means at the tail end 2 of the jib i. Opp¬ osite ends of the two topping lines 7 are respectively attached to one of the pulleys 11 and to one arm of a yoke 19 supporting the fourth pulley Ik and the two topp¬ ing lines are trained around the first and fifth pulleys 11 and 15.The mounting platform is mounted above a fixed ring gear 20 and provided with a pinion 21 meshing with the ring gear 20. A motor 22 carried by the mounting plat¬ form k is operable to drive the pinion 21 to thereby cause a rotation of the mounting platform 4 about a ver¬ tically extending axis 23 through the centre of the ring gear 20. Part 24 of the mounting platform 4 serves as a counter-weight' for at least partly balancing loads' carr¬ ied by the load hook 8.The upper members 10 of the two triangular frames 16 serve as rectilinear guides for the yoke19 connecting the two topping lines 7 to the fourth pulley 14 so as to allow the fourth pulley 14 to move backwards and forwards along a rectilinear path between the two pulleys 11 of the first pulley means at the tail end 2 of the jib 1 and the second and third pulleys 12 and 13 at the head end 3 of the jib 1. A light-weight hydraulic piston-cylinder 6 extends from the jib 1 to the mounting platform 4.As shown in Figure 2, when the hoisting line 9 supports a load L there is an anti-clockwise turning moment of L.x, where x is the horizontal distance between the load hook 18 and the axis of the shaft 5. However, as shown, a loading of L is transmitted from the hoisting line 9 to each of the topping lines 7 through the fourth pulley 14 and, as the horizontal distance between the axis of the shaft 5 and the line of action of the topping lines 7OM - 7 -extending between the first and fifth pulleys 11 and 15 is approximately y, the clockwise turning moment resist¬ ing the load L is approximately 4L.y. The force there¬ fore required to be exerted by the hydraulic piston- cylinder assembly 6 is thus the difference between value of these clockwise and anti-clockwise turning moments and so topping can be effected with very little effort. In the alternative arrangement of the crane, shown in Figure3, there is only one topping line 7 and a load L suppor- ted by the load hook 18 induces a tension of 2L in this single topping line 7. In this case, the topping line 7 must be capable of withstanding twice the loading in the hoisting line 9.Clearly, from reference to both illustrated embodiments, it is advantageous if the .hoisting line 9 extending from the hoisting winch 8 to the second pulley 12 passes through or close to the axis of the shaft 5 so as to en¬ sure that the clockwise turning moment exerted by the topping line of lines 7 is not substantially counteracted by the tension in the hoisting cable 9 extending between the jib 1 and the hoist 8.As shown in Figure 3, the centre distance 24 between the shaft 5 and the first pulley 11 is greater than the cen¬ tre distance 25 between the shaft 5 and the fifth pulley 15. Thus, when the jib 1 is elevated, as shown in Figure4, the first pulley 11 moves to an end position.along¬ side the fifth pulley 15 such that the axes of the first and fifth pulleys (Hand 15) lie on a radial plane 26 containing the axis of the shaft 5. On further upward tilting movement of the jib 1, the tensile loading in the topping -line 5 urges the jib to return to the posi¬ tion it occupies for the arrangement shown in Figure 4. | CLAIMS A crane, comprisin :-a jib (i) having a tail end (2) and a head end (3);first pulley means (ll) mounted on the tail end (2) of the jib (i), second and third pulley means (12 and 13) mounted on the head end (3) of the jib (i),,and fourth pulley means (14) reciprocable between the first pulley means (ll) at the tail end (2) of the jib (l) and the second and third pulley means (12 and 13) at the head end (3) of the jib (1);mounting means (4) for supporting the jib (l) for pivotal movement about a horizontal axis (5) ext¬ ending transversely of the jib (i);a double-acting, piston-cylinder assembly (6) ext¬ ending between the jib (i) and the mounting means (4) for pivoting the jib (l) about the horizontal axis (5);fifth pulley means (15) fixedly mounted op the mounting means (4) beϊow the first pulley means (ll) at the tail end (2) of the jib (l);at least one topping line (7) extending around the first and fifth pulley means (ll and 15) and having~ opposite ends respectively connected to the fourth pulley means (14) and to one of the first and fifth pulley means (ll and 15);a hoisting winch (8); anda hoisting line (9) extending from the hoistingO Λ,„ winch (8) to the second pulley means (12), around the second and fourth pulley means (12 and 14), from the fourth pulley means (14) and around the third pulley means (13) to depend from the head end (3) of the jib (i).2. A crane, according to Claim 1, characterised in that the first, second, third and fourth pulley means (ii, 12, 13 and 14) are supported so that the or each topping line (10) acts on the fourth pulley means (14) along an axis which is disposed above the horizontal pivotal axis (5) of the jib (i).3. A crane, according to Claim 1 or Claim 2, charac¬ terised in that:-the number of topping lines (7) equals the number of lengths of the hoisting line (9) extending from the fourth pulley means (14) to the second and third pulley means (12 and 13); andthe first and fifth pulley means (ll and 15) con¬ tain pulleys for each of the topping lines (7) so that the topping lines (7) are each subjected to the same loading as the hoisting line (9).4. A crane, according to any preceding claim, charac¬ terised in that guide means (iO) for the fourth pulley means (14) extend along a rectilinear axis between the first pulley means (ll) at the tail end (2) of the jib(l) and the second and third pulley means (12 and 13) at the head end (3) of the jib (l). 5. A crane, according to any preceeding claim, charac¬ terised in that the first pulley means (ii) and the fifth pulley means (15) are disposed at different distances (24 and 25) from the horizontal pivotal axis (15) so that the first pulley means (ll) are movable into an end position alongside the fifth pulley means (15) so that the hori¬ zontal pivotal axis and the axes of the first and fifth pulley means (ll and 15) lie in the same plane (26). | MORRISON R; SPEEDCRANES LTD | MORRISON R |
WO-1979000917-A1 | 1,979,000,917 | WO | A1 | XX | 19,791,115 | 1,979 | 20,090,507 | new | F02N9 | null | F02B3, F02N9 | F02N 9/04, R02B 3/06 | IMPROVEMENTS IN COMPRESSED AIR STARTER | A compressed air starter including pneumatically operating starting valves for diesel engines, whereby includes one main starting valve connected to the cylinder head of the engine and provided with a valve body, which co-operates with a valve seat in order to alternatively open and close an inlet opening for compressed air to one cylinder, whereby during the start up of the engine, starting air (compressed air) continuously is supplied to the main starting valve, said valve body including one servo piston, which is controlled by servo air from a supply of servo air, which servo air is acting on the servo piston during moments related to the working phase of the engine. The object of the invention is to simplify the pipe arrangement for the compressed air at a diesel engine with several cylinders where it is usually arranged a main distributor for distributing the servo or pilot air, which controls the starting valves. The invention consists of a magnetic valve (17), which is connected to the main starting valve (8, 9, 10) and has a valve slide, which in one position (I-II) connects the supply (16) of servo air with a compression face of the servo valve (10), said servo valve hereby being activated to drive the valve body (8, 9) to the opening position and that, in a second position (II-III) of the valve slide, it controls the outlet from the supply (16) of servo air so that the servo piston drives the valve body (8, 9) to a closing position, said magnetic valve (17) being controlled by electric signals from a transmitter (20) controlled by the crank shaft or by an axis (22) rotating in accordance with the working phase of the engine. | IMPROVEMENTS IN COMPRESSED AIR STARTERThis invention relates to a compressed air starter including pneumati¬ cally operating starting valves for diesel engines, whereby includes one main starting valve connected to the cylinder head of the engine and provided with a valve body, which co-operates with a valve seat in order to alternatively open and close an inlet opening for compres¬ sed air to one cylinder, whereby during the start up of the engine, starting air (compressed air) continuously is supplied to the main starting valve, said valve body including one servo piston, which is controlled by servo air from a supply of servo air, which servo air is acting on the servo piston during moments related to the working phase of the engine.The object of the invention is to simplify the pipe arrangement for the compressed air at a diesel engine with several cylinders where it is usually arranged a main distributor for distributing the servo or pilot air, which controls the starting valves. Ordinary arrangements means that the piping must be doubled because of it is a need of sepa¬ rate pipes for the compressed air and separate pipes transporting the servo air. By this invention it is possible to reduce the length and the amount of pipes by that it only will be necessary with a short branch pipe for taking out the servo air from the main piping for the compressed air and this branch pipe is branched closely to the start¬ ing valve of each cylinder. It is also possible to achieve a more se¬ cure and more simple controlling of the starting procedure, which also applies for reversing the engine. The invention will also simpl fy the possibility of braking the engine with compressed air in the event that the engine must be stopped for reversed driving direction, which means that when the invention is used with a diesel engine for a ship the braking distance of the ship will be very much reduced. The invention is characterized by that a magnetic valve is connected to the main starting valve ancl has a valve slide, which in one position connects the supply of servo air with a compression face of the servo valve, said servo valve hereby being activated to drive the valve body to the opening and that, in a second position of the valve slide, it controls the outlet from the supply of servo air so that the servo piston drives the valve body to a closing position, said magnetic valve being control-O PI led by electris signals from a transmitter controlled by the crank shaft or by an axis rotating in accordance with the working phase of the engine.According to another embodiment of the invention the outlet from the supply of servo air is closed in said second position of the valve slide and the pressure face of the servo piston is hereby released of pressure. By this embodiment the piping is more simplified over the embodiment stated in claim 1.According to a third embodiment of the invention the supply of servo air is connected with the opposite side of the servo piston in said second position of the valve slide. The movement of the servo piston will hereby be controlled distinctly by the servo air instead of for instance the return stroke of the servo piston being carried out by means of a compression spring.According' to still another embodiment of the invention the electric signals are produced by a capacitive transmitter placed in front of a sector formed plate, which is mounted on said axis, whereby the rela¬ tive position of said sector and its size of angle determines the moment of generation of the signal and its length (duration). The signals in this way will give a very reliable function with great possi bilities to so adapt the servo air that it acts on the servo piston in the precise moment and with a length of time which is exact long enough The relevant parameters are the size of the sector and also its rota¬ ting time in relation to the crank shaft. The relative position of the plate may easily be adjusted and moreover it is possible to construct the sector formed plate so that its angle may be varied or adjusted. Components of these kinds are very reliable in their operation and can stand vibrations and shocks.In the case of several cylinders, which is most common, there is one capacitive transmitter for each magnet valve. Alternatively, one single transmitter may be used, which is connected to each one of the magne¬ tic valves via an electric distributor, which means that it is only necessary to arrange on.capacitive transmitter for each engine. An embodiment of the invention will now be described with reference to the enclosed drawings.Fig. 1 is thereby a section of a part of a cylinder head in which there is installed a main starting valve of known type.Fig. 2 is a partly diagramatically cross-section of a starting valve including a servo piston, whereby the embodiment is mounted on the valve house of the starting valve. The impulse transmitter and the piping is shown diagramatically.With reference to Fig. 1 there is shown a cylinder head 1 of a usual diesel engine. A main starting valve generally designated with 2 is placed in the cylinder head. The main starting valve is of a known type but shall be described shortly. It includes a sleeve 3, which is inser¬ ted in a hole through the cylinder head 1 and with close fitting to the inner. surface of the hole, for instance by jointing rings 4. The sleeve 3 has also a closed fitting in a hole 5, which goes into the top of the cylinder. Starting air under high pressure is inserted through a channel 6 and an inlet 7 into the sleeve. Within the sleeve there is a valve bo¬ dy including a shaft 8 and a valve disc 9. The compressed air, which enters the sleeve 3, can pass out through the opening 5 when the valve disc 9 opens the corresponding opening in the under end of the sleeve. The shaft 8 is in the upper end connected to a servo piston 10, which is forced upwards by a compression spring 11. A space within the sleeve is above the servo piston 10 and the servo air can be inserted to that space through a channel 12. The upper end of the sleeve 3 is covered by a cap 13.The operation of the main starting valve is as follows: Starting air or compressed air is supplied continuously during the starting procedure of the engine through, the channel 6 but the valve body will not be affected to move in any direction because the starting valve is balan- ced by equal areas of the servo pistons 10 and the valve disc 9. Further, the compression spring 11 acts upwards preventing the valve disc 9 from being moved to opening position. When servo air is supplied via the channel 12 to the upper side of the servo piston, the balancing action will be ceased and the valve shaft 8 with the valve disc 9 will be quickly moved downwards, so that the main starting valve is open and starting air or compressed air may pass from channel 6 through inlet 7 and- through the inner space of the sleeve 3 and over the val disc 9 and through the opening 5 and into the upper end of the cyli The engine piston (not shown) will hereby be pressed downwards from initial top position whereby the engine will start running.An embodiment of the invention will now be described with reference Fig. 2. Fig. 2 shows, at right side, a section through a part of a c linder head with its main starting valve, whereby 8 designated the s of the valve and 9 designates its valve disc and 10 designates the s piston. There are also the inlet channel 6 for the starting air for ressed air and an inlet channel 12 for the servo air. The starting a is supplied to channel 6 from a supply pipe 14, which has a branch p 15 leading to the channel 16. From the supply pipe 14 there is a sec branch pipe 16, from which the servo air is passed in order to contr the servo piston 10 and the supply is carried out via the channel 12 The control of supply of servo air is carried out by a magnet valve, which is generally designated with 17. The magnet valve has a slide (not shown), which has two end positions so that in one of these end positions the two ports designated with the arrows I and II are conn ted, whereby the supply of servo air to channel 12 is carried out, a that in the second end position, when, the ports designated with the arrows II and III are connected, channel 12 is vented and the port a the arrow I is closed. The slide of the magnet valve 17 is controlle according to the working phase of the cylinder to which the main sta ting valve 8, 9 and 10 belongs. The control of the magnet valve 17 i carried .out by electric pulses, which are supplied by a.circuit, whi includes the leads 18 and 19.The pulses are supplied by a capacitive transmitter 20, which is pla in front of a sector formed plate 21, which is fastened on a shaft 2 which is at right angle to the plate and which is rotating in time t the rotation of the crank shaft. The capacitive.transmitter is mount excentric in relation to the axis 22 and thus also- excentric in rela tion to the centre of rotation of the sector formed plate 21. The fo of the sector is shown in Fig. 2 by the section A-A. The sector form plate 21 is mounted in a ring and which is suspended by a stubb axis via spokes (not shown). The ring 31 has a peripheric groove, in which the sector formed plate 21 is mounted. The s'tubb axis 32 and thus the rimg 31 is rotated by the axis 22. In order to drive the plate 21 in the rotational movement of the ring, a shoulder 33 is placed in the groove of the ring. The position of the shoulder 33 thus determines the rela¬ tive position of the sector formed plate in relation to the angular position of the crank shaft and in relation to the position of the capa¬ citive transmitter 20. The capacitive transmitter produces an electric pulse when the sector formed plate is in front of the transmitter but as soon as the plate has passed, the electric pulse or the signal will be ceased. The supplied electric signal arrives to the magnetic valve 17, which adjusts the slide so that the ports at the arrows I and II are connected and thus servo air is supplied from the branch pipe 16 via.channel 12 to the upper side of the servo piston 10. Hereby the valve disc 9 is opened and starting air is inserted in to the cylinder of the engine. When the piston of said cylinder has reached its bottom dead centre, the sector formed plate 21 will pass over the transmitter20, whereby the electric signal accordingly is ceased. This means that the magnetic valve 17 wi]] hold a different position meaning that its slide is closing the connection between the ports at the arrows I and II and will open a connection between the ports at the arrows II and III, which means that the pressure is released above the servo piston 10, whereby the main starting valve is closed and the supply of starting air is cut off.When the engine shall be.started in reversed direction (backward mo¬ tion) the magnet valve 17 shall open for supply of servo air at another angular position of the crank shaft (known per se). The correct position of the sector formed plate 21 in relation to the angular position of the crank shaft is adjusted by that a second shoulder 39 is mounted on the other side of the sector in the groove of the ring 31. This shoulder 39:t. will drive the plate during the reversed motion, so that the electric signal is produced during a different moment than that which applies to forward motion of the engine.When the engine has several cylinders, the same amount of transmitters 20 are mounted in front of the rotation area of the sector formed plate21. Alternatively, one transmitter may be used, whereby, however, the number of revolutions of the sector formed plate must be higher and j. relation to the number of cylinders. It is also to take into considera tion whether the engine is a two-stroke cycle engine or a four-stroke cycle engine. When, thus, one transmitter is used for several cylinder a distributor must be used for distribution of the electric signals fr the only transmitter and such a distributor is known per se and used w the usual Otto-cycle machines.As can be seen from the above description, one magnet valve is mounted to each main starting valve and hereby only a short pipe 16 will be necessary to supply servo air to the servo valve and control it. It, thus, will be unnecessary to have two different pipings along for the air as is taught by the known art. In Fig. 2 there is shown only sche¬ matically a magnet valve, but it is of known type and it shall be note that there are many different types which can be used. The specific construction of the magnet valve may be dependent on the type of main starting valve to be used and thereby the operation and the form of the servo piston 10. Thus, in the shown embodiment, one side of the servo piston is pressurized when the servo piston shall be moved in on direction and the pressure will be released from this side of the pis¬ ton when the piston is performing its return stroke. However, it is possible, in an alternative embodiment, that one side of the servo piston is pressurized for carrying out the motion in one direction whereas the other side of the piston is pressurized for performing the return stroke of the servo piston. If so, a different type of slide of the magnetic valve 17 must be used than the one schematically shown an described above.Further on it is possible within the scope of the invention to use an alternative form of signal to be supplied to the magnet valve.Thus, it is. possible to use an impressed voltage on the magnet valve to keep it in one of the two positions, while the magnet valve will have its second position when the ypltage is null. This control may be carried out by switches of known type which are controlled to operate according to the working phase of the engine. Also, it is possible to control the. signal by a photo-cell.When starting up for reversed motion of the engine, it is possible to alter the signals by that the order between the signal transmitter and the cylinders are changed and this can be accomplished by an electric switching means between the transmitters and the magnet valve. This means that a signal from one transmitter will reach the magnet valve of for instance a fifth cylinder instead of the magnet valve of the first cylinder. | CLAIMS:1. Improvements in compressed air starter for diesel engines includi a main starting valve connected to a cylinder head and including a val body, which co-operates with a valve seat for opening and closing of a inlet for compressed air to the cylinder of the engine, whereby compres sed air during the starting operation continuously is supplied to the main starting valve and whereby the valve body includes a servo piston, which is controlled by servo air from a supply, which servo air is acti on the servo piston during moments which are related to the working pha se of the engine, c h a r a c t e r i z e d by that a magnet valve is connected to the main starting valve and has a valve slide, which in one position connects the supply of servo air with a pressure side of the servo piston, so that it can drive the valve body to an opening position and which valve slide in a second position controls the supply of servo air so that the servo piston drives the valve body to a closin position, said magnet valve being controlled by electric signals from a transmitter controlled by the crank shaft or a shaft rotating synchro¬ nously with the crank shaft.2. Improvement according to claim 1, c h a r a c t e r i z e d by that the supply of servo air is closed and that the pressure side of the servo piston is vented in said second position of the valve slide.3. Improvement according to claim 1, c h a r a c t e r i z e d by that in said second position of the valve slide the supply of servo air is connected with the opposite side of the servo piston. r4. Improvement according to claim 1, c h a r a c t e r i z e d by that the electric signals are produced by a capacitive transmitter, which is mounted in front of a sector formed plate, which is mounted on said axis and rotates thereby, whereby the angular position of the sector and the size of the angle determines the moment of generation of the signal and its length.5. Improvement according to claim 4, whereby the engine includes se¬ veral cylinders, c h a r a c t e r i z e d by that one capacitive transmitter is incorporated with each one of the magnet valves and that the transmitters are mounted along a circular path in front of theIJUREAO PI rotating plane of the sector formed plate.6. Improvement according to claim 4, whereby the engine has several cylinders, c h a r a c t e r i z e d by that the capacitive trans¬ mitter is connected with a magnet valve for each main start valve via an electric distributor.7. Improvement according to claim 4, c h a r a c t e r i z e d by that the sector formed plate is mounted freely rotating in a ring in its plane and concentric with the ring, whereby the ring is fastened on said rotating axis and has at least one shoulder, which drives the sector formed plate in at least one direction of rotation.8. Improvement according to claim 7, c h a r a c t e r i z e d by that the ring has a second shoulder, which drives the sector formed plate in an opposite direction of rotation and which shoulder is so positioned, that the sector formed plate will have a position in relation to the angular position of the crank shaft, which position corresponds to reversed motion of the engine.9. Improvement according to claim 1, c h a r a c t e r i z e d by that the electric signal is an impressed voltage, which is changed in time and length by a switching menas, which is controlled in relation to the working phase of the crank shaft.IJUREA^OMPI | HELLEMAA H; NORDSTJERNAN REDERI AB; SAMUEL O | HELLEMAA H; SAMUEL O |
WO-1979000927-A1 | 1,979,000,927 | WO | A1 | EN | 19,791,115 | 1,979 | 20,090,507 | new | A44B19 | null | A44B19 | A44B 19/38 | DEVICE FOR CONNECTING THE ENDS OF A SEPARABLE ZIPPER | An improved device for connecting the ends of a separable zipper having opposed strings or rows of interlocking teeth or elements including specially adapted terminals which facilitate the engagement of the ends of the zipper and initial movement of a slider to fasten the zipper teeth. The terminals are engagable by being brought together in a direction substantially perpendicular to the zipper rows. Compared to the conventional pin-and-socket terminal arrangement wherein the pin must be threaded through one relatively small port of the slider and then into the socket, the terminals are relatively large and essentially self-aligning during engagement. Once engaged, the terminals are free to rotate relative to each other, thus permitting the opposed rows of zipper elements to self-align as the slider is urged forward to engage the rearmost ends of the zipper elements. | DEVICE FOR CONNECTING THE ENDS OF A SEPARABLE ZIPPER This is a continuation-in-part of U. S. patent application serial number 940,255, filed September 7, 1978, which in turn is a continuation-in- part of abandoned U. S. patent application serial number 895,935, filed April 13, 1978. All of the subject matter of said prior applications is hereby incorporated by reference herein to the extent such subject matter is consistent with the following description of the presently preferred embodiments of the invention.The present invention pertains generally to slide fasteners and more particularly to the type of slide fastener commonly known as a zipper which has opposed strings or rows of interlocking elements or zipper teeth which are brought into interlocking engagement or fastened by movement of a slider in one direction along the rows and disengaged or unfastened by movement of the slider in the opposite direction.The present invention addresses the problem of reducing the difficulty involved with the initial engagement of the ends of a separable zipper on a jacket or similar garment, but it will be appreciated that the solution provided by the present invention has useful application to the entire field of slide fasteners without limitation to garments, which will be discussed by way of example herein. The task of initiating the operation of a conventional separable zipper requires a certain degree of care and dexterity so that .many children find the task to be impossible to perform and even adults sometimes find the task to be awkward, inordinately time consuming and frustrating. Conventional separable zippers for jackets and similar garments are typically arranged for right-handed operation of the slider by the wearer. The zipper teeth are arranged in rows along the edges of flexible supporting sheets, commonly known as tapes or stringers, ' which are sewn to the left and right< ξ RE lTOMFI , WIIPPOO . front vertical edges of the jacket so that the rows of teeth can be interleaved or brought into interlocking engagement by operation of the slider. A terminal pin is provided at the end of each row of teeth at the bottom of the jacket. In the case of a typical right-handed separable zipper, the slider is installed on the right row of teeth and a socket or U-shaped member is installed on the terminal pin at the end of the right row of teeth. The socket serves both as a stop for the slider and as a means for receiving the terminal pin at the end of the left row of teeth. Once the left terminal pin is properly inserted in the socket, the rows of teeth will be aligned and ready to be brought into interlocking engagement in the conventional manner by the forward movement of the slider up the rows of teeth. The task of initiating operation of the conventional right-handed separable zipper proceeds by inserting the left terminal pin through the left port of the slider down into the socket and then pulling the slider forward up the rows of teeth while holding the left terminal pin firmly in the socket by grasping the adjacent stringer or fabric. If the left terminal pin is not initially inserted fully into the socket, the slider will likely refuse to move forward because the teeth adjacent to the terminal pins will not be properly aligned. On the other hand, if the left terminal pin is initially inserted fully into the socket but is not held firmly in the socket, the forward movement of the slider will likely pull the left terminal pin free from the socket, thus preventing the fastening of the zipper. The foregoing problems have been addressed in certain respects by the prior art. For example, in place of the conventional terminal pins and socket, U. S. Patent No. 2,203,005 employs separable end-connecting members which enable proper alignment of the interlocking elements or teeth for engagement by the slider and which, once properly fastened, will not pull free from each other because of the forward movement of the slider. However, the approach of U. S. Patent No. 2,203,005 has not been adopted to any significant extent apparently because initial engagement of the specialized end- connecting members is no less difficult, if at all, in comparison with the conventional terminal pins and socket. In order to interconnect such end- connecting members, substantial care and dexterity are required to align and engage parts that are as small or smaller than a conventional terminal pin and its associated slider port and socket terminal. Furthermore, the interengagement of such specialized end-connecting members can not be achieved while the adjoining ends of the zipper elements are substantially parallel. Rather, it is necessary that the end-connecting members first be positioned at a wide angle during insertion of a relatively small pivot pin of one end-connecting member into a slot or opening of the other end-connecting member, whereupon only then can the .end-connecting members be rotated to bring the adjoining ends of the zipper elements into parallel alignment for passage through the front ports of the slider. The foregoing problems are solved in accrodance with the present invention as claimed by providing at the ends of the rows of zipper teeth terminals which operate in a manner similar to that of conventional snap fasteners that have cooperating annular snaps which are mated by merely bringing them together in the direction perpendicular to the plane of the adjoining fabric and then pressing them into engagement between thumb and forefinger. As with such snap terminals, the terminals of the present invention can be effortlessly fastened or engaged with a minimum of attention to alignment of the terminals during fastening since they naturally tend to self- align by virtue of their juxtaposition at corresponding positions on the opposed garment edges. Once a portion of one terminal is inserted into or nested within cooperationg portions of the other terminal, the ends of the rows of teeth will then be or will readily become aligned for interengage ent by the slider as it is pulled forward. The cooperating or nesting portions of the terminals are relatively large, preferably at least several times larger than the size of one of the front ports of the slider, such that relatively little dexterity is required to bring the terminals into operative engagement. There is no need to feed or pass anything through the slider in order to operatively engage the terminals and align the rearmost ends of the zipper rows in front of their corresponding slider ports. In addition, there is no tendency for the terminals of the present invention to separate in response to the mere forward movement of the slider during initial engagement of the rearmost ends of the rows of zipper teeth as is the case with the conventional pin-and-socket type zipper end connectors. It will therefore be appreciated that the principal advantage of the invention over prior-art separable zippers is the substantial simplification in the act of engaging the ends or terminal portions of the zipper. The terminals of the present invention are sufficiently large and easy to operate such that even children who are incapable of fastening a conventional pin-and- socket separable zipper can bring the terminals of the present invention into engagemen properly with little attention to alignment and can pull the slider forward up the rows of zipper teeth without the risk that the terminals will pull free of each other.The presently preferred way of carrying out the invention is described in detail below with reference to drawings which illustrate five specific embodiments, in which:OMPIΛ. WIPO FIGURE 1 is perspective view of a first embodiment of the present invention showing first and second zipper terminals aligned just prior to engagement, the first terminal or slider base terminal carrying a slider adapted to interengage conventional rows of zipper teeth, the second termina or receiving terminal being adapted to mate with the first terminal in the indicated manner;FIGURE LA is a front elevational view of a conventional slider used in the present invention;FIGURE 2 is a perspective view showing the terminals i operative engagement and the slider moved slightly forward up the rows o zipper teeth;FIGURE 3 is a plan view of the terminals with the rearmos zipper teeth in interlocking engagement;FIGURE 4 is a view in cross-section taken along line IV-IV o FIGURE 3 in the direction indicated;FIGURE 5 is a view in cross-section taken along line V-V o FIGURE 3 in the direction indicated;FIGURE 6 is a perspective view of a second embodiment of the present invention showing a slider base terminal and a receiving termina aligned just prior to engagement, the view being similar to FIGURE 1 but with the slider removed in order to illustrate various details of the slider bas terminal;FIGURE 7 is a view in cross-section as the terminals of FIGUR 6 would appear when operatively engaged with the slider in its rearmos position on the slider base terminal, the view looking in the direction indicate from line VTI-VII of FIGURE 6;FIGURE 8 is an enlarged view of a portion of FIGURE 7; FIGURE 9 is a front elevational view of another slider bas terminal and associated slider carried thereon; FIGURE 10 is a perspective view of the mate to the terminal oFIGURE 9, the terminals of FIGURES 9 and 10 representing a thir embodiment of the present invention;FIGURE 11 is a perspective view of a fourth embodiment of th present in **vention illustrating the top front surfaces of a slider base termina and associated receiving terminal aligned just prior to engagement;FIGURE 12 is a perspective view of the bottom surface of th slider base terminal of FIGURE 11 separate from its receiving terminal wit the addition of a slider shown in phantom lines as it would appear when carrie in its rearmost position thereon;. W wIi FIGURE 13 is a plan view of the bottom surface of the slider base terminal of FIGURE 12;FIGURE 14 is a top plan view of a fifth embodiment of the present invention illustrating a slider base terminal and a receiving terminal in operative engagement;FIGURE 15 is a view in cross-section taken along line XV-XV of FIGURE 14 in the direction indicated; andFIGURE 16 is a view in cross-section taken along line XVI-XVI of FIGURE 14 in the direction indicated. Referring to FIGURES 1-5, a device for connecting the ends of a separable zipper is illustrated and designated generally by reference numeral 10. The zipper includes interlocking elements or teeth arranged in adjacent rows 12 and 14 in the conventinal manner along the respective edges of flexible supporting sheets or stringers 16a and 16b. Installation of the zipper in a suitable garment is achieved in a conventional manner, such as by sewing the stringers 16a and 16b to the respective right edge 18a and left edge 18b of a garment shown in phantom in FIGURES 1-3. The terms left and right are used herein with reference to the point of view of a wearer of the garment. The device 10 comprises a first terminal or slider base terminal 20 and a second terminal or receiving terminal 22, which terminals can be operatively engaged or brought together into working relationship in a manner similar to the operation of a conventional snap fastener such that the slider base terminal 20 is aligned over and then pressed into the receiving terminal 22 in the manner indicated. As seen in FIGURE 1, the slider base terminal 20 is adapted to carry a conventional slider 24 which is manually operable by means of a handle 26 pivotally mounted in a longitudinal slot 27 atop the slider 24. When the terminals 20 and 22 are disengaged, the slider 24 is normally carried on a base or generally disc-shaped platform 28 which, in the present example, forms an upper surface portion of the terminal 20. The slider 24 includes top and bottom plates 30 and 32 held in spaced-apart parallel planes by a center post 34 which forms the leading edge of the slider 24 as it moves forwardly.As seen in FIGURE 2, when the slider 24 is moved forwardly, it progressively forces the teeth in the opposed rows 12 and 14 into interlocking engagement. As seen in FIGURE 1A, the slider plate 30 has downwardly extending right and left side rims 36a and 36b and the bottom slider plate 32 has upwardly extending right and left side rims 38a and 38b. The rims 36a and 38a form a right side slot through which the stringer 16a passes and the rims 36b and 38b form a left side slot through which the stringer 16b passes, as isOMPI Λ. WIPO « conventional in the zipper art. As the slider 24 moves forward, the teeth in' the opposed rows 12 and 14 enter respective right and left slider ports 39a and39b formed between the front edges of the respective side rims and the center post 34. The manner in which the slider 24 engages and disengages the teeth in the opposed rows 12 and 14 is generally known and thus will not be elaborated on further. From the foregoing, however, it will be appreciated that the slider 24 can be readily moved from the position seen in FIGURE 2 to its rearmost position on the slider base terminal 20 because the platform 28 is made to lie in the same plane as the adjacent portions of the stringers 16a and 16b whenever the terminals 20 and 22 are operatively engaged. Since the stringers 16a and 16b are ordinarily flexible, the full length of each stringer 16a and 16b will not necessarily lie in a single plane. However, portions of the stringers 16a and 16b will lie in what will be referred to herein as the slider working plane when they pass through the slider 24. The term slider working plane is intended to mean that plane defined by the intersection of longitudinal and transverse axes of the slider 24, the longitudinal axis lying in the direction of slider movement as indicated by the dashed line L in FIGURE 2 and the transverse axis bisecting the slider ports 39a and 39b as indicated by the dashed line T in FIGURE 1A. The slider base terminal 20 includes a raised shelf 40 which serves as a guide track for slidably cooperating with the upper rims 36a and 36b so as to keep the slider 24 in general forward alignment when situated in its rearmost position thereon. The platform 28 further includes a notch 42 for receiving the center post 34 of the slider 24 in the manner shown in FIGURE 1. The terminal 20 includes a guide segment 44 which defines the rearmost end of the right row 12 of zipper teeth. The guide segment 44 serves in the manner of a cam to guide the leading edge of the center post 34 into operative proximity with the rearmost zipper tooth 12a of the right row 12. Similarly, the terminal 22 includes a guide segment 46 which defines the rearmost end of the left row 14 of zipper teeth. The guide segment 46 serves to guide the leading edge of the center post 34 into operative proximity with the rearmost zipper tooth 14a of the left row 14, provided the terminals 20 and 22 are operatively engaged and rotationally oriented relative to each other in the position shown. It is presently preferred that the guide segment 44 and the raised shelf 40 have a eommon cδlinear right edge 48a for a smooth transition in the movement of the slider 24 exiting from and returning to the terminals 20 and 22. The shelf 40 also preferably has a straight left edge 48b at its rearmost position and a generally S-shaped curved edge 49 leading from the edge 48b to the left edge of guide segment 44. The curved edge 49 permits a slight lateral or rotationalOM movement of the slider 24 with respect to terminal 20 as the center post 34 of the slider 24 is guided between the guide segments 44 and 46 which tends to cause the terminals 20 and 22 to rotate slightly relative to each other.In accordance with a unique feature of the invention, the terminals 20 and 22 are engaged or nested in a manner similar to that of a snap fastener by pressing the terminals 20 and 22 together after first aligning them in the manner indicated in FIGURE 1 while the slider 24 is carried in its rearmost position on the platform 28. The nesting or mating portions of the terminals 20 and 22 are preferably generally annular in shape so that the terminals 20 and 22 can be brought together without having to first align the two zipper rows 12 and 14 at any particular angle to each other as will be appreciated more fully from the description that follows.Referring again to FIGURE 1, the slider base terminal 20 includes curved wall 50 extending downward from the periphery of the platform 28. The wall 50 preferably includes a cuff 52 projecting radially outward from a cylindrical surface 54 of the wall 50. In this embodiment, the cuff 52 is provided only through a semicircular arc around the rearward half of the cylindrical surface 54. The receiving terminal 22 includes a curved mating wall 56 extending upward from the periphery of a generally circular floor 58. The wall 56 preferably includes an upper interior cylindrical surface 60 of a first diameter and a lower interior cylindrical surface 62 of a second diameter, the second diameter being greater than the first diameter. The wall 56 includes an upper peripheral rim 64 which with the cylindrical surface 60 defines an aperture 65 for receiving the mating wall 50 of terminal 20. The terminals 20 and 22 are brought into operative engagement by first seating the cuff 52 on the upper peripheral rim 64 of the wall 56 and then pressing the terminals 20 and 22 together until the bottom of the wall 50 abuts the floor 58, which is designed to occur when the rearmost portions of the stringers 16a and 16b have become essentially coplanar with the previously defined slider working plane when the slider 24 is in its rearmost position on terminal 20. Accordingly, the term operative engagement and terms of similar import are used herein to mean that the terminals 20 and 22 (and their counterparts in subsequently described embodiments) are mated or nested but not necessarily in any particular relative rotational position to each other nor are they necessarily interlocked. It will be appreciated, therefore, that the generally cylindrical construction of the terminals 20 and 22 permits them to be engaged when the adjacent ends of the zipper rows 12 and 14 are in a nonparallel orientation. In order to facilitate guiding terminal 20 into the terminal 22, the cuff 52 is generally frustoconieal so that it tapers with increasing diamete in moving axially upward along the wall 50 to a maximum diameter at a generally radially oriented shelf 66 which interconnects the conical surface o the cuff 52 with the cylindrical surface 54 of the wall 50. The diameter of the cylindrical surface 54 is slightly smaller than the diameter of the upper interior cylindrical surface 60 of the terminal 22, and the maximum diameter of the cuff 52 is slightly greater than the diameter of the surface 60 such tha forcing the terminals 20 and 22 together causes the cuff 52 to compress slightly radially and/or causes the wall 56 to expand radially as the cuff 52 slidably passes within the surface 60. The degree of compression of the cuff 52 relative to the expansion of the wall 56 depends on the properties of th materials employed in fabricating the terminals 20 and 22, a relatively rigid and resilient plastic being a preferred material. When the shelf 66 passes beyond the surface 60, the cuff 52 and wall 56 resiliently return to their normal dimensions with the shelf 66 abutting an annular shoulder 68 whic interconnects the two cylindrical surfaces 60 and 62. Once the slider 24 is moved forward up the rows 12 and 14 of zipper teeth, inadverten disengagement of the terminals 20 and 22 is then prevented by virtue of the shelf 66 abutting the annular shoulder 68 at the rearward portions of the terminals 20 and 22 combined with the locking action of the rearmost zipper teeth 12a and 14a tending to keep the forward portions of the terminals 20 an 22 locked in the engaged position shown in FIGURE 2. In addition, the guide segments 44 and 46 can optionally be adapted to interlock with each other to further insure against inadvertent disengagement of the terminals 20 and 22, as will be decribed below with reference to FIGURES 3 and 4. However disengagement of the terminals 20 and 22 can readily be achieved when the slider 24 is situated in its rearmost position by pulling upward (in the view o FIGURE 1) on the portion of the garment hem or edge 18a adjacent to the slider base terminal 20 and simultaneously downward on the portion of the garmen hem or edge 18b adjacent to the receiving terminal 22, which causes the forward portions of the terminals 20 and 22 to begin to separate since no locking action is then being provided by the unfastened zipper teeth. Such pulling action on the garment edges 18a and 18b causes the terminals 20 and 22 continue to^. tilt out of axial alignment until the cuff 52 can slip past the shoulder 68 permitting the terminals 20 and 22 to pull free from each other.It will be appreciated from the foregoing that the terminals 20 and 22, once engaged, are kept essentially in coaxial alignment by the relatively snug fit of the slidably abutting walls 50 and 56. In accordance withΛ- an important feature of the device 10, the mating walls 50 and 56- define circular arcs subtending angles in excess of 180 degrees so that, once engaged, the only relative movement of the terminals 20 and 22 that can occur will be rotational and not translational. Thus, pulling the slider 24 forward away from the terminals 20 and 22 to fasten the zipper rows 12 and 14 will not cause terminal 20 to move forward relative to terminal 22 because the forward portions of surface 54 will abut the cooperating portions of surface 60.However, it is also a desireable feature of the device 10 that, while being carried in its rearmost position on the terminal 20 with the terminals 20 and 22 operatively engaged, the slider 24 is carried within the nesting portions of the , terminals 20 and 22. Accordingly, the preferred mating walls 50 and 56 are not continuous through a full 360 degrees, but are provided with gaps 69a and 69b at their forward portions to permit the slider 24 to exit from the nesting portions of the terminals 20 and 22 as it moves forward to engage the zipper rows 12 and 14. One advantage of this preferred arrangement is that, while the slider 24 is carried in its rearmost position on the terminal 20, the axis of relative rotational movement of the terminals 20 and 22 passes approximately through the center of the slider 24 which is snugly encompassed within the cylinders defined by walls 50 and 56. Thus, if the zipper rows 12 and 14 are not aligned in parallel when it is desired to fasten them together, pulling forwardly on the handle 26 and rearwardly on the receiving terminal 22 will automatically cause the terminals 20 and 22 to rotate until the rows 12 and 14 are substantially parallel, whereupon the slider 24 is permitted to exit forwardly through the aligned gaps 69a and 69b in the walls 50 and 56. Most preferably, the gaps 69a and 69b in the forward portions of the walls 50 and 56 are just slightly wider than the maximum width of the slider 24 so that it will not exit through the gaps 69a and 69b until they are perfectly aligned, thus assuring that the guide segments 44 and 46 will pass through the two front ports 39a and 39b of the slider 24 on opposite sides of the center post 34. If the terminals 20 and 22 are initially brought together with the rearmost ends of the zipper rows 12 and 14 well out of parallel, at right angles for example, then the leading edge of the center post 34, as the user pulls forwardly on the slider handle 26, will slidably bear against the cylindrical surface 60 as the terminals 20 and 22 begin to rotate into alignment. It will be appreciated that the foregβing preferred features of the device 10 permit the terminals 20 and 22 to be snapped into engagement even when the wearer is in a sitting position during which the zipper rows 12 and 14 are ordinarily misaligned.OMPI /,, WIPO In order to facilitate pulling rearwardly on the terminal 22, a tab70 is provided at the rear thereof for grasping, for example, between the thumb and index finger of the left hand of the wearer. The provision of the slot 27 atop the slider 24 is believed to facilitate the rotational action of the terminals 20 and 22 by permitting the point of pivotal attachment of the handle 26 to the slider 24 to move forward of the axis of rotation. As the slider 24 begins to move forwardly, the center post 34 slidably engages the facing surfaces of the guide segments 44 and 46 which in turn pass through the slider 24 and are brought into engagement as seen in FIGURES 2 and 3 because the interior passageway of the slider 24 narrows progressively. As the slider 24 continues forwardly, the zipper teeth in the rows 12 and 14 are progressively brought into interlocking engagement in the conventional manner.Referring now to FIGURES 3 and 4 in conjunction with FIGURE 2, additional features of the preferred zipper terminal device 10 will be described. After the slider 24 has been pulled forward up the zipper rows 12 and 14, the terminals 20 and 22 will remain locked in engagement by virtue of the insertion of a tongue 72 on guide segment 46 into a cooperating groove 74 in guide segment 44. The mating of the tongue 72 and groove 74 occurs automatically with a final slight rotation of the terminals 20 and 22 as the rearmost interior surface of the left upper rim 36b of the slider 24 pushes counterclockwise on the guide segment 46 while the rearmost interior surface of the right upper rim 36a pushes clockwise on the guide segment 44. As previously mentioned, even without the tongue-and-groove locking feature of the guide segments 44 and 46, the interlocked rearmost zipper teeth 12a and 14a will tend to keep the forward portions of the terminals 20 and 22 in engagement while the cuff 52 (FIGURE 1) of terminal 20 abuts the annular shoulder 68 of terminal 22 to keep the rearward portions of the terminals 20 and 22 locked in engagement.To further assist in securing the terminals 20 and 22, the guide segment 44 preferably interlocks with the zipper tooth 14a in like manner as the various other zipper teeth of the opposed rows 12 and 14 interlock with each other. In particular, the guide segment 44 includes a forwardly extending projection 76 evident in FIGURE 1, which is adapted to engage a mating indentation in the rearward portion of the zipper tooth 14a in the manner depicted in FIGURE 3.With particular reference to FIGURES 3-5, a preferred technique will now be described for securing the terminals 20 and 22 to the stringers 16a and 16b and the adjacent garment edges 18a and 18b. Extending radially outward from the upper forward portions of the terminals 20 and 22 are wings( OM 80 and 82, respectively. The wings 80 and 82 each include top (80a, 82a) and bottom (80b, 82b) layers of a folded flange. As exemplified in FIGURE 5, the wing 82 has a top layer 82a and a bottom layer 82b joined at a bend or fold 82c. Disposed between the layers 82a and 82b is the rearmost corner of the stringer 16b. Although other means of attachment are also feasible, it is presently preferred for sake of simplicity that the respective wings 80 and 82 be glued to their respective stringers 16a and 16b and that the wing-stringer assemblies then be securred to their respective adjacent garment edges 18a and 18b (shown in phantom in FIGURE 3) by sewing. Accordingly, slotted openings 84 are provided in the wings 80 and 82, which openings register in the respective top and bottom layers of the wings 80 and 82 to permit a needle and thread (not shown) to pass therethrough. As exemplified in FIGURE 5, the exterior faces of the wings 80 and 82 may be curved between openings 84 to facilitate guiding the point of the needle into any of the openings 84, since they are most likely obscured from view by the garment edge 18a or 18b to be attached thereat.Referring briefly again to FIGURE 4, it will be seen that the stringers 16a and 16b are provided with beaded edges 86a and 86b, respectively, in accordance with one of several well-known prior-art techniques for securring the individual zipper teeth to the stringers 16a and 16b. (It will, of course, be appreciated that the invention can be practiced using other suitable slide-fastening interlocking elements and associated means for attachment to the edges of a garment.) The guide segments 44 and 46 include hollow interiors for accepting the rearmost portions of the beaded edges 86a and 86b so that attachment of the wings 80 and 82 to the respective stringers 16a and 16b will automatically self-align the guide segments 44 and 46 with the respective rows 12 and 14 of zipper teeth.An additional feature of the inventive device 10 which is apparent from FIGURES 1 and 4 involves the provision of an L-shaped member 88 extending forwardly from the wall 56 and the floor 58 of the terminal 22. The L-shaped member 88 gives added support to the guide segment 46 and adjoining wing 82 to resist flexing at the point of attachment of the wing 82 to the rim 64 of the terminal 22. The placement of the L-shaped member 88 also conveniently permits it to serve as a guide chute for the slider 24, as will be appreciateαVfrom the view of FIGURE 2.A second embodiment of the invention will now be described with reference to FIGURES 6-8, wherein a zipper terminal device is illustrated and designated generally by reference numeral 110. In order to simplify the description of the device 110, parts that function in a similar manner to corresponding parts in the above-described device 10 are designated using similar reference numerals. The following description will focus only on the most important differences of the device 110 with respect to the above- described device 10. It will be appreciated that, while they are not shown i the similar view of FIGURE 6, the rows 12 and 14 of zipper teeth of FIGURE 1 would be provided in essentially the same manner along the beaded edges 186 and 186b of the respective stringers 116a and 116b.The most significant difference between the device 110 and the above-described device 10 is the inclusion of a slider retaining mechanism comprising a spring member 190 suspended from the slider base terminal 120 so that it will lie within the interior passageway 191 of the slider 124 and retain the slider 124 in its rearmost position on the terminal 120 unless the terminals 120 and 122 are operatively engaged in the position shown in FIGURE 7. Th spring member 190 includes a catch 192, which extends into an opening 194 i the bottom plate 132 of the slider 124 when the spring member 190 is unflexe as shown in phantom in FIGURE 8, whereby the forward movement of the slider 124 is prevented by virtue of the catch 192 contacting a wall 196 of the bottom plate 132. The spring member 190 includes an arm 198 extending through an opening 200 in a rearward portion of the wall 150 of terminal 120. When the terminals 120 and 122 are operatively engaged, the slider 124 is released for forward movement by a projection 202 extending upward from rearward portion of the wall 156 of terminal 122 to flex the spring member 190. The terminal 120 preferably includes a lip 204 which extends downward fro the rear of the shelf 140 in order to cover the arm 198 to prevent accidental release of the slider 124. The lip 204 and the adjacent portion of terminal wal 150 form a narrow gap into which the projection 202 extends when the terminals 120 and 122 are operatively engaged, thereby pushing the arm 198 upward to flex the spring member 190 thus lifting the catch 192 out of the opening 194. As seen best in FIGURE 6, the upper peripheral rim of the wall156 includes two beveled surfaces 164a and 164b which serve to guide the slide base terminal 120 down into operative engagement with the receiving terminal 122. The spring flexing projection 202 extends upward from the upper bevele surface 164a to provide a curved cam surface 206 which is slidably engaged by the spring a?m 198 to gradually flex the spring member 190 as the terminals 120 and 122 are rotated to bring the guide segments 144 and 146 into operative proximity. Thus, the slider 124 will not be released for forward movement until the guide segments 144 and 146 are aligned for passage through the front ports of the slider 124 on opposite sides of the center post 134. As the slider base terminal 120 is rotated clockwise with respect to the receiving terminal 122, the arm 198 rides up along cam surface 206 to the top of the projection 202 thereby lifting the catch 192 out of the opening 194, as depicted in FIGURE 7. It is clearly evident from the foregoing description of the device110 that one important advantage of such a slider retaining mechanism is that the slider 124 will not be released to exit forwardly through the gaps 169a and 169b in the walls 150 and 156 until the relative rotational position of the terminals 120 and 122 is appropriate for fastening the zipper. Another important advantage of such a slider retaining mechanism is that the slider 124 and slider base terminal 120 can be controlled together as a unit using the slider's handle 126, which is conveniently pivotable and longitudinally moveable within the slot 127. Thus, for example, when the terminals 120 and 122 are separated and the slider 124 is captured on the terminal 120 by virtue of the spring catch 192 extending down into the opening 194, engagement of the terminals 120 and 122 is easily achieved by grasping the handle 126 with one hand and the wing 182 of terminal 122 with the other hand and then merely forcing the terminals 120 and 122 together.When compared to the device 10 of FIGURES 1-5, the operation of the device 110 of FIGURES 6-8 more nearly approximates the workings of a conventional snap fastener as will be appreciated from the following description of additional features of the device 110. It will be seen fromFIGURE 6 that the cuff 152 is coextensive with the entire periphery of the wall150, which is disposed through an arc substantially in excess of 180 degrees. During engagement of the terminals 120 and 122, the cuff 152 is guided by the beveled edges 164a and 164b through the receiving aperture 165 and down past the innermost surface 160 of terminal 122 thereby compressing the cuff 152 and/or expanding the wall 156 until the outermost edge of the cuff 152 passes beyond the surface 160, whereupon the cuff 152 and the wall 156 resiliently return to their normal dimensions. At this point, terminals 120 and 122 are locked against axial movement but are free to rotate relative to each other. It will of course be appreciated that the distance from the floor 158 to the shoulder 168 will preferably be only slightly greater than the distance from the bottom of the wall 150 to the outermost edge of the cuff 152 so that, as the bottom of the wall 150 snaps into abutment with the floor 158, the terminals120 and 122 contemporaneously become operatively engaged and interlocked against axial movement without having to rotate the terminals 120 and 122 relative to each other. The terminals 120 and 122 are readily disengaged by pulling upward on the handle 126 of the slider 124, when situated on the terminal 120, while holding down on terminal 122 with opposing forces sufficiently strong to recompress the cuff 152 a d/or reexpand the wall 156 until the cuff 152 can again pass within the surface 160. In order to facilitate this mode of release, the cuff 152 is provided with a curved upper edge 166 for reducing the force required to pull the terminals 120 and 122 apart. In addition, it may be desirable to provide axial slits 208 radially spaced apart around the wall 156 for increased flexibility. Such slits 208 are particularly advantageous where the terminals 120 and 122 are fabricated from a relatively rigid material, such as steel.In comparing the two embodiments 10 and 110, it will be appreciated that in both cases the slider base terminal (20 or 120) is snapped into engagement with its receiving terminal (22 or 122), whereas the mode of release employed by device 10 differs somewhat from that employed by device 110. In the ease of the device 10, the terminals 20 and 22 are disengaged by tilting them out of coaxial alignment by forcing their forward portions apart until the cuff 52 of terminal 20 can be withdrawn from beneath the shoulder 68 at the rearward portion of terminal 22. In the case of device 110, the terminals 120 and 122 are snapped out of engagement while generally maintaining the terminals 120 and 122 in coaxial alignment. Such snap-release is achieved by grasping the slider handle 126 or the wing 180 with one hand and the wing 182 with the other hand and pulling in opposite directions. In either case, the disengagement of the respective terminals of devices 10 and 110 requires no special concentration or dexterity. In both cases, the respective terminals readily and automatically release from each other in response to moderate forces tending to pull them apart. However, the snap-release action of the terminals 120 and 122 tends to apply slightly more stress to the wing 182 of device 110 than is applied to the wing 82 of device 10. Accordingly, as seen in FIGURE 6, the L-shaped member 188 is preferably permanently secured to the lower wing plate 182b for added support.In the following description of several additional embodiments of the invention illustrated in FIGURES 9-15, it will be appreciated that the zipper teeth and associated stringers, which are not shown, can be attached to the terminafs in the same manner as with the first embodiment of the invention shown in FIGURES 1-5. It will also be appreciated that the wings (380, 382, 480, 482, 580, 582) and guide segments, (344, 346, 444, 446, 544, 546), which are merely shown schematically as solid members in FIGURES 9- 15, preferably have provisions for receiving the stringers in a manner similar to that depicted in FIGURE 4. A third embodiment of the invention will now be described with reference to FIGURES 9 and 10 wherein parts that function in a similar manner to previously described parts are designated using similar reference numerals.As seen in FIGURE 9, the slider 324 is carried above the platform 328 of the slider base terminal 320. This arrangement eliminates the need for a gap in the wall 350 as is required in the first two embodiments of the invention in which the slider is carried partially within the nesting portion of its slider base terminal. Furthermore, the mating wall 356 of the receiving terminal 322 of FIGURE 10 is provided through a complete 360° are or ring. It will therefore be appreciated that when the terminals 320 and 322 of this embodiment are operatively engaged, the slider 324 is carried in its rearmost position above and entirely outside of the nesting portions defined by the annular walls 350 and 356 of the terminals 320 and 322. The structural simplicity of this third embodiment of the invention, though not as compact as the previously described embodiments, makes it comparatively less expensive to fabricate. The slider 324 is held in proper alignment when in its rearmost position on the slider base terminal 320 by means of a guide track 340, which is affixed atop the platform 328, and cooperating L-shaped flanges 341a and 341b, which extend downward from the bottom of the slider 324. The guide track 340 appears generally T-shaped in the view of FIGURE 9 and preferably tapers to a pointed forward end in the manner of guide track 440 to be described below in conjunction with FIGURE 11.The terminals 320 and 322 are adapted to be snapped into engagement by merely pressing the slider base terminal 320 down through the receiving aperture 365 and into the terminal 322. The wall 350 of terminal 320 has an outwardly curved peripheral surface 366 which abuts a cooperating recess or indented surface 368 along the interior of the wall 356 of terminal322. The interior dimension of the upper bevelled rim 364 of terminal 322 and the cooperating portions of the wall 350 of terminal 320 are adapted so that the wall 350 will contract slightly and/or the wall 356 will expand slightly so as to allow the engagement of the terminals 320 and 322. When engaged, however, the terminals 320 and 322 are essentially free to rotate relative to each other so that the guide segment 346 can be positioned to pass into the left front slider port 339b just to the left of the center post 334. The guide segment 346 is supported over and just forward from the rim 364 by means of the wing 382 which in turn cantilevers from its L-shaped supporting wall 388.A fourth embodiment of the invention will now be described with reference to FIGURES 11-13 wherein parts that function in a similar manner to previously described parts are designated using similar reference numerals. will be appreciated that the slider 424 (partially visible in phantom in FIGURES 12 and 13) is held in proper orientation on the slider base terminal 420 by means of a guide track 440 (seen in FIGURE 11) which cooperates with flanges (not shown) on the bottom of the slider 424 in a similar manner to the guide track 340 and flanges 341a and 341b of the previously described embodiment as illustrated in FIGURE 9. To the rear of the guide track 440 is a rim 443 which serves as a stop for the slider 424. Like the previous embodiment of FIGURES 9 and 10, the slider 424 is supported in its rearmost position on a platform 428 above and entirely outside of the nesting portions of the terminals 420 and 422, as will be apparent from FIGURES 11 and 12. The wings 480 and 482 and guide segments 444 and 446 are therefore supported above the plane of the platform 428, the wing 480 cantilevering from a supporting shelf 445 and the wing 482 cantilevering from an L-shaped supporting wall 488. The slider base terminal 420 includes spiral-shaped bottom walls or surfaces 450a and 450b which are adapted to slidably abut complementary walls or surfaces 456a and 456b of the receiving terminal 422 during engagement of the terminals 420 and 422. By bringing the surfaces 450a and 450b into contact with the respective surfaces 456a and 456b and rotating the terminals 420 and 422 relative to each other until the guide segment 446 is aligned for passage through the left front port 439b of the slider 424, locking or latching members 466a and 466b on the bottom of terminal 420 become partially engaged with complementary members 468a and 468b down within the aperture 465 of terminal 422. Thereafter, as the slider 424 is moved forwardly beyond the guide segments 444 and 446, a final slight rotation of the terminals 420 and 422 causes the latching members 466a and 466b of terminal 420 to become completely engaged with the respective latching members. 468a and 468b of terminal 422. Preferably, when the slider 424 is in its rearmost position, it extends forward slightly beyond the front edge of surface 450a so that the right side of the center post 434 abuts the adjacent edge of the guide segment 444 as depicted in FIGURE 13. Thus, when the terminal 420 is rotated fully clockwise with respect to terminal 422, the left side of the center post 434 will abut the guide segment 446, thereby assuring that the zipper rows are perfectly aligned in front of their respective slider ports prior to moving the slider 424 fβrward.It will be appreciated that the generally cone-like arrangement of the terminals 420 and 422 greatly facilitates guiding them into operative engagement. The receiving aperture 456 defined by the upper peripheral rim 464 of terminal 422 provides an easy target for the bottom portion of terminal 420. Furthermore, the dual-spiral construction of the cooperating surfaces of the terminals 420 and 422 tends to promote rotation in the proper direction for interlocking the terminals 420 and 422 merely by the force of pressing the terminals 420 and 422 together. A zipper terminal device 510 in accordance with a fifth embodiment of the invention will now be described with reference to FIGURES 14-16 wherein parts that function in a similar manner to previously described parts are designated using similar reference numerals. The slider employed in this embodiment is illustrated by the phantom outline 524 in FIGURE 14. When in it rearmost position as shown, the slider 524 is carried forward and entirely outside of the nesting portions of the terminal 520 and 522. For this purpose, the slider base terminal 520 is provided with guiding and retaining walls 540 which provide a slider receptacle on both sides of a central web 528. The web 528 is inserted between the plates of the slider 524 in a manner similar to the way in which the platform 28 is inserted between the plates 30 and 32 of the slider 24 of FIGURE 1. When in its rearmost positon, the slider 524 is held in proper alignment by the walls 540 with the center post 534 of the slider 524 resting in a notch 542 in the web 528. As seen in FIGURE 15, the slider base -terminal 520 includes a raised annular portion 550 adapted to mate with an annular recessed portion 556 of the receiving terminal.522. The nesting or mating portions of the terminals 520 and 522 include peripheral rims 566 and 568, respectively, which operate in the manner of a snap fastener to hold the terminals 520 and 522 in operative engagement while permitting relative rotational movement thereof. The operation of the device 510 proceeds as follows. With the slider 524 in its rearmost position on the terminal 520 as depicted in FIGURE 14, the terminals 520 and 522 are pressed or snapped into operative engagement as seen best in the view of FIGURE 15. The exterior faces of the terminals 520 and 522 are provided with shallow recesses 551 and 557 to facilitate grasping the respective annular nesting portions 550 and 556 between the thumb and index finger of the user while snapping the terminals 520 and 522 into engagement. Once engaged, the terminal 522 is rotated slightly counterclockwise with respect to the terminal 520 to the approximate position seen in FIGURE 14 wherein the guide segment 546 has become aligned for passage through the respective front port of the slider 524. This relative rotation will tend to occur automatically as the user pulls downward on the terminals 520 and 522 provided they are not grasped too tightly. Thereafter, the slider 524 can be pulled up the rows of zipper teeth (not shown). As the slider 524 passes the guide segments 544 and 546, they are first forced apart■*gUREAOMPI WIPO .t slightly by the center post 534 and then brought back tightly together as th passageway within the slider 524 narrows. The guide segment 544 preferabl includes a tongue portion 572 which fits into a cooperating groove 574 in th guide segment 546 as seen best in FIGURE 15, thereby interlocking the fron portions of the terminals 520 and 522 when the zipper teeth (not shown) ar fastened. To further assist in interlocking the terminals 520 and 522 as will b appreciated best from the view of FIGURE 16, an inner edge 583 of the win 582 can be nested within a cooperating groove 585 in the adjacent edge of th terminal 520. In FIGURE 16, the edge 583 is shown in the position just prior t its entering the groove 585. In addition, the edge 583 can be extended dow around the upper periphary of the adjoining annular nesting portion 556 t interlock with a cooperating portion of the groove 585 as seen best in FIGUR 15.In accordance with an important feature of the presen invention, the nesting portions 550 and 556 are relatively large compared t the conventional terminal pin (not shown) which would be used with the slide 524 in a conventional pin-and-socket separable zipper. In FIGURE 14, th pertinent parts of which are generally accurately scaled, the diameter of th receiving aperture 565 (shown in dotted outline) of the nesting portion 556 i approximately equal to the width of the slider 524. It will be appreciated therefore, that the area of the receiving aperture 565 is several times large than the area of one of the slider ports. Accordingly, aligning and engagin the nesting portions 550 and 556 of the terminals 520 and 522 is significantl easier than the act of feeding a terminal pin (not shown) into the respectiv front slider port in a comparably sized prior-art separable zipper.It will be appreciated that the size differences are even mor advantageous when comparing the previously described four embodiments t the prior art. For example, it will be appreciated that the receiving apertur 65 of the device 10 of FIGURE 1 has a diameter at least as large as the overal length of the slider 24. Thus, it should be readily apparent that the area of th receiving aperture 65 of the device 10 is very much greater than the area o one of the slider ports, such as the left slider port 39b.Therefore, each of the above-described embodiments of th invention greatly reduces the care and dexterity required in connecting th ends of a separable zipper. Rather than having to first feed a relatively smal terminal pin through one port of a slider as is done with conventional pin-and socket type separable zippers, relatively large and substantially self-alignin terminals are first fastened and then, if need be, rotated until the rows o zipper teeth are properly aligned for interfastening by the slider.O WI Those skilled in the art will appreciate that the presently illustrated five embodiments are merely exemplary of the great variety of alternate embodiments contemplated by the present invention. For example, the present invention can be practiced using a terminal arrangement wherein the nesting portions are disposed to one side of the slider when in its rearmost position so that the axis of rotation of the terminals does not intersect the line along which the slider moves, as is the case with each of the presently illustrated embodiments. Furthermore, other terminal devices are contemplated wherein the slider is carried in its rearmost position on the terminal having the female rather than the male structure of the nesting portions, so that the term receiving terminal as used herein is not intended to be limited to terminals having the female structure. Other modifications and alternatives are within the spirit and scope of the present invention as defined by the appended claims. What is claimed is: | CLAIMS1. A device for connecting the ends of a separable zipper of the type having first (12) and second (14) opposed rows of teeth and a slider (24) for engaging and disengaging the rows of teeth, each row of teeth being disposed along the edge of a supporting sheet (16a, 16b) , the slider having first5 (39a) and second (39b) adjacent ports at the front thereof which lead to a common passageway within the slider, the ports being adapted to receive the respective first and second rows of teeth as the slider is moved -forward whereby the teeth in the opposed rows are progressively brought into interlocking engagement within the passageway, the slider having a center post10 (34) at the front thereof between the ports, the center post being adapted to progressively disengage the rows of teeth as the slider is moved rearwardly along the rows, the slider having two mutually perpendicular main axes, one being a longitudinal axis (L) lying in the direction of slider movement and the other being a transverse axis (T) bisecting the ports, the longitudinal and15 transverse axes intersecting each other to define a slider working plane, the device having first (20) and second (22) terminals disposed at the respective rearward ends of the first and second rows of teeth, the first terminal including means (28) for carrying the slider when the rows of teeth are fully disengaged, one of the terminals having portions (60, 64) defining an aperture20 (65) for receiving cooperating portions (52, 54) of the other terminal such that insertion of the cooperating portions into the receiving aperture by relative movement of the terminals in the direction substantially perpendicular to the slider working plane couples the terminals in operative engagement, characterized in that the area defined by the receiving aperture (65) is at least25 about sev ral times larger than the area defined by one of the slider ports (39b).O . W W 2. A device for connecting the ends of a separable zipper of the type having first (12) and second (14) opposed rows of teeth and a slider (24) for engaging and disengaging the rows of teeth, each row of teeth being disposed along the edge of a supporting sheet (16a, 16b), the slider having first (39a) and second (39b) adjacent ports at the front thereof which lead to a common passageway within the slider, the ports being adapted to receive the respective first and second rows of teeth as the slider is moved forward whereby the teeth in the opposed rows are progressively brought into interlocking engagement within the passageway, the slider having a center post (34) at the front thereof between the ports, the center post being adapted to progressively disengage the rows of teeth as the slider is moved rearwardly along the rows, the slider having two mutaully perpendicular main axes, one being a longitudinal axis (L) lying in the direction of slider movement and the other being a transverse axis (T) bisecting the ports, the longitudinal and transverse axes intersecting each other to define a slider working plane, the device having first (20) and second (22) terminals disposed at the respective rearward ends of the first and second rows of teeth, the first terminal including means (28) for carrying the slider when the rows of teeth are fully disengaged, one of the terminals having portions (60, 64) defining an aperture (65) for receiving cooperating portions (52, 54) of the other terminal such that insertion of the cooperating portions into the receiving aperture by relative movement of the terminals in the direction substantially perpendicular to the slider working plane couples the terminals in operative engagement, characterized in that the terminals (20, 22) are adapted so that they can be brought together into operative engagement to align the rearmost end (46) of the second row of teeth in front of the second slider port (39b) solely by relative translational movement of the terminals.3. The device of Claim 2 wherein the terminals (20, 22) are further characterized in that no part of the second terminal (22) must be passed through any portion of the slider (24) in order to operatively engage the terminals and align the rearmost end (46) of the second row of teeth in front of the second slider port (39b).4. The device of Claims 1 or 2 further characterized in that the terminals (20, 22) include slidably cooperating surfaces (54, 60) for permitting relative rotational movement of the terminals when the terminals-■ REXD*OMPI ./., WIPO , are operatively engaged with the slider (24) in its rearmost position on the firs terminal (20), the axis of rotational movement being substantiall perpendicular to said slider working plane, the terminals being adapted t permit their operative engagement solely by relative translational movemen along the rotational axis while the terminals are rotationally positione relative to each other within a range of angles including the relative rotationa position wherein the rearmost ends (44, 46) of the first and second rows o teeth are aligned in front of the respective first and second slider ports (39a 39b).5. The device of Claim 4 further characterized in that th first and second terminals (20, 22) include respective first and second matin walls (50, 56) , one such wall (56) defining the receiving aperture (65) and th other such wall (50) defining the cooperating portions (52, 54) that are inserte into the receiving aperture during coupling of the terminals, the mating wall including means-(66, 68) for interlocking the terminals against separation whe the rows of teeth are fastened.6. The device of Claim 5 further characterized by means (50 on the first terminal (20) abutting means (58) on the second terminal (22) t stop the relative translational movement of the terminals during coupling upo reaching a point such that at least the rearmost end (46) of the second row o teeth is brought into the slider working plane, whereby the terminals are the operatively engaged.7. The device of Claim 6 further characterized in that th terminal interlocking means (66, 68) becomes operative as the terminals (20 22) initially become operatively engaged without having to rotate th terminals relative to each other.*- 8. The device of Claim 5 further characterized in that th terminal interlocking means (466a, 466b, 468a, 468b) become operative onl after rotating the operatively engaged terminals (420, 422).O 9. The device of Claim 5 further characterized in that the slider (24) is carried in its rearmost position at least partially within the mating walls (50, 56) wherein the mating walls are provided with gaps (69a, 69b) at the front thereof for passage of the slider therethrough.10. The device of Claim 5 further characterized in that the slider (324) is carried in its rearmost positon entirely outside of the mating walls (350, 356) wherein each mating wall is disposed through a full 360° .11. The device of Claim 10 further characterized in that the slider (324) is carried in its rearmost position above the mating walls (350, 356) so that the rotational axis of the terminals (320, 322) passes through the slider.12. The device of Claim 10 further characterized in that the slider (524) is carried in its rearmost position adjacent to the mating walls (550, 556) so that the rotational axis of the terminals does not pass through the slider.13. The device of Claim 5 further characterized by means (190, 192, 194, 196, 198, 200, 202, 204, 206) for retaining the slider (124) on the first terminal (120) when the first and second terminals (120, 122) are disengaged wherein the retaining means is adapted to release the slider for forward movement when the terminals are operatively engaged.14. The device of Claim 13 further characterized in that the retaining means (190, 192, 194, 196, 198, 200, 204, 206) is adapted to release the slider (124) only when the terminals (120, 122) are operatively engaged and rotationally positioned so that the rearmost end (146) of the second row of teeth is alig ed in front of the second slider port.OMPI /., WIPO . 15. The device of Claim 5 further characterized in that the first terminal (20) includes a guide segment (44) at the rearmost end of the first row (12) of teeth and the second terminal (22) includes a guide segment (46) at the rearmost end of the second row (14) of teeth, one such guide segment including a tongue portion (72) and the other such guide segment including a groove portion (74), the groove portion being adapted to receive the tongue portion to interlock the terminals against separation once the slider (24) has moved forwardly beyond the guide segments.OMP | FRIEDBERG M | FRIEDBERG M |
WO-1979000942-A1 | 1,979,000,942 | WO | A1 | XX | 19,791,115 | 1,979 | 20,090,507 | new | B01D13 | G01N27 | B01D57, B01D61, G01N27 | B01D 57/02, G01N 27/447C4 | APPARATUS AND PROCESS FOR CONTINUOUS FLOW ISOELECTRIC FOCUSING | A method and apparatus for isoelectric focusing of fluids. In accordance with the disclosed method, the flow of fluids to be processed is established in a first direction. This flow of fluids is streamlined by providing a plurality of permeable microporous membranes (52-60) which define generally parallel channels oriented in the first direction. An electrical potential is applied across the streamlined channels of flowing fluid, and isoelectric focusing is achieved on the fluids during the flow thereof since the membranes (52-60) allow interchange of fluid constituents therebetween while providing the desired streamlining. An approximation of plug type flow is achieved within the streamlined channels; i.e., flow having an approximately uniform cross-sectional characteristic. In the preferred embodiment of the method of the invention, a recirculation path is established for each of the streamlined channels, such that the fluid flowing out of each channel is recirculated back to the beginning of the channel. Preferably, this is achieved by pumping (400) the fluids in each of the recirculation paths, and also providing cooling (300) for the fluids during the recirculation thereof. In this manner, a number of passes are effected to obtain the desired degree of isoelectric focusing. The cooling, which is performed during the recirculation, serves to minimize problems with dissipation of Joule heat during the isoelectric focusing of the fluids in the streamlined channels. Also, in the preferred embodiment of the invention, the first direction is downward such that the streamlined fluids flow under the influence of gravity to permit gravity equilibrium of fluid levels in the channels across the streamlining membranes (52-60). | DescriptionIsoelectric Focusing Method and ApparatusTechnical FieldThis invention relates to techniques for the sepa- ration and/or purification of biological materials and, more particularly, to a method and apparatus for isoelectric focusing.Isoelectric focusing ( IEF ) also sometimes called electrofocusing, is an electrophoretic technique that is recognized as being a powerful method for the analysis and micropreparative separation and purifica¬ tion of various biological materials, including proteins, peptides, nucleic acids, viruses, and even some living cells or cell organelles. The principle of IEF is based on the fact that certain biomaterials, such as those listed above, are amphoteric in nature, i.e. are positively charged in acidic media and negatively charged in basic media. At a particular pH value, called the isoelectric point, they have a zero net charge. In other words, the isoelectric point is the pH value at which they undergo a reversal of net charge polarity. In a pH gradient such materials will migrate under the influence of a d.c. electric field until they reach the pH of their isoelectric point where they become immobilized by virtue of their zero net charge. Thus, they focus into narrow zones, defined by the pH of the medium and the electric field applied.IEF techniques have been greatly advanced by the development of suitable buffer systems which form stable pH gradients in the electric field. Such buffers are usually composed of a random mixture of amphoteric sub¬ stances having isoelectric points covering a wide spectrum of pH values. In the electric field, these components of the buffer mixture are also focused according to their isoelectric points, thereby establish¬ ing a stable pH gradient. A commercial mixture of such amphoteric substances called Ampholine is available from LKB Produ ter AB, a Swedish Company. Other buffer systems are also compatible with IEF. The electric field in IEF thus has two simultaneous and overlapping functions; these being the establishment of the pH gradient and the focusing of the biomaterials to be separated. In terms of time sequence, the establishment of final focusing of the biomaterials cannot be achieved before a stable pH gradient is formed, i.e. before the components of the buffer mixture are focused.Background Art While IEF is widely practiced, it is still limited by the quantities which can be processed and, to appli¬ cant's knowledge, IEF is at present used only as an analytical or micropreparative technique. There have been various prior attempts to increase the capacity of IEF. Two recent symposia, where some of the approaches were described, are as follows: (1) P. G. Righetti: Progress in Isoelectric Focusing and Isotachophoresis, North Holland/American Elsevier, 1975 and (2) J. P. Arbuthnott and J. A. Beeley, Isoelectric Focusing, Butterworth, 1975. These volumes also summarize the current status of IEF.IEF is most often practiced in static, batch-type instruments where the fluid is stabilized by either gels or density gradients established by a non-migrating solute such as sucrose. In such instruments, the capacity for product separation is generally limited by the size of the apparatus to between 1 and 10 mg per2 cm of apparatus cross-section for each component of the sample applied. Apparatus cross-section cannot be arbitrarily enlarged because of the need to dissipate the Joule heating generated by the electric field. Thus, for larger scale preparative work, it would appear that continuous flow instruments are advan¬ tageous. Unfortunately, continuous flow electro- phoresis in free solutions is plagued by severe dis¬ tortions of boundaries of separating materials, caused by several factors: viz., (1) The parabolic nature of liquid flow through confined channels due to viscous drag (flow is fastest through the center of the channel, and decays in a parabolic fashion towards the walls) . (2) Electro-osmosis at the walls superimposes another type of parabolic flow, this being in a direction perpendicular to the parabolic profile induced by the viscous drag. (3) Density gradients arising from temperature or sample concentra¬ tion gradients can cause convective flow of fluid. The disruptive effects of these three factors have been amply described in the literature (cf. , for example, K. Hannig et al. : Hoppe-Seyler s Z. Physiol. Chem. Vol. 356, 1209, 1975).To overcome these difficulties in IEF, two prin¬ ciples of fluid stabilization were tried: stabiliza¬ tion by porous media and stabilization by density gradients Csee e.g. J. S. Fawcett, Annals of the New York Academy of Sciences, 209, 112-125, 1973). However, throughput was found to be only comparable to that achievable in static systems. One reason for the limited throughput is that in IEF equilibrium focusing is reached only assy ptotically. The rate of eleσtro- phoretic migration of each charged species decreases progressively as it approaches its isoelectric point. At the same time, the conductivity of the system decreases as the focused components are less conductive of electricity than when far removed from their iso- electric point. Thus, to obtain sufficient focusing, a relatively long residence time is required, and this is ostensibly achievable either by low flow rates or large - ά-apparatus size. A further reason for limited throughput is the dissipation of Joule heat in continuous flow electrophoresis instruments.It is an object of the present invention to overcome the stated prior art problems and to set forth an IEF technique which exhibits an improved capacity of product separation and purification.Disclosure of InventionThe present invention is directed to a method and apparatus for isoelectric focusing of fluids. In accor¬ dance with the method of the invention, the flow of fluids to be processed is established in a first directio This flow of fluids is streamlined by providing a plurali of permeable microporous membranes which define generally parallel channels oriented in the first direction. An electrical potential is applied across the streamlined channels of flowing fluid, and isoelectric focusing is achieved on the fluids during the flow thereof since the membranes allow interchange of fluid constituents there- between while providing the desired streamlining. An approximation of plug type flow is achieved within the streamlined channels; i.e., flow having an approximately uniform cross-sectional characteristic. In the preferred embodiment of the method of the invention, a recirculatio path is established for each of the streamlined channels, such that the fluid flowing out of each channel is re¬ circulated back to the beginning of the channel. Pre¬ ferably, this is achieved by pumping the fluids in each of the recirculation paths, and also providing cooling for the fluids during the recirculation thereof. In this manner, a number of passes are effected to obtain the desired degree of isoelectric focusing. The cooling, which, is performed during the recirculation, serves to minimize problems with dissipation of Joule heat during the isoelectric focusing of the fluids in the stream¬ lined channels. Also, in the preferred embodiment of the BU RfcOΛIPI invention, the first direction is downward sucti. that the streamlined fluids flow under the influence of gravity to permit gravity equilibrium of fluid levels in the channels across the streamlining membranes. In accordance with the apparatus of the invention, there is provided an enclosure having a plurality of in¬ let ports for receiving the process fluids and a plurality of associated outlet ports opposing the inlet ports. In¬ let and outlet separator means are provided for respec- t±vely separating the flow of fluids which enter at the inlet ports and exit at the outlet ports. A plurality of permeable membranes are disposed between respective ones of the inlet and outlet separator means and generally parallel to the direction of flow of said fluids. As pre- viously stated, these membranes serve to streamline the flow of fluids while allowing interchange of fluid con¬ stituents therebetween. The apparatus also includes means for applying an electrical potential transverse the direction of flow of said fluids in the enclosure. In the preferred embodiment of the apparatus of the invention, the streamlining membranes are ion non- selective microporous filters having pore sizes in the range of 0.2 to 50 microns. The spacers and membranes are preferably oriented in a vertical position, and process fluids are circulated by means of a multichannel pump operating in conjunction with a plurality of re¬ circulated tubes which recirculate fluids from each of the outlet ports back to the corresponding inlet ports. The fluids are thus gravity fed through the enclosure. Also, in the preferred embodiment of the apparatus of the invention, cooling means are coupled to the plurality of recirculation tubes for cooling the recirculating process fluids. Means for monitoring the properties of the fluid may also be provided in conjunction with the recirculation tubes. -6-In accordance with a particular embodiment of the apparatus of the invention, the enclosure is defined by a stack of adjacent substantially flat parallel spacers having apertures therein which together form a cavity, and a pair of electrode compartments mounted on opposing ends of the stack, the electrode compartments defining the cavity ends. The spacers have inlet and outlet slots which define the inlet and outlet ports at oppos¬ ing ends thereof, these ports communicating with the cavity. As stated, inlet and outlet separator means respectively separate the flow of fluids which enter at the inlet ports and exit at the outlet ports. These separator means may comprise, for example, separator spacers which are alternately positioned between the first mentioned spacers, the separator spacers having smaller apertures than the first mentioned spacers so that they extend into the cavity defined by the first mentioned spacers and constitute the desired fluid separating means. In this embodiment, the plurality of parallel permeable membranes are mounted in the cavity between the spacers and are operative to streamline the flow of fluids through the cavity. First and second electrode means are respectively mounted in the opposing electrode compartments, and a pair of electrode- confining membranes separate the cavity from the electrode compartments. The electrode compartments contain electrode buffer solution, and the electrode- confining membranes are of a type which does not allow free passage of fluid while readily allowing passage of electric current.In accordance with the techniques set forth, appli¬ cant obtains the achievement of various objectives, some of which are listed as follows:1. Provision for an apparatus and process for pre- parative IEF based on continuous flow principle where¬ in (.i) stabilization of flow of the liquid against convection, (ii) stabilization of flow against electro- osmosis at the walls of the vessel, and (iii) an approxi¬ mation of plug flow through the apparatus are achieved by means of microporous membranes which subdivide the apparatus into a plurality of subcompartments or chan¬ nels, the membranes being oriented parallel to the electrodes and parallel to the direction of flow of liquid through the apparatus.2. Provision for an apparatus and process for IEF 0 wherein there is an operational mode of continuous re-' cycling of the processed fluid through the individual channels of the apparatus, and a corresponding set of heat-exchange reservoirs. This recycling mode of opera¬ tion results in a separation of the function of electro- phoretic focusing ^carried out in the multimembrane IEF apparatus itself) from that of dissipation of Joule heat generated by the electric current (carried out in a heat exchange) . This separation of functions permits scaling up of the apparatus, for it is the need to dis- 0 sipate the Joule heat that limits the power input and size of most other electrophoretic equipment.3. Provision for an apparatus and process for con¬ tinuous IEF wherein unlimited residence time for achievement of final focusing equilibrium is available, 5 independent of the size of the apparatus and rates of flow. This is achieved through the principle of re¬ peated recycling of the processed fluid through the multimembrane IEF apparatus and the heat-exchange.4. Provision for a process consisting of pre- 0 focusing of the buffer components in IEF before the addition of sample. The sample free-buffer can be con¬ tinuously recycled until its focused equilibrium is approached. The sample is only then added. This has several advantages: (i) decreased time of exposure of 5 the sample material to processing, which is of impor¬ tance for many labile biomaterials; (ii) the possibilityBUR£4 ^_ 0MPI. A■v W}P0 of adding the sample only to that compartment having a pH nearest to the isoelectric point of the desired component of the sample which can result in significant shortening of the processing time; (iii) avoidance of any extreme pH value which may again cause inactivation of labile biological materials.5. Provision for a process for continuous flow single pass IEF, encompassing a first stage of re¬ cycling focusing of the buffer mixture to establish the stable pH gradient, followed by a single pass continuous flow focusing of the sample material.6. Provision for an apparatus for continuous flow IEF in a recycling mode with pH and/or ultraviolet con¬ centration sensors in at least one of the fluid flow channels for continuous monitoring of the focusing process and possible feed back control of the focusing process.7. Provision for an apparatus and process for IEF in recycling mode whereby the voltage applied to the IEF apparatus is continuously increased as the conductivity of the buffer system decreases as a result of the focusing so as to maintain a constant power input, con¬ sistent with an allowable maximum temperature rise of the processed fluids. Further features and advantages of the invention will become more readily apparent from the following detailed description when taken in conjunction with the accompany¬ ing drawings.Brief Description of Drawings FIG. 1 is a cross-sectional view of an isoelectric focusing apparatus in accordance with an embodiment of the invention.FIG. 2 is an elevational exploded view of an input/ output spacer, a separator spacer, and a channel- separating membrane of the apparatus of FIG. 1. -gm VmE_0fΛP FIG. 3 is a plan view of an alternate input/output spacer.FIG. 4 is a block diagram of a continuous flow iso¬ electric focusing apparatus in accordance with an embodiment of the invention.FIG. 5 illustrates, one above another, end and side views of an embodiment of the heat exchanger of FIG. 4.Best Mode for Carrying Out the Invention The present invention is based in part on the dis- covery that adequate stabilization against fluid convec¬ tion and wall electroosmosis can be achieved in a con¬ tinuous flow IEF apparatus by subdividing the internal volume of the apparatus with a plurality of microporous membranes oriented parallel to the direction of flow of liquid through the apparatus. Fluid convection generally arises from density differences due to concentration or temperature gradients within the fluid. Concentration gradients are generally due to unequal distribution of the sample and temperature gradients arise due to Joule heating. Electroosmosis is a well known phenomenon of liquid flow along the walls of the vessels due to their electrokinetic or zeta potential. The disruptive effects on electrophoretic instruments of electroosmosis and of the parabolic flow profile have been documented, e.g. by Hannig et al. In the present invention the subdivision of the internal volume of the IEF apparatus by a plural¬ ity of membranes effectively limits the convection only to the volume elements within the individual subcompart- ments or channels formed between adjacent membranes. The membranes thus serve to streamline the flow of liquid through the apparatus. The membranes serve an additional important purpose; i.e., they regulate the uniformity of flow in planes perpendicular to the direction of the electric field. It is well known that due to viscous drag liquid flow through a channel assumes a parabolic flow velocity profile, provided the flow is within the regime of laminar rather than turbulent flow. Thus, liquid flow would be expected to be substantially higher near the center of a processing unit than near the electrodes. This tends to cause continuous mixing of the apparatus content. In the present invention para¬ bolic flow is still present, but is limited to the narrow subcompartments or channels between adjacent mem¬ branes. This tends to transform what would otherwise be a parabolic flow profile to an approximation of plug flow, characterized by substantially equal flow velocity across the processing enclosure. In the context of the present technique, plug flow and prevention of electroosmosis are important in -the direction perpendicular to that of the electrophoretic migration, i.e. the direction of the electric field. Parabolic flow within any plane at equal electric poten¬ tial is of lesser consequence and can be minimized e.g. by insertion of plastic screening of webbing into each membrane-defined subcompartment. There will be no elec¬ troosmosis within such a plane as it is at equal electric potential. It is also helpful to initially distinguish between two types of electroosmosis; i.e., electroosmosis at the walls of a vessel and electroosmosis across the membranes. Electroosmosis at the walls is known to be destructive of sharpness of resolution because it tends to impose a para¬ bolic flow profile within the chamber (e.g. Hannig et al) . Microporous membranes of the type employed for the parti- tioning in the disclosed technique can also give rise to an electroosmotic flow in the direction perpendicular to their plane. In the context of the present technique, this electroosmosis will depend on the inherent zeta potential of the membranes themselves, which is usually minimal, but also on the pH and solute concentration gradients across the membranes. This will vary in the apparatus and is not readily predictable. It is however far less destructive of the sharpness of resolution as the flow is uniformly distributed across the whole cross- section of the apparatus and does not give rise to a parabolic velocity profile. For example, observation of colored solutions of hemoglobin in the apparatus have shown no evidence of wall electroosmosis. Electroosmosis across the separator membranes is evident as it estab¬ lishes a pressure gradient across the membranes, i.e. fluid height in the various reservoirs may not be equal even at pumping flow rates.The subdivision of the apparatus by means of the membranes prevents the formation of a continuous pH gradient, there being significant convection and mixing within each channel or subcompartment. Instead, a stepped gradient is obtained, the pH varying signif¬ icantly from subcompartment to subcompartment.The temperature increase of processed fluid by the Joule heat can be experimentally measured or calculated. It is well known that a watt of electric power is equiv¬ alent to 14.3 calories per minute. Knowing the power input into the IEF apparatus and the rate of liquid flow, the temperature rise is readily calculated. If the apparatus is operated at constant power, rather than constant voltage, the voltage will be progressively increasing in the early stages of focusing until a steady state is reached. The increase in voltage may result in a shift of the pH values in each subcompartment but once equilibration is reached, the voltage will remain constant, and there will be no further major drifts in pH distribution.Referring to FIG. 1, there is shown an apparatus 10 in accordance with an embodiment of the invention and which is useful in practicing the method of the invention. An enclosure 20 is defined by a stack of substantially flat parallel input/output spacers 31, 32, 33 40. In the present embodiment, the spacers are substantially rectangular in shape and have a central aperture therein, as can be seen in FIG. 2, which illustrates a represen¬ tative input/output spacer 32. Between adjacent pairs of input/output spacers are located a separator spacer and a permeable membrane. There are, in the FIG. 1 embodiment, actually eleven separators spacers and nine permeable membranes, designated by reference numerals 41, 42, 43 51 and 52, 53, 54 60, respectively, with the two extra separator spacers at 41 and 51 being at the ends of the stack. The separator spacers 41-51 and the membranes 52-60 may conform in their external shape to the input/output spacers 31-40, as can be seen in FIG. 2 which shows representative separator spacer 42 and membrane 52, the separator spacers 41-51 have shorter apertures than the input/output spacers, 31-40, and the permeable membranes 52-60 have no matching apertures. The spacers and membranes are clamped together, by means not shown, between a pair of end-plates 13 and 14. The end-plates 13 and 14 have recessed regions 19 and 20 which define opposing electrode compartments that house negative and positive electrodes 17 and 18. Electrode- confining membranes 15 and 16 respectively cover the compartments 19 and 20 which contain electrode buffer solutions, and ports 17 in end-plates 13 and 14 are provided for circulation of the electrode buffer solu¬ tions and venting of gaseous products of electrolysis.Accordingly, it is seen in FIG. 1 that the apertures in spacers 31-40 and 41-51 together form a cavity, and the electrode compartments 19 and 20 on opposing ends of the stack enclose the cavity ends, so that the spacer frames and electrode compartments con¬ stitute the enclosure 20, The smaller apertures of separator spacers 41-51 mean that portions of these spacers protrude into the cavity and define separator means whose function will become apparent. Also, the permeable membranes 52-60 divide the cavity of enclosure 20 into a number of channels. Each input/output spacer 31, 32, 33 40, has a respective inlet port, desig¬ nated 61, 62, 63 70 and a respective outlet port designated 71, 72, 73 80, with the inlet and outlet ports associated with inlet/outlet spacer 32 being shown in FIG. 2. Attachment for tubing at each inlet and outlet port, as will be described, is facilitated by stainless steel needles embedded in the inlet and outlet ports, as illustrated in FIG. 2 at 161 and 171.The illustrated number of ten channels is arbitrary and can be made greater or lesser, depending on the number of fractions desired, although at least six channels are preferred for most applications. The spacers and the end-plates can be made of non-conductive materials such as plexiglass or other polymeric compositions. The separator spacers 41-51 protrude into the cavity and pro¬ vide a diffuser zone (e.g. D in FIG. 1) to permit estab¬ lishment of laminar flow within each channel. These separator spacers may be formed, for example, of 0.025 cm. thick mylar. The separator membranes 52-60 should allow free flow of fluids and passage of the sample material in the fluids. They can be of filter paper, or of various types of commercially available filtering membranes or battery separator membranes, for example the 5 micron nominal pore size filter manufactured by the Millipore Corp. of Bedford, Mass. For optimal function they should have a pore size of not less than o.2 microns, to allow free passage of fluid, and of not more than 50 microns to act as effective barriers for flow streamlining. The electrode-confining membranes 15 and 16 should have quite different characteristics, as they should not allow free passage of fluid or of the sample material but should still allow passage of electric current. Dialyzing membranes of regenerated cellulose of the type used in passive dialysis are suitable. A more preferred alternative is to use ion-selective membranes of the type used in electrodialysis. The positive electrode should be bounded by an anion permeable membrane, and the negative electrode by a cation permeable membrane. These ion selective membranes 15 and 16 have the advantage of lower passive diffusivity of ions across themas compared to cellulosic membranes, and are there¬ fore to be preferred. The electrodes 17 and 18, can be of platinum wire, platinum foil, or any other suitable electrode material. The electrode buffer fluids may be a dilute solution of a strong acid, such as sulfuric or phosphoric acid, in the positive electrode compart¬ ment and a dilute solution of an alkali, such as sodium hydroxide, in the negative electrode compartment, as is conventional for IEF instruments.The length of the protrusion of the separator spacers 41-51 into the cavity of enclosure 20 may be of the same order or magnitude as the width of the cavity. This provides a sufficient length of diffuser zone for avoidance of local turbulence adjacent to the inlet and outlet ports and permits the establishment of laminar flow.An alternative version of the input/output spacers 31-40 is shown in FIG. 3. The spacer, designated by reference numeral 135, is formed on a screen support 118, the outside periphery of which is impregnated with a polymeric material to form the frame 119. One suitable screen material is Monodur 400 Standard, manufactured by Industrial Fabrics Corp. of Minneapolis, Minn., which is constituted by nylon monofilament of 210 microns diameter, with a mesh opening of 400 microns and overall screen thickness of .017 . The polymeric material used for the formation of the frame 119 is applied to completely fill the mesh opening to achieve impermeability to fluid, thereby leaving the open central aperture with just screening so that fluid flow is allowed therein. The screen functions to hold the microporous membranes 52-60 (FIG. 1) roughly parallel and provide further support therefor. Each of the spacers, as 135, has an inlet port and an outlet port, these being respectively designated by reference numerals 163 and 173 in the case of the illustrated input/output spacer 135. Each such input/output spacer has provision for a plurality of flow ducts (ten in the present instance, consistent with the embodiment of FIG. 1) , only one of which communicates with the aperture in each spacer via that spacer's inlet port and that spacer's outlet port. For example, the flow ducts 115 and 105, in the illustrated input/output spacer 135, communicate with the inlet and outlet ports 163 and 173, respectively. Using this scheme, each of the input/output spacers, separator spacers, and membranes of FIG. 1 would have small circular apertures or flow ducts corresponding to 101-110 and 111-120 in FIG. 3. Using this type of spacer, fluid flow may be established through the end-plates 13 (FIG.l) which are provided with coextensive ducts and means for tubing attachment. An advantage of this type of spacer is that they permit greater flow of processed fluid than those shown in FIG. 2, as the diameter of the channels is not limited by the thickness of the spacers. It will be understood that various other spacers or structural elements can be employed consistent with the spirit and scope of the invention.The type of apparatus illustrated in FIG. 1 is preferably employed as part of an overall apparatus or system for continuous flow IEF operation. Such a system is shown in FIG. 4 which includes an apparatus 10 (of FIG. 1) having ten input and output tubes for recircula¬ tion of the process fluids. Circulation is in closed loop fashion through a heat exchanger 300. The illus- trated heat exchanger contains the same number of individual reservoirs as there are channels or compartments in the apparatus 10 (although in practice two additional reservoirs will be provided for cooling of the electrode buffer fluids) . These reservoirs can be located within a single container and refrigerated by means of circulating brine from a coolant source 301. Each reservoir is coupled by suitable tubing to a corresponding port of the apparatus 10. The fluid is fed by gravity from the reservoirs to the apparatus 10. The return of the effluents from the apparatus 10 to the cooling reservoirs is accomplished by a multichannel pump 400 which may be of a commercially available type. The return lines can be provided with sensors 500 to measure the temperature, pH and/or ultraviolet absorption in one or more of the fluid streams, and can be recorded on a multichannel recorder 600, or other data collecting devices. D.C. electric current is supplied to the apparatus 10 by a power supply 700.This system of FIG. 4 continuously recycles the contents of the individual reservoirs of heat exchanger 300 through the corresponding channels or compartments of the apparatus 10. It will be understood that a variety of data collections can be used, for example, visual observation, multichannel recorders, data printers, etc. The temperature of the outflowing streams can be sensed, and logic employed to regulate the power input to the apparatus 10. Such a technique would assure that the processed fluids will not be exposed to an excessive temperature rise. Moreover, as during focusing the conductivity of the fluids decreases, it will assure a maximum power input at all times, consonant with an acceptable temperature rise. Further logic can be incorporated, if desired, using sensors measuring the pH or ultraviolet absorption through each channel in conjunction with automatic control. In the preliminary stages of focusing, these parameters will be continuously changing but will reach a steady state when final-SU EOMPIA> WiPO equilibrium is reached, whereupon an indicating signal can be produced. It can be noted that there is some advantage in having a gravity feed into the IEF apparatus 10 and return of fluid flow to the reservoirs by means of a pump. This permits gravity equilibration of fluid levels in the channels across the membranes of the apparatus 10. Such minor fluid level differences could arise from unequal pumping rates of the multichannel pump. In other situations, one may wish to pump the fluid into the unit and return the fluid by gravity or have separate pumps to both feed and withdraw the fluid from the MSIEF apparatus. It will be understood that the described recycling mode of operation can be replaced by having a single pass continuous flow mode of operation, this being achieved, for example, by cascading two or more IEF apparatuses 10. This mode may be advantageous if ultimate equilibrium is not necessary and a relatively crude fractionation is sufficient.FIG. 5 illustrates a possible configuration of a ten reservoir heat-exchanger 300 which can be employed in the present invention. Quick-connect ports, 331, permit easy access to the individual glass reservoirs, 332, housed within a transparent plastic enclosure, 333. Coolant circulation is provided through ports, 334. Such an arrangement permits easy visual inspection of fluid levels in each channel and any color differences arising from focusing of colored sample materials.In a preferred mode of operation using the system described in conjunction with FIG. 4, the solutions are gravity fed from the reservoirs to the IEF apparatus 10 which is vertically oriented, i.e., its membranes are in the vertical direction. The selected buffer, suitable for establishment of a stable pH gradient, can be loaded into all but the two reservoirs used for the electrode buffers. A 0.05% to 0.5% solution of Ampholines, previously described, can be used for this purpose. Circulation through the apparatus is established and the liquid levels in the reservoirs allowed to equil¬ ibrate across the membranes of the apparatus. The remaining two reservoirs are filled with a dilute solution of strong acid for the anode compartment and a dilute solution of a strong base for the cathode compart¬ ment, as is customary for IEF techniques. These electrod rinses are allowed to flow upward through the IEF apparatus 10 to permit venting of gases generated by electrolysis. The preferred direction of flow of the processed fluid is downward through the apparatus as this is the direction of possible electrodecantation of sample materials along the membranes. To eliminate air entrappe in the IEF apparatus, the direction of pumping can be reversed during the priming procedure until all air is cleared from the tubing. After equilibration of fluid flow and temperature, electric power is applied. Typically, a gradient of 5 to 50 volts/cm is sufficient to cause rapid equilibration. The maximum power input is mainly limited by the allowable temperature rise in the apparatus due to Joule heating. Continuous or periodic temperature monitoring may be used. Typically, a reservoir temperature of 4°C is maintained and a temperature rise of less than 10°C will not damage most biomaterials.It is possible to add the sample material to be focused to all reservoirs at the beginning of the operati as is common procedure in batch type operations. This wi cause some of the material to be exposed to extremes of p in the compartments adjacent to the electrodes as the pH shift is faster than the migration of the sample material This may damage some pH sensitive biomaterials. A preferred mode of operation is to allow at least a partia pH equilibration of the buffer to occur with the sample material added only to the channel or compartment having a pH relatively close to its presumed isoelectric point. In practice, the heat exchanger reservoirs will have a substantially larger capacity than the internal total volume of the IEF apparatus 10. This ratio may be of the order of 10:1 to 100:1. The bigger the ratio, the longer it will require to equilibrate the contents of the reservoir. It is desirable to have sufficient flow rate to recycle the whole content of the reservoirs in one to two hours at the most, but more rapid rates of recirculation are often possible. The equilibration of the reservoirs will always lag behind the equilibration of the outflow of the IEF apparatus 10. This, once the latter is equilibrated, as attested by constancy of the solutes in each effluent channel, it is not necessary to wait for the equilibration of the reservoir contents. The outflow from the IEF apparatus 10 can be simply shifted to another series of reservoirs, receiving the finally equilibrated materials. Sensing of the pH or sample concentrations can be obtained through periodic with¬ drawals of aliquots and measurements of pH or ultraviolet absorption, as most biomaterials absorb in the ultraviolet region. This monitoring is simplified if the system is provided with in line sensors.Alternate modes of operation exist and may be applicable if relatively crude fractionation suffices and ultimate equilibration is not needed. One such alternate mode is to add the material to be fractionated to the system only after pH equilibration of the buffer is already achieved and then process it in single pass without recycling. Another alternate mode, as above-stated, is to avoid recycling of buffer and sample altogether and cascade the contents of the reservoirs through two or more IEF instruments 10, the sample being added either to the total volume, or at an intermediate stage, for instance between the first and second IEF apparatuses, after partial equilibration of buffer is already achieved. These modes of operation increase the throughput, as mixin within the reservoirs is avoided but are not likely to yield the same final equilibration as the recycling mode. Other similar combinations of recycling and single pass processing modes are possible.EXAMPLE IIn this example there is demonstrated the estab¬ lishment of a stable pH gradient in a sample-free Ampholine containing buffer and the subsequent focusing of a single protein in this buffer. The recycling mode was used with a 10 channel IEF apparatus of the type described in conjunction with FIG. 1. Each input-output spacer was made of plexiglass having an inside length of 24 cm, width of 2 cm, and thickness of 0.2 cm. The separator spacers were made of mylar, 0.025 cm thick, and had an inside length of 20 cm. Thus the total internal volume of the ten spacer assembly was approximately 108 m The twelve heat-exchange reservoirs were maintained at 4°C and had a capacity of 125 ml each. Polyvinyl chlorid battery separator membranes with a nominal pore size of 5 microns were used, manufactured by the Porvic Corp. of United Kingdom. Ion permselective membranes manufactured by Ionics, Inc. of Watertown, Mass. were used as electrode membranes. A multichannel peristaltic tubing pump was used for recirculation of th-eprocessed fluids at a consta rate of approximately 1 ml/ in per each channel. A constant field of 100 volts was applied across the cell, corresponding to an approximate potential of 30 volts/cm. The apparatus was loaded with 1,000 ml. of distilled water containing 2 ml. of Ampholine, 3.5 to 10 pH range, obtained from the LKB Produkter A. B. of Sweden. This volume corresponded to about tenfold the volume of the IEF apparatus 10, each reservoir containing 100 ml. At the flow rate of 1 ml/min, about 100 min were required for complete recirculation' of each reservoir. Dilute sulfuric acid and sodium hydroxide were used in the electrode compartments. At first, the apparatus was allowed to reach a focusing equilibrium with Ampholines alone, followed by the addition of 3 grams of hemoglobin into the channel #5 and its focusing determined.Hemoglobin was chosen because of its color, permitting easy visual observation and spectrophotometric quanti- tation. During its preparation it was saturated with carbon monoxide gas to decrease its tendency to air 0 oxidation. Channel 5 was chosen because its equil¬ ibrated pH was distinctly different from the isoelectric pH of hemoglobin (approximately pH 7.4). The pH of all ten channels outflowing from the apparatus was period¬ ically measured by withdrawal of aliquot samples. The pH 5 of channels 1 and 3, outflowing from the reservoirs and inflowing into the IEF apparatus was continuously monitored by two in line pH sensors. This permitted one to determine not only the focusing in the IEF apparatus itself, but also the time necessary for the equilibration 0 of the reservoirs themselves.The data are presented in Table 1, column 1 listing the time of sampling, column 2 the current through the cell at 100 volts, and the remaining columns the pH of the specified flow channels. 5 From the inspections of pH data, it can be seen that a relatively stable pH gradient in the effluent channels is established within the first 90 minutes of recircu¬ lation. This pH gradient did not substantially change over the next 4.5 hours. Complete equilibration of the30 whole system required considerably longer or approximately 4 hours as indicated by the constancy of pH of inflowing channels 1 and 3 and the constancy of current consumption. This is obviously due to the unavoidable mixing of reservoir contents. Thus, while theoretically only about35 100 min. would have been required for complete exchange of reservoir contents, actually this time was substantially-BUREA,OMPI. . Wlp0 ^' TABLE IEquilibration of pH valiαes in recycling IEFTime Current pH in effluent channels , number pH in Mamp Inflowing Channels1 2 3 4 5 6 7 8 9 10 1 30 130 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.15 min 45 3.21 4.18 4.48 5.38 5.88 6.86 7.13 9.27 9.74 9.84 - -30 min 23 3.08 4.19 4.48' 5.16 5.70 6.63 8.07 9.20 9.46 9.56 7.51 8.90 min 16 3.26 4.20 4.49 5.09 5.57 6.58 7.53 8.83 9.07 9.32 3.79 5.2 hrs 13 3.23 4.24 4.65 5.33 5.95 7.00 7.87 8.99 9.30 9.58 3.67 4.4 hrs 10 3.09 4.22 4.75 5.33 5.85 7.50 8.64 8.75 9.14 9.20 3.25 4.6 hrs* 10 2.93 4.21 4.72 5.32 5.72 7.08 8.08 8.49 8.99 9.33 3.15 4.6.5 hrs 23 2.84 4.28 4.73 5.29 6.02 7.22 7.68 8.45 9.30 9.77 3.15 4.7.5 hrs 10 2.84 4.28 4.71 5.23 6.03 7.17 7.58 8.82 8.98 9.36 3.11 4.*3 gram hemoglobin added after this measurementlonger. After 6 hours of continuous operation, the last two hours with a fully equilibrated system, the sample of 3 grams of hemoglobin dissolved in 30 ml of water was added to reservoir #5. The recycling mode was shifted to a sample collection mode after 90 minutes of sample recycling without interruption of flow or current. Equilibration of the sample is accelerated by its greater density than buffer: the protein containing solutions being denser will remain layered on the bottom of the reservoirs and their remixing substantially decreased. The 90 minutes recycling were therefore sufficient for a complete recycling of each protein containing reservoir. It will be noticed that the addition of the protein caused a temporary increase of current and also a slight shift in the pH values of the protein-containing channels 6 and 7. This pH shift is due to the contribution of the protein itself to the overall buffering capacity of the processed fluid. The protein distribution in the collected ten frac¬ tions of 100 ml each was determined spectrophotometrically and was as follows:Fractions 1-5 : no detectable color Fraction 6 : 2.6 gm hemoglobin/100 ml. Fraction 7 : 0.39 gm hemoglobin/100 ml. Fractions 8-10: no detectable color This example indicated that it is possible to sharply focus most of the protein sample applied into a single channel, with some overflow into a second adjacent channel. The calculated temperature rise at the beginning of the experi¬ ment, when no protein was present, was of the order of 20°C, confirmed by actual measurements. At the end of the experi¬ ment, the calculated temperature rise was less than 2°C.EXAMPLE IIIn this example a large scale fractionation of an artificial mixture of carbon monoxide treated hemoglobin and serum albumin was carried out. Albumin was made visible by the addition of a small quantity of Bromphenol Blue dye which stains it blue. In this case an eight channel apparatus was used, having a different type of spacer.The cavity within the spacers was 17 cm long and 6 cm wide2 with an effective membrane area of about 100 cm . The total internal volume of the 8 spacer apparatus was of the order of 160 ml. Together with all the tubings, pumps, et the total capacity of the apparatus, exclusive of the heat exchange reservoirs was 350 ml. Plastic webbing was used to prevent excessive bulging of the membranes and aid in equilibration of liquid flow in each channel. The heat exchange reservoirs had each a capacity of 1,000 ml and a total of 8 liters was processed. This represents a 50:1 ratio of processed fluid versus internal volume of the IEF apparatus 10. The Ampholine concentration was 0.2%. After initial equilibration of the pH values in the reservoirs, a mixture of 24 gm each of albumin and hemoglobin was added only to the reservoir closest to pH 7. The expected isoelectric points of albumin is about pH 4.8, and that of hemoglobin about pH 7.4. Hemoglobin is known to rapidly denature at acid pH values while albumin is more stable.Maintaining a recirculation rate of 10 ml/min per channel, preequilibration of the buffer was allowed to proceed at 150 volts for 2 hours at which time the albumin-hemoglobin mixture was added to reservoir #5 and the fractionation continued for a total of 19 hours, the pH distribution in the effluent streams at various times is set forth in Table II. Table II Equilibration of pH values in recycling IEF Time pH in effluent channels, number1 2 3 4 5 6 7 845 min 5.04 5.26 6.40 6.75 7.00 8.07 9.15 9.7075 min 4.66 4.90 5.77 6.46 6.91 7.76 8.99 9.582 hrs* 3.78 4.27 5.01 5.96 7.05 8.34 9.03 9.364 hrs 3.66 4.36 5.08 6.07 8.04 9.09 9.34 9.966 hrs 3.58 4.46 5.70 6.30 7.35 9.29 9.55 10.3519 hrs 3.56 4.32 5.38 6.58 8.07 9.07 9.77 9.92*protein added after this measurementTable III Optical densities of effluent channels, number » Time Measurement 1 2 3 4 5 6 7 8 6 hrs O.D.at 541 nm .028 .108 .241 .327 .422 .027 .018 .006 O.D.at 610 nm .028 .227 .083 .048 .134 .007 .009 .007 ratio 541/610 — .48 2.90 6.81 3.15 3.8619 hrs O.D.at 541 nm.025 .175 .238 .330 .419 .024 .020 .008 O.D.at 610 nm.020 .235 .085 .051 .132 .017 .014 .006 ratio 541/610 — .50 2.80 6.47 3.17Tables II and III indicate that equilibration of both pH and protein distribution was reached already after 6 hours processing, i.e. 4 hours after the addition of the protein. Considering the flow rate, this corresponds to a 2.4-fold recycling of the total reservoir volume of 8,000 ml. Remarkable constancy of equilibration was maintained over the next 13 hours. From the optical data, particu¬ larly the ratios of absorption at 541/610 nm, it is evident that most of the albumin was confined to channel 2 while hemoglobin was confined to channels 4 and 5. The effluent of channel 3 was mainly hemoglobin with traces of albumin added. There is also a highly sig¬ nificant and consistent difference in the 541/610 ratio between channels 4 and 5. This points to a partial separation of two species of hemoglobin. The data were confirmed by analytical IEF in polyacrylamide gels. Albumin was found only in channels 2 and 3, hemoglobin in channels 3-5. While albumin gave a single blue line, hemoglobin gave a plurality of lines, the main two lines being a clearly red one, and a slightly more alkaline brownish line. It is this partial oxidation product..of., hemoglobin which accounted for the difference in observed ratios. Quantitation of the analytical run was not attempted. This example clearly demonstrates the rela¬ tively high capacity of the invented apparatμs and process, even though the resolution of albumin and hemo¬ globin was incomplete. It is believed that this was due to the use of only an eight channel apparatus, insuffi¬ cient for complete resolution, and possible excessive protein loading. | (received by the International Bureau on 25 September 1979 (25.09.79))1. A method for isoelectric focusing of fluids con¬ taining buffering components capable of establish¬ ing a stable pH gradient in an electric field, com¬ prising the steps of: establishing a flow of said fluids in a first direction; streamlining the flow of said fluids in said first direction by providing a plurality of perme¬ able membranes which define generally parallel chan- nels oriented in said first direction; and applying an electrical potential across the streamlined channels of flowing fluids.2. The method as defined by claim 1 further comprising the step of establishing a recirculation path associ- ated with each of said streamlined channels such that fluid flowing out of each channel is recircu¬ lated back to the beginning of said channel.3. The method as defined by claim 2 further comprising the step of pumping the fluids in each of said recirculation paths to establish continuous flow therein.4. The method as defined by claim 3 further comprising the step of cooling said fluids during the recircu¬ lation thereof.5. The method as defined by claim 1 wherein said first direction is downward such that said streamlined fluid flow is under the influence of gravity.6. The method as defined by claim 2 wherein said first direction is downward such that said streamlined fluid flow is under the influence of gravity. 7. The method as defined by claim 3 wherein said first direction is downward such that said streamlined fluid flow is under the influence of gravity.8. The method as defined by claim 4 wherein said first direction is downward such that said streamlined fluid flow is under the influence of gravity.9. The method as defined by claim 3 further comprising the step of monitoring the fluid properties in said recirculation paths.10. The method as defined by claim 4 further comprising the step of monitoring the fluid properties in said recirculation paths.11. The method as defined by claim 5 further comprising the step of monitoring the fluid properties in said recirculation paths.12. The method as defined by claim 8 further comprising the step of monitoring the fluid properties in said recirculation paths.13. The method as defined by claim 3 further comprising the step of extracting fluids after a desired number of recirculations.14. The method as defined by claim 4 further comprising the step of extracting fluids after a desired number of recirculations.15. The method as defined by claim 5 further comprising the step of extracting fluids after a desired number of recirculations. 16. The method as defined by claim 8 further comprising the step of extracting fluids after a desired number of recirculations.17. The method as defined by claim 12 further comprising the step of extracting fluids after a desired number of recirculations.18. The method as defined by claim 2 further comprising the step of adding fluids to be processed to said fluids containing said buffering components after said buffering components have been focused to establish a pH gradient therein.19. The method as defined by claim 3 further comprising the step of adding fluids to be processed to said fluids containing said buffering components after said buffering components have been focused to establish a pH gradient therein.20. The method as defined by claim 4 further comprising the step of adding fluids to be processed to said fluids containing said buffering components after said buffering components have been focused to establish a pH gradient therein.21. The method as defined by claim 5 further comprising , the step of adding fluids to be processed to said fluids containing said buffering components after said buffering components have been focused to establish a pH gradient therein. 22. The method as defined by claim 8 further comprising the step of adding fluids to be processed to said fluids containing said buffering components after said buffering components have been focused to establish a pH gradient therein.23. Apparatus for isoelectric focusing of fluids com¬ prising, in combination: an enclosure having a plurality of inlet ports for receiving said fluids and a plurality of associ- ated outlet ports opposing said inlet ports; inlet and outlet separator means for respec¬ tively separating the flow of fluids which enter at said inlet ports and exit at said outlet ports; a plurality of permeable membranes disposed between respective ones of said inlet and outlet separator means and oriented generally parallel to the direction of flow of said fluids so as to streamline the flow of fluids as between said inlet and outlet separator means while allowing interchang of fluid constituents therebetween; and means for applying an electrical potential transverse the direction of flow of said fluids in said enclosure.24. Apparatus as defined by claim 23 wherein said streamlining membranes are ion non-selective micro- porous filters having pore sizes in the range of 0.2 to 50 microns.25. Apparatus as defined by claim 23 further comprising a plurality of recirculation tubes for recirculating fluids from each of said outlet ports back to the corresponding inlet port. 26. Apparatus as defined by claim 24 further comprising a plurality of recirculation tubes for recirculating fluids from each of said outlet ports back to the corresponding inlet port.27. Apparatus as defined by claim 23 wherein said spacers and membranes are oriented in a vertical position.28. Apparatus as defined by claim 24 wherein said spacers and membranes are oriented in a vertical position.29. Apparatus as defined by claim 25 wherein said spacers and membranes are oriented in a vertical position.30. Apparatus as defined by claim 26 wherein said spacers and membranes are oriented in a vertical position.31. Apparatus as defined by claim 29 wherein said process fluids are recirculated by means of a multi¬ channel pump to a position above said inlet ports, whereby said fluids are gravity fed to said inlet ports.32. Apparatus as defined by claim 30 wherein said process fluids are recirculated by means of a multi¬ channel pump to a position above said inlet ports, whereby said fluids are gravity fed to said inlet ports. 33. Apparatus as defined by claim 25 further comprising cooling means coupled to said plurality of recircu¬ lation tubes for cooling the recirculating process fluids.34. Apparatus as defined by claim 26 further comprising cooling means coupled to said plurality of recircu¬ lation tubes for cooling the recirculating process fluids.35. Apparatus as defined by claim 29 further comprising cooling means coupled to said plurality of recircu¬ lation tubes for cooling the recirculating process fluids.36. Apparatus as defined by claim 30 further comprising cooling means coupled to said plurality of recircu- lation tubes for cooling the recirculating process fluids.37. Apparatus as defined by claim 31 further comprising cooling means coupled to said plurality of recircu¬ lation tubes for cooling the recirculating process fluids.38. Apparatus as defined by claim 32 further comprising cooling means coupled to said plurality of recircu¬ lation tubes for cooling- the recirculating process fluids.39. Apparatus as defined by claim 25 further comprising means for monitoring the properties of the fluids in said recirculation tubes. 40. Apparatus as defined by claim 31 further comprising means for monitoring the properties of the fluids in said recirculation tubes.41. Apparatus as defined by claim 33 further comprising means for monitoring the properties of the fluids in said recirculation tubes.42. Apparatus for isoelectric focusing of process fluids comprising, in combination: an enclosure defined by a stack of substantially flat parallel spacers having apertures therein which together form a cavity, and a pair of electrode compartments on opposing ends of said stack which enclose the cavity ends; said spacers having inlet and outlet ports at opposing ends thereof which communicate with said cavity; inlet and outlet separator means for respectively separating the flow of fluids which enter at said inlet ports and exit at said outlet ports into a plurality of channels; a plurality of substantially parallel permeable membranes mounted across opposing ones of said inlet and outlet separator means, said membranes being operative to streamline the flow of said fluids through said enclosure and guide the flow of said fluids in said channels as substantially plug- ype flow, while allowing interchange of fluid constituents between said channels; first and second electrodes respectively disposed in said pair of electrode compartments, said elec¬ trodes being operative to apply an electric poten¬ tial to the fluids flowing in the channels defined by said spacers and membranes, said potential being applied transverse the direction of flow of said fluids in said channels; and a pair of electrode-confining membranes enclosing said first and second electrodes in said electrode compartments and operative to isolate said process fluids from said electrodes while allowing passage of electric current through said process fluids.43. Apparatus as defined by claim 42 wherein said streamlining membranes are ion non-selectrive microporous filters having pore sizes in the range of 0.2 to 50 microns, and wherein said separator means comprise separator spacers located between adjacent ones of said first mentioned spacers.44. Apparatus as defined by claim 42 further comprising a plurality of recirculation tubes for recirculating fluids from each of said outlet ports back to the corresponding inlet port.45. Apparatus as defined by claim 43 further comprising a plurality of recirculation tubes for recirculating fluids from each of said outlet ports back to the corresponding inlet port.46. Apparatus as defined by claim 42 wherein said spacers and membranes are oriented in a vertical position.47. Apparatus as defined by claim 43 wherein said spacers and membranes are oriented in a vertical position.48. Apparatus as defined by claim 44 wherein said spacers and membranes are oriented in a vertical position. 49. Apparatus as defined by claim 45 wherein said spacers and membranes are oriented in a vertical position.50. Apparatus as defined by claim 44 wherein said process fluids are recirculated by means of a multichannel pump to a position above said inlet ports, whereby said fluids are gravity fed to said inlet ports.51. Apparatus as defined by claim 48 wherein said process fluids are recirculated by means of a multichannel pump to a position above said inlet ports, whereby said fluids are gravity fed to said inlet ports.52. Apparatus as defined by claim 44 further comprising cooling means coupled to said plurality of recircu¬ lation tubes for cooling the recirculating process fluids.53. Apparatus as defined by claim 45 further comprising cooling means coupled to said plurality of recircu- lation tubes for cooling the recirculating process fluids.54. Apparatus as defined by claim 48 further comprising cooling means coupled to said plurality of recircu¬ lation tubes for cooling the recirculating process fluids.55. Apparatus as defined by claim 49 further comprising cooling means coupled to said plurality of recircu¬ lation tubes for cooling the recirculating process fluids. 56. Apparatus as defined by claim 50 further comprising cooling means coupled to said plurality of recircu¬ lation tubes for cooling the recirculating process fluids.57. Apparatus as defined by claim 51 further comprising cooling means coupled to said plurality of recircu¬ lation tubes for cooling the recirculating process fluids.58. Apparatus as defined by claim 44 further comprising means for monitoring the properties of the fluids in said recirculation tubes.59. Apparatus as defined by claim 50 further comprising means for monitoring the properties of the fluids in said recirculation tubes.60. Apparatus as defined by claim 52 further comprising means for monitoring the properties of the fluids in said recirculation tubes.61. The method as defined by claim 1, wherein said buffering components comprise a mixture of amphoteri substances having a range of isoelectric points.62. The method as defined by claim 2, wherein said buffering components comprise a mixture of amphoteri substances having a range of isoelectric points.63. The method as defined by claim 3, wherein said buffering components comprise a mixture of amphoteri substances having a range of isoelectric points.64. The method as defined by claim 4, wherein said buffering components comprise a mixture of amphoteri substances having a range of isoelectric points. 65. The method as defined by claim 61, wherein the application of said electrical potential across the streamlined channels is operative to establish a gradient of pH steps from channel to channel.66. The method as defined by claim 62, wherein the application of said electrical potential across the streamlined channels is operative to establish a gradient of pH steps from channel to channel.67. The method as defined by claim 63, wherein the application of said electrical potential across the streamlined channels is operative to establish a gradient of pH steps from channel to channel.68. The method as defined by claim 64, wherein the application of said electrical potential across the streamlined channels is operative to establish a gradient of pH steps from channel to channel.69. The method as defined by claim 61, wherein said plurality of permeable membranes define at least six channels.70. The method as defined by claim 62, wherein said plurality of permeable membranes define at least six channels.71. The method as defined by claim 67, wherein said plurality of permeable membranes define at least six channels.72. The method as defined by claim 68, wherein said plurality of permeable membranes define at least six channels.73. The method as defined by claim 69, wherein each of said recirculation paths is adapted to hold at least ten times as much fluid as its respective channel. 74. The method as defined by claim 70, wherein each of said recirculation paths is adapted to hold at least ten times as much fluid as its respective channel.75. The method as defined by claim 71, wherein each of said recirculation paths is adapted to hold at least- ten times as much fluid as its respective channel.76. The method as defined by claim 72, wherein each of said recirculation paths is adapted to hold at least ten times as much fluid as its respective channel.77. The method as defined by claim 73, further comprisin the step of adding fluids to be processed to said fluids containing said buffering components after said buffering components have been focused to establish a pH gradient therein.78. The method as defined by claim 74, further comprisin the step of adding fluids to be processed to said fluids containing said buffering components after said buffering components have been focused to establish a pH gradient therein.79. The method as defined by claim 75, further comprisin the step of adding fluids to be processed to said fluids containing said buffering components after said buffering components have been focused to establish a pH gradient therein.80. The method as defined by claim 76, further comprising the step of adding fluids to be processed to said fluids containing said buffering components after said buffering components have been focused to establish a pH gradient therein. 81. Apparatus as defined by claim 42 wherein said plurality of channels comprises at least six channels,82. Apparatus as defined -by claim 44 wherein said plurality of channels comprises at least six channels,83. Apparatus as defined by claim 52 wherein said plurality of channels comprises at least six channels,84. Apparatus as defined by claim 58 wherein said plurality of channels comprises at least six channels,85. Apparatus as defined by claim 44 wherein each recir- culation path is adapted to hold at least ten times as much fluid as its respective channel.86. Apparatus as defined by claim 82 wherein each recir¬ culation path is adapted to hold at least ten times as much fluid as its respective channel. STATEMENTUNDERARTICLE19Claim 1 has been amended to more clearly recite that it is a method for isoelectric focusing of fluids containing buffering components capable of establishing a stable pH gradient in an electric field. Claims 18-22 have been amended to remove what would now be redundant language and better define the process whereby buffering components are initially focused to establish a pH gradi¬ ent. Claims 60-86 have been added. Claim 60 is similar to claims 58 and 59. In claims 61-64, the buffering components are recited as comprising a mixture of amphoteric substances having a range of isoelectric points. In claims 65-68 the application of electrical potential across the streamlined channels is defined as being operative to establish a stepped pH gradient. In claims 69-72 the plurality of permeable membranes are recited as defining at least six channels. In claims 73-76, each recirculation path is defined as being adapted to hold at least ten times as much fluid as its respective channel. In claims 77-80, there is further defined the step of adding fluids to be processed after focusing of buffering components to establish a pH gradient therein. In claims 81-86 similar types of limitations are set forth as depending from apparatus claims.^OMp | BIER M | BIER M |
WO-1979000943-A1 | 1,979,000,943 | WO | A1 | XX | 19,791,115 | 1,979 | 20,090,507 | new | F16J15 | B63H23 | B63H23, F16J15 | F16J 15/32B3, F16J 15/32G | ANNULAR SEAL | An annular seal against the flow of fluid along a shaft (4). There is a rigid ring (15) with flexible flanges (10, 11) respectively radially inwards and outwards of the ring (15), one of which carries a sealing contact lip (9) against the shaft while the other is connected to a surrounding mounting (13). | .1.ANNULAR SEALThis invention relates to annular seals against the flow of fluid along a shaft, for example for a marine propeller shaft where it is necessary to provide .seals against the entry of sea water, and against the escape5. of lubricating oil from a bearing housing in either direction along the shaft.British Patent Specification No. 1478273. (Howaldtwer e) teaches an annular seal in the form of an elastomeric member but such a seal has been capable of sufficient10. deformation due to pressure differences across it to displace it from its correct sealing position, and to cause it to rub on the shaft causing losses.According to the present invention, an annular seal against the flow of fluid along a shaft which is15. rotatable in a surrounding mounting, comprises a relatively rigid ring and relatively flexible flanges which are respectively radially inwards and outwards of the ring, one of which flanges is connected to the shaft or-mounting, while the other carries a sealing contact lip against the20. mounting or the shaft? the flanges having radial clearance with the shaft and mounting to be capable of deformation to permit variation of the radial clearance between the shaft and the mounting during rotation of the shaft without losing the seal.25. In accordance with the present invention, the relatively rigid ring will be substantially undeformed in use, and that ring can conveniently be located in one axial direction against a support on the mounting, so that the inner and outer flanges tend not to distort30. sufficiently to impair the efficiency ofOMPI /., ΛVIPO . ) the seal. One problem with such a shaft seal is to accommodate what is effectively non-concentricity of the shaft about its axis of rotation, possibly due to whirling load or to static loads, but with the present invention the5. flexible flanges can accommodate such non-concentricity and maintain the seal.Conveniently, one or each of the radially inner and outer flanges extends from the relatively rigid ring in a direction having a substantial component parallel with the10. axis of the shaft, so that radial flexing is possible against little resistance even though axial location is provided between the relatively rigid ring and the support on the mountintAccording to another aspect of the present invention, an annular seal has a flexible flange with a reinforced bead15. at its radially inner or outer edge, which bead is engaged in an annular groove in a mounting, the groove having a neck for the flange which neck is about the same width as the reinforcemei within the bead to prevent removal of the bead from the groove. The bead is conveniently moulded around the reinforcement20 which may be a circumferentially extending metal or plastics wire, or a circumferentially extending metal or plastics helical coil.The groove may be defined between two mounting components one of which is assembled with the other, after the reinforced25. bead has been located, and then conveniently the groove has•VO PI /,_ WIPO .-. •3. three surfaces pressing on the bead which surfaces are distributed around the reinforcement.The invention may be carried into practice in various ways, and certain embodiments will now be described by way 5. of example, with reference to the accompanying drawings of which:FIGURE 1 is a sketch of a horizontal section through' a part of a previously proposed annular shaft seal:FIGURES 2, 3 and 4 are sketches corresponding to FIGURE 1 10. of annular seals embodying the invention;FIGURES 5, a, b, and c, are sketches showing one way of engaging a reinforced bead on the annular seal in a mounting groove; andFIGURES 6, a, and b are sketches showing a different 15. form of reinforced bead on the annular seal.In the type of annular lip seal shown in FIGURE 1, a marine propeller shaft 4 has a surrounding collar 5 and- rotates within a cylindrical mounting 2, which may be a part of the ship's hull. 20. In order to prevent flow of fluid along the annular space between the mounting and the sleeve 5, an annular seal blocks that space, and that consists of a radially outer thick rim 1 engaged in a groove in the mounting 2, a diaphragm part 8 extending radially inwardly, and then axially to a sharp lip25. 9 at its inner end which rubs on the shaft, as the shaft rotates•v-to effect the seal. A coil spring 3 extending annularly around the part of the diaphragm opposite the lip 9 holds the lip against the shaft. The bend in the diaphragm is designed to be towards the area of higher pressure P and away from the area of lower pressure P_.Difficulties with that type of seal can arise due to the shaft surface being apparently eccentric about the5. axis of rotation, the two limiting positions being indicated in FIGURE 1 at 6 and 7. That apparent eccentricity can cause leakage of fluid through the seal if the seal cannot flex easily to accommodate it, but if flexure of the seal is too easy, then an excessive difference in pressure between10. P and P., can deform the diaphragm part 8 of the seal, and that can have the effect of 'lifting the lip 9, • or bringing the rear surface of the diaphragm into contact with the shaft sleeve 5, to cause substantially increased frictional losses during rotation.15. These disadvantages are overcome in accordance with the design of FIGURE 2, which has essentially three components, namely a relatively rigid ring 15, and separate radially outer and radially inner elastomeric flanges 10 and 11.The outer flange 10 has reinforced radially outer and20. radially inner beads engaged in respective grooves in the surrounding mounting 13, and in the rigid ring 15. The main part of the outer flange 10 extends in a cylinder generally parallel with the axis of the shaft.The inner elastomeric flange is similarly supported25. at its racially outer edge from the ring 15, and it also extend; .5 .generally parallel with the shaft axis, but for an axial length only about half that of the flange 10, and it has at its lower edge the conventional sealing lip 9 urged against the surface of the shaft sleeve 5 by a coil spring 12.5. The mounting 13 has a radially inwardly extending flange 20 providing an axial locating surface for the ring 15, but the flange 20 is apertured at 21 so that the low pressure P., has access to the face of the outer flange 10.The ring 15 is of metal or of a plastics material which10. is rigid relatively to the elastomeric material of the flanges 10 and 12, and so does not distort in response to substantial pressure differences between P, and P_, and indeed it is axially located against the flange 20. It is however free ■ to move radially due to flexure of the flanges 10 and 11 in the15. most favourable direction due to their principal lengths being parallel with the shaft axis.Thus variations in the position of the surface of the sleeve 5, as shown at 6 and 7, are easily accommodated by flexing of the inner flange 11, and there is no tendancy to distort the20. seal so that the surface of the flange 11 leading to the lip 9 comes into contact with the surface of the sleeve 5.The inner flange 11 conveniently includes wear resistant compounds which reduce the wear as sliding occurs between the lip and the sleeve at the expense of some loss in the25. flexibility of the material. A preferred wear resistant compound • consists of from 50% to 70% P.T.F.E. by volume, from 10% to 30% j < -/υU 4ό' PCT/GB79/0006. 6 .graphite by volume, and from 10% to 30% bronze by volume. This mixture may be in the form of a mixed powder present in a percentage of between 5 and 30 in a nitrite rubber or plastics or other elastomer stable in sea and fresh water5. and forming the body of the flange 11.In the modification shown in FIGURE 3 the outer flange 10 is of convolutedform with a first part extending axial'ly in one direction and a second part extending axially in the other direction so that the two reinforced beads are10. axially in line with one another.In the modification shown in FIGURE 4, instead of havin an external rigid ring 15 clamped to inner and outer elastomeric flanges 10 and 11, the two flanges are formed by a common annular diaphragm of elastomeric material, as15. indicated at 16 which is moulded around a relatively rigid plastics or metal reinforcing ring 17. It is possible in th embodiment for the wear resisting compound to be included only in the part of the elastomeric flange between the ring 17 and the lip 9.20. FIGURE 5 shows how any of the radially inner or outer edges of an elastomeric flange can be in the form of a bead moulded around an edge reinforcement shown in FIGURE 5a_ as a circumferential metal wire 21 of circular cross section. •That can easily be engaged in an annular groove defined25. between co-operating edges of the mounting 13, and an end •*• . .flange 14 bolted to it as shown in FIGURES 2 and 3. The cross section of the groove consists of a main part in the form of a rectangle with a neck leading to it by way of a pair of outwardly inclined sides, so that the walls of the5. groove press on the external surface of the bead 20 at the three points indicated at x in FIGURE 5b namely at the two inclined sides and the opposite face of the rectangular portion. The neck has a width indicated at y_ in FIGURE 5b approximately equal to (e.g. between 2 and 2/3 times) the10. diameter of the wire reinforcement 21 so that once the end flange 14 has been bolted to the mounting 13, it is not possible to displace the flange rim from the mounting..An alternative form of reinforcement shown in FIGURE 6a_ and b is of metal or plastics wire in the form of a helical15. coil extending circumferentially around the-edge of the flange in order to permit some circumferential flexibility to enable the bead to be easily fitted in the groove while the bead is rather stronger than in FIGURE 5 because of the continuous elastomeric material around the coils of the helix.20. The flange 20 of FIGURES 2 and 3 could be used also in the embodiment of FIGURE 4, but it is not essential in all applications, and particularly in the moulded arrangement of FIGURE 4.In all embodiments the outer flange 10 is more25. flexible than the inner flange 11, whether by choice of the material or by design of the lenths and thicknesses of the flanges. The inner flange 11 only needs to flex enough to maintain the seat at 9, whereas relative movement between the shaft and the housing is accomodated 5. by the outer flange 10.10.OMPI | AMENDED CLAIMS(received by the International Bureau on 10 September 1979 (10.09.79))1. An annular seal against—the flow of fluid along a shaft (4) which is rotatable in a surrounding mounting (13), characterised by a relatively rigid ring' (15) and relatively flexible flanges (10, 11) which are respect¬ ively radially inwards and outwards of the ring, one of which flanges -is connected to the shaft or mounting while the other carries a sealing contact lip (9) against the mounting or shaft; the flanges having radial clearance with the shaft and mounting to be capable of deformation to permit variation of the radial clearance between the shaft and the mounting during rotation of the shaft without losing the seal, the relatively rigid ring being movable, relative to the ring in a radial direction.2. A seal as claimed in Claim 1 in which the outer flange has greater radial flexibility than the inner flange.3. A seal as claimed in Claim 1 or Claim 2 in which the inner and outer flanges are of elastomeric material.4. A seal as claimed in Claim 3 n which at least the radially inner flange contains wear resisting compound.5. A seal as claimed in Claim 4 in which the wear resisting compound includes some or all of P.T.F.E., graphite, and bronze.6. A seal as claimed in Claim 5 in which the wear resisting compound comprises between 50% and 70% by x volume of P.T.F.E. between 10% and 30% by volume of graphite and between 10% and 30% by volume of bronze. 7. A seal as claimed in any of the preceding claims in which the radially inner and outer flanges are parts of a single piece of elastomeric material which is moulded around the relatively rigid ring.8. A seal as claimed in any of Claims 1-6 in which the relatively rigid ring is clamped to the inner edge of the outer flange and to the outer edge of the inner flange.9. A seal as claimed in any of the preceding claims in which the radially outer flange is longer than the radially inner flange.10. A seal as claimed in any of the preceding claims in which the/or each flange extends with a substantial component parallel with the shaft axis.11. A seal as claimed in any of the preceding claims including a support (20) on the mounting for locating the relatively rigid ring in one axial direction.12. An annular seal having a flexible flange (20) with a reinforced bead (21) at its radially inner or radially outer edge which bead is engaged in an annular groove in a mounting, the groove having a neck for the flange which neck is about the same width as the reinforcement of the bead. | BAKER G; GLACIER METAL CO LTD; HILL A | BAKER G; HILL A |
WO-1979000944-A1 | 1,979,000,944 | WO | A1 | EN | 19,791,115 | 1,979 | 20,090,507 | new | B23P15 | B21D53 | B21D53, B23P15, F28D7, F28F9 | B21D 53/02B, B23P 15/26, F28D 7/02D, F28F 9/02 | A METHOD FOR MANUFACTURING A TUBE ARRAY FOR A HEAT EXCHANGER | A tube array for a tubular heat exchanger comprises (i) a cylindrical container (2) having an inlet opening (5) and an outlet opening (6) for a through-flowing fluid, (ii) a plurality of helically coiled tubes (9) which extend axially of the container and which are adapted for a through-flow of another fluid and (iii) a tube mounting member (11) at each end portion of the container for securing the respective ends of the helically coiled tubes (9) and for forming a header for the other fluid flowing through said tubes. Said mounting members have the shape of a tubular sleeve (11) the longitudinal axis of which extends coaxially with the longitudinal axis of the container and are provided with a plurality of tube mounting openings (10) over its peripheral surface in which the ends of the respective tubes (9) are adapted to be permanently secured A method for manufacturing such a tube array according to the invention is substantially distinguished by the step of securing a tubular sleeve (11) with one of its ends, which is closed, to either end of an elongated shaft (13), introducing a rotatable mandrel (16, 16a) into the opposite open end of both the sleeves (11), inserting one end of at least one of the tubes (9) into an associated opening (10) in one of the tubular sleeves (11) and then rotating the mandrels (16, 16a) and thus the sleeves (11) and the shaft (13) connected therewith while winding the tube (9) around the shaft in a helical path towards the other sleeve (11) so as to form a first tube layer around the shaft (l3), after which the other end of the tube (9) is inserted into an associated opening (10) in the other tubular sleeve (11) and finally the two tube ends are permanently secured in the respective sleeve (11), furthermore one or more layers of tubes (9), if desired, being wound helically in the same way between further openings in the tubular sleeves (11) located axially beyond the openings (10) for the tubes (9) in the first layer. | A METHOD FOR MANUFACTURING A TUBE ARRAY FOft ftHEAT EXCHANGERThe present invention refers to a method for manufacturing a tube array for a tubular heat exchanger of the kind comprising a substantially cylindrical container, at one end having an inlet opening and at the other an outlet opening for a through-flowing fluid, a plurality of helically coiled tubes extending axially .of the container and adapted for a through-flow of another fluid preferably in opposite direction to the first-mentioned fluid, and a tube mounting member at each end portion of the container for securing the respective ends of the helically coiled tubes and for forming a header for the other fluid flowing through said tubes, said mounting members having the shape of a tubular sleeve the longitudinal axis of which extends coaxially with the longitud¬ inal axis of the container and has a plurality of tube mounting openings over its peripheral surface in which the respective tube ends are adapted to be permanently secured such as by soldering.In a well-known heat exchanger of 'this kind each tube mounting member is constituted by a plane tube plate at right angles to the container axis, said plate forming together -with the container end wall a header for the fluids-flowing through the helically coiled tubes. For the reasons of manufacture and strength such a tube plate has a relatively great diameter and thickness, which makes the tube mounting member expensive to manufacture. In the manufacture of such a heat exchanger the helically coiling of the tubes is carried out as a separate operation before the tube ends are inserted and secured into the openings in the tube plates. Normally the winding is carried out such that the txibes are wound in superimposed layers, the first layer being wound around a separate elongated cylindrical core supported by a winding machine. After the winding of the tubes the tube ends are simultaneously inserted into associated openings in the tube plates, which is a work which requires time and precisioIn another known heat exchanger each mounting member is made as a thick-walled, part-spherical tube plate with its concave - 2 -space turned outwards, the cup-shaped tube plates each being connected to a separate, corresponding cover portion for forming a header for the outlet and inlet, respectively, for the fluid flowing through the tubes. Also in said heat exchanger the coiling of the tubes must be carried out in a separate operation before the mounting of the tube plates. The coiling is' carried.out such that a first helically coiled tube layer is wound on a mandrel, after which said tube layer is removed from the mandrel and inserts into engagement with the internal surface of a cylindrical casing. After that, the next following layer is wound on a mandrel of smalle diameter than the preceding one, after which said tube layer is introduced concentrically in the preceding tube layer within the cylindrical casing. This procedure is repeated unt l a required number of tube layers has been obtained. 3efore the tube ends are inserted and secured into the cup-shaped tube places a centre core is mounted. Similar to the first-mentioned known heat exchanger, said design of the tube mounting means requires a pre-coiling of the tube array and a time-consuming simultaneous insertion of the tube ends into the cup-chaped tube plates, which normally are manu¬ factured by stamping of a circular blank of relatively great thick¬ ness, which causes great material expenses.■ In a still further known heat exchanger the tube mounting members are made as an annular tube chamber located in each end portion of a container and forming a header. These annular headers are connected through branch pipes to an inlet at one end of the container and an outlet at the other end thereof. The manufacture of such an annular chamber is complicated, however, and is usually carried out by joining to annular halves by an extensive soldering operation of the securing of the tubes in one of that annular halve The very coiling of the tubes also is carried out in this case as a separate operation before the mounting of the tubes and is in principle made in the same way as in the above mentioned heat ex¬ changer with plane tube plates. An object of the present invention is to provide an improved heat exchanger which allows a simplified manufacture of the heat exchanger as a whole and particularly an improved tube mounting member for such a heat exchanger.In accordance with the present invention, this object as ell as other objects obvious to those skilled in the a-rt are obtained by securing a tubular sleeve with one of its ends, which is closed, to either end of an elongated shaft,introducing a rotatable mandrel into the opposite open end of both the sleeves and brought into driving engagement with the sleeve, inserting one end of at least one of the tubes into an associated opening in one of the tubular sleeves and then rotating the mandrels and thus the sleeves and the shaft connected therewith while winding the tube around the shaft in a helical path towards the other sleeve so as to form a first tube layer around the shaft, after which the other- end of the tube is inserted into an associated opening in the other tubular sleeve and finally permanently securing the two tube ends in the respective sleeve, furthermore one or more tube layers, if desired, being wound helically in the same way between further openings in the tubular sleeves located axially beytnd the openings for the first tube layer.An essential advantage of the invention is that the assembly of the tube array in principle can be made in one single continuous working operation, i.e. the tubes can be secured in the tube mount¬ ing members and wound helically around a central shaft. Thus the tube mounting members made as tube sleeves actively co-operate in the very winding phase of the tubes in that they are brought to rotate as a unit with the shaft mounted between the tube sleeve by means of the mandrels, which are adapted to be introduced into said sleeves, 'when inserting the tube ends into the openings in the tubu¬ lar sleeves the ends of the tubes are upset against the driving mandrels introduced into said tubular sleeves, said mandrels thus also serving as a stop member defining the insertion depth of the tube ends into the tubular sleeves. Ey way of example, the method according to the invention will be further described below with reference to the accompanying drawings, in which fig. 1 is a partially sectioned side elevation of view of a tube heat exchanger manufactured according to the in¬ vention and fig. 2 is a fragmentary side view of two tubular sleeves according to the invention with rotatable driving mandrels inserted therein.The -heat exchanger generally designated 1 in Fig. i comprises an external cylindrical container 2 with dome-shaped end portions 3 and ^ . The end portion 3 is provided with an inlet 5 for a first fluid flowing through the container, while the other end portion 4 is provided with an outlet β for the same fluid. The container 2 accommodates a cylindrical internal casing 7, which in its turn envelopes the portion of a tube array 8 which contains helically coiled tubes 9- The tubes 9 are preferably constituted by copper tubes having a substantially oval cress-sectional shape and another fluid is adapted to flow through said tubes in a direction preferably opposite the direction of flow of the first-mentioned fluid through the container 2.Either end of each tube 9 is inserted into and secured by sol¬ dering into an associated opening 1C in a tube mounting member 11, which has the form of a cylindrical tubular sleeve which forms a header for the through-flowing other fluid. The heat exchanger com¬ prises one such tubular sleeve 11 at either end of the container 2. Since the tubular sleeves 11 are of similar design only one of them will be described in detail below.Each tubular sleeve 11 is manufactured preferably from a cy¬ lindrical copper tube blank, in a pressing operation being provided with a corrugated or wave-shaped wall surface as seen in a longitu¬ dinal section of the sleeve.According to a prefered embodiment of the heat exchanger the openings 10 in the tubular sleeve 11 are stamped in sets in axially spaced radial planes 12 through the tubular sleeve 11, said ope¬ nings 10 being formed in such way that the ends of the tubes 9 will be oriented obliquely inwardly to the center axis of the header formed by said tubular sleeve and away from a plane dis¬ posed at right anglesto the container shaft A and within the inner end of the respective tubular sleeve 11. Owing thereto, very good flow-characteristics are obtained at the tubular sleeve 11 serving as inlet header as well as the similar tubular sleeve 11 serving as outlet header. In the embodiment according to Fig. 1 each tubular sleeve has six axially spaced sets of openings 10, evenly distributedaround the periphery of the sleeve wall. Each such set may comprise e.g. 7-15 openings 10. Furthermore, the openings 10 in the various radial planes 12 are arranged in straight rows parallel to the axis of the tubular sleeve 11 for providing open passages between the rows so as to facilitate the work with soldering the ends of the tubes to the sleeves 11.The two tubular sleeves 11 are arranged in mutual concentric relationship and mutually connected or releasably coupled together by means of a central elongated shaft 13 in the form of e.g. a steel tube. The inner end of the sleeves is closed by an end wall 14, which on its inside is provided with suitable coupling means 15 for driving co-operation with a mandrel lβ, iβa, v.hich is to be in¬ serted into the tubular sleeve for a purpose to be further described below.As is evident from fig. 1 the tube array 9 of the heat ex¬ changer preferably comprises a plurality of superimposed and in different radial layers helically coiled tubes 9, between each layer being layed a plurality of circumferεntially distributed andaxially extending wire or band-shaped spacing elements17, which keep the tube layers spaced a distance suitable from a view-point of flow. Between the inner tube layer and the tube shaft 13 and between the outer tube layer and the surrounding inner casing 7 are also arranged a plurality of circumferentially distributed and axially extending spacing elements which also can be made of wires or bands 17 or still better ridges or . protuberances formed on the outer surface of the tubular shaft 13 and the inner surface of the inner casing 7 , re¬ spectively. Common to said inner and outer spacing elements is that they have half the thickness or height of the wires laid between the tube layers for making the flow conditions uniform around the exterior of the tubes 9.In order to improve the flow conditions of the first- entionei fluid flowing exteriorly of the helically coiled tubes and hence the heat exchange with the other fluid the tubes have substantially oval cross-sectional shapes with an axis ratio of about 7:12.The inner casing 7 surrounding the tube array 8 has at one ent a plurality of holes 18 for removal of air between the inner casing and the cylindrical container portion 2 when test pressurizing or starting the heat exchanger for thus preventing eventual rupture or deformation of the thin-walled inner casing 7-The preferred embodiment of the heat exchanger according to the present invention is manufactured and assembled in the following way.The tube mounting members 11 are manufactured by cutting cylindrical copper tube blanks of standard diameter into suit¬ able lengths and inserting said blanks into a forr. press, in which the cylindrical wall of each tube blank is given 'a corrugated or wave-like shape in longitudinal section. The tube mounting openings 10 are then made by stamping and one end of the tubular sleeve 11 is provided with an end wall 14, the inner surface of which is formed with suitable coupling means 15. The closed ends of the tubular sleeves 11 are rigidly secured to or releasably coupled together through a central tubular shaft 13, the two sleeves 11 and the shaft 13 thus forming a continuous unit.After that, one of the tubular sleeves 11 is slid onto a rotatably driven mandrel iβ (see fig. 2), at its outer end having complementary coupling means t-o the coupling means 15 of the tubular sleeve for co-operation therev/ith but not illustrated in the drawing Into the other tubular sleeve 11 is inserted another mandrel l6a, which also has coupling means for co-operation with the coupling means 15 of the other tubular sleeve 11 and which when rotating the first mandrel 16 is brought to rotate together therewith. After mounting of the unit consisting of the two tubular sleeves 11 and the shaft 13 between the mandrels lβ, iβa the winding of the tubes 9 is started. This is carried out in such a way that one end of one or possibly more tubes 9 from a supply roll are inserted each into an opening in the set of openings 10 which lie in the radial plane 12 closest to the inner end wall 1 4 ■of the tubular sleeve. The end of the tube or tubes 9 is inserted into engagement with the mandrel iβ and l6a, respectively, which has' substantially the same diameter as the inner diameter of the tubular sleeve 11, thereby deforming the tube ends slightly so as to 'secure them in the respective opening 10 while extending a predetermined distance into the tubular sleeve. The driving mandrel 16 then is brought to rotate the entire unit, the tube or tubes 9 being helically coiled in a first layer around the shaft 13, on which, if desired, thin axially extending spacing elements of wire or band shape have been previously applied. It is to be noted that the tubes 9 at their bending point for the helical coiling are slightly flattened so as to obtain a slightly oval cross-sectional shape, whereby the flow conditions for the surrounding first fluid are improved.When reaching the opposite tubular sleeve 11, the tube or tubes 9 are cut and inserted in a corrεponding manner into associ¬ ated openings 10 in the first radial set of openings. The next tube layer is coiled in the same way, the spacing wires 17 first being applied onto the preceding tube layer. In the continued winding operation all the openings 10 in the first radial set are connected to the adjacent radial set of openings 10. If desired, the winding can be carried out alternately, i.e. the tubes 9 are coiled alter¬ nately to the left and to the right. When all tubes 9 have been coiled the tube ends are fixed by soldering along the- passages which have been formed between the tube rows in the axial direction of the tubular sleeves. After soldering the obtained tube array 8 is mounted into the inner casing 7 which then is mounted in the containei 2 in a suitable way..\_ -•— .( ■ - - From the above-stated description it is evident that the present invention suggest a tubular heat exchanger which,as far as material and manufacture is concerned, implies great savings when compared with the previously applied methods in the present field. The new design of the headers of the heat exchanger also has impliei improved flow conditions for the fluid flowing through the helically coiled tubes 9-The present invention is not limited to the above-described embodiment but can be varied within the scope of the accompanying claims. | C l a i m s1. A method for manufacturing a tube array for a tubular heat exchanger of the kind comprising a substantially cylindrical con¬ tainer, at one end having an inlet opening and at the other an * outlet opening for a through-flowing fluid, a plurality of helically coiled tubes extending axially of the container and adapted for a through-flow of another fluid preferably in opposite direction to the first-mentioned fluid, and a tube mounting member at each end portion of the container for securing the respective ends of the helically coiled tubes and for forming a header j the other fluid flowing through said tubes , said mounting members having the shape of a tubular sleeve, the longitudinal axis cf which extends coaxially with the longitudinal axis of the container and has a plurality of tube mounting openings over its peripheral surface on which the respective tube ends are adapted to be permanently. secured such as by soldering, characterized by securing a tubular sleeve with one of its ends, which is closed, to either end of an elongated shaft, in¬ troducing a rotatable mandrel into the opposite cpen end of both the sleeves and brought into driving engagement with the sleeve, inserting one end of at least one of the tubes into an associated opening in one of the tubular sleeves and then rotating the mandrels and thus the sleeves and the shaft connected therewith while winding the tube around the shaft in a helical path towards the other sleeve so as to form a first tube layer around the shaft, after which the other end of the tube is inserted into an associated opening in the other tubular sleeve and finally permanently securing the two tube ends in the respective sleeve, furthermore one or more tube layers, if desired, being wound helically in the same way between further open¬ ings in the tubular sleeves located axially beyond the openings for the first tube layer.2. A method according to claim 1, characterized in that before- the coiling of each tube layer wire or band-like spacing elements (17) are applied axially to the coiling shaft (13) and on top of the preceding tube layer or the coiling shaft (13), respectively. 3. A method according to claim 1 or 2, characterized in that as tube (9) is utilized a copper tube with circular cross-sectional shape, said tube at the bending point for the helically coiling at the sametime being flattened to a substantially oval cross-sectional profile.4. A method according to any of claims 1-3, characterized in that the tubular sleeve (11) in a pressing operation is given a wave-like wall shape in longitudinal section.5. A method according to any of claims 1-4, characterized in that the ends of the tubes (9) inserted into the openings (10)in the tubular sleeves are upset against the mandrel (iβ, 16a) inserted in the respective sleeve, said mandrels thus serving as a step means determining the insertion depth of the tube ends into the tubular sleeve (ll). | ELGE VERKEN AB; ERIKSSON H | ERIKSSON H |
WO-1979000955-A1 | 1,979,000,955 | WO | A1 | EN | 19,791,115 | 1,979 | 20,090,507 | new | B41F31 | G01S9, G01F23 | B41F31, B41F33 | B41F 31/02C, B41F 33/00 | INK LEVEL CONTROL | An ink level control for a printing press is disclosed having an ultrasonic ink level sensor (30) to receive an echo signal representative of the level of the ink in the ink fountain. A control is provided whereby the ink level is maintained at a desired operating level and conditions of excessively low and high ink levels are also detected by the sensor. An echo loss detection network (110) is provided to warn the operator and inhibit ink feeds. The control is designed to prevent overflow of the ink fountain (12). | INK LEVEL CONTROLField of the InventionThis invention relates to an apparatus for con¬ trolling the ink level in an ink fountain used in a printing press such as the viscous ink in art offset litho- graphic press.Background of the InventionThe ink consumption in a modern, high -speed print¬ ing press is very large and as a result, ink is frequently pumped to the press in pipes installed for that purpose. Most offset printing inks are quite viscous, and are comparable to very thick molasses in this respect. As a result, ink neither flows readily, nor seeks its own level quickly. When the valve in the ink line is opened to introduce additional viscous ink into an ink fountain used in a printing press, the new ink takes a long time to level out.Ink generally is considered an active substance in the sense that the ink sets when allowed to stand and dries when exposed to air. In addition, ink is sticky and readily adheres to all commonly used materials. These properties pose a difficulty in sensing ink level since the ink has a tendency to accumulate or build up on any sensing member or component with which the ink comes into contact.-BU EAUOMPI fr y, RWNiAP70\0 -7y Typically, the ink fountain or reservoir in an offset printing press is constructed in the form of a trough such as shown in U. S. Patent 3,848,529 to Gegen- hei er et al, which is assigned to the same assignee of this invention. The ink trough is formed by a flat blade which forms a nip with a fountain roller. A feature of such reservoir is that the surface of the ink contained therein is not flat, but usually undulates while the pres is in operation at a frequency in the range from 0.25 to once a second. This undulation is produced by a ratchet action of a fountain roller and makes it difficult to sense the ink level.Ink fountains in many printing presses are commonly equipped with ink agitators which improve ink distribution, prevent the formation of surface skin and improve feeding of the ink to the nip between the flat blade and the fountain roller. The main element of an in agitator may be in the form of a conically shaped roller which is caused to rotate while traveling to and fro the length of the ink fountain. Such roller is illustrated i the aforementioned Gegenheimer et al patent. The presenc of an agitator produces a wave in the ink of a height which may be of the order of an inch or even more. When the ink is so disturbed, its surface quivers and undulate so as to make it difficult to sense ink level.The space above the ink fountain must be kept relatively clear to allow room for the operator of the printing press to clean the fountain or to enable ink to be fed manually for occasions when special or spot colors are necessary. As a result, the sensing of ink level mus be done in such manner that the area or space over the in fountain is not unreasonably obstructed.When multi-color printing presses having many ink fountains are involved, a plurality of ink level con- trol systems are employed. On any particular printing operation, however, it may not be necessary to use all of the ink fountains. As a result, some of the unused fountains may not have any ink and the ink level control must be able to sense such condition to avoid system malf nctioning.A large number of automatic ink level sensor designs have been proposed. Ink level sensors may use floating, tactile, capacitance, pneumatic or ultrasonic techniques. U.S. Patent 3,025,793 describes an ink level control for a newspaper press utilizing a float operated ink feed valve. Although such an approach is workable in newspaper presses, which utilize relatively thin or low viscosity inks, the float concept is not feasible in commercial presses requiring thicker inks. A major diffi¬ culty encountered with a floating device resides in the accumulation of ink on the float, eventually rendering it inoperable. The float also tends to take up a large amount of space, particularly when such float is directly connect¬ ed to operate an ink flow control valve.The U.S. Patent 3,373,052 and the previously mentioned Gegenhei er et al patent are examples of ink level controls wherein a tactile type sensor detects the ink level by touching the ink. Such sensor does not cir¬ cumvent the difficulties due to ink activity and, as a result, the sensor tactile element must be periodically cleaned for reliable operation. In the aforementioned Gegenheimer et al patent, a tactile sensor is employed to monitor the height of the wave of ink generated by an agitator, thereby overcoming the difficulty posed by the waves in measuring the ink level. Gegenheimer et al also discloses the use of an adjustable timer to limit the duration of ink feed to over¬ come the difficulty posed by the high ink viscosity which prevents an even ink level from being quickly established when the ink valve is opened. In one form for such timer, adjustable feed pulses are applied through a relay to actuate the ink valve. The width of the feed pulses and the intervals between the pulses can be selected.A number of prior art systems employ sensors which avoid ink contact by using the capacitance principl In one approach, such as disclosed in the U.S. Patent 4,010,683, a plate is mounted above the ink fountain to form an electrical capacitor with the ink fountain blade. Since the permitivity of ink differs significantly from air, the capacitance will vary the ink level and thus pro vides a non-contacting method for detecting ink level. This sensor design has a disadvantage in that the sensor must be located within approximately an inch of the ink surface, thus obstructing access to the fountain.A pneumatic ink level measuring system is avail able in the form of a vertical tube which is inserted int the ink fountain. The tube is connected to a source of air and the pressure in the tube is monitored to obtain a measure of ink level. This concept is satisfactory for low viscosity, inks but difficult to apply to highly vis¬ cous offset printing press inks.Ultrasonic techniques for detecting the level o liquids are well known and have been applied to ink level controls in a limited liquid contacting manner. A genera description of ultrasonic techniques can be found in an article entitled Ultrasonic Instruments for Level and Flow in the September, 1974 issue of Instrumentation Technology. Ultrasonic systems for determining liquid level utilize one of two basic approaches. In a first liquid contacting type, a detector provides an on-off signal whe the liquid comes into contact with the ultrasonic sensor; see, for example, U.S. Patent 3,520,186 to Adams et al. The liquid level may interrupt ultrasonic waves or cause change in the dampening characteristics of an ultrasonic transducer when it is contacted by the liquid. Contact b the detector with ink, however, is not desirable.In another type of ultrasonic level detector, a echo ranging principle is employed, such as described in the U.S. Patent 3,985,030 to Charlton. A pluse of ultra¬ sonic energy is directed to a transducer toward the liqui ϊUK surface. A receiver listens for an acoustic echo and the time required for the echo to return provides a measure of the distance between the ultrasonic transducer and the liquid surface. In the Charlton patent, a loss of echoes is detected and used to override an automatic level indi¬ cator by registering a maximum liquid level depth.Summary of the InventionIn an ink level control in accordance with the invention, the ink level is sensed remotely with an ultra- sonic pulse-echo technique. An accurate ink level control is provided capable of detecting ink level even in the presence of a quivering, undulating ink surface and an agitator- wave, while providing operational safeguards for reliable and fail-safe operation. As described with reference to one embodiment for an ink level control in accordance with the invention, an ultrasonic transducer is selected of a type capable of operating within normally encountered space restraints near the ink fountain of a printing press. The transducer can be remotely spaced from an ink fountain to enable ac¬ cess for cleaning, yet can be mounted within the available space and provide a reliable sensor of the ink surface as a result of acoustic pulses directed at the ink. Acoustic reflections from the ink are detected and processed to produce a measured ink level signal representative of the ink level in the fountain. An averaged or smoothed measur¬ ed ink level signal is compared with a reference represent¬ ative of a normally desired ink level in the fountain and the comparison used to provide an ink feed signal. The ink feed signal is thereupon converted to ink feed pulses separated by intervals of a predetermined duration. Various ink feed limitations are applied to assure the proper feed of ink in a manner whereby the ink fountain is prevented from overflow. With such controls an accurate, non-contacting ultrasonic ink level sensor can be used to maintain the ink level at a desired level while preventing an excessive feed of ink to the fountain.As further described with reference to a prefer red embodiment of the invention, an echo loss detection network is used to detect when echoes are not received. Such loss may arise from the passage of the agitator's in wave in the path of the ultrasonic beam. When an echo loss occurs, a simulated ink feed signal is produced to maintain normal operation of the ink level control. In th event the echo loss persists longer than a particular tim an alarm is generated.The echo loss detector is particularly useful during field installation of the ink control when the ul¬ trasonic transducer is aligned at the ink surface. The echo loss detector is visually monitored by observing an alarm light energized by an activated echo loss detector. Accurate alignment of the transducer may then be achieved by angularly moving the transducer to determine its angu¬ lar operating range over which an echo can be obtained. The transducer is then fixed at a midway position of the operating range. This procedure, when carried out for transverse planes which are also normal to the ink surfac provides a convenient technique for using and field align ing of a narrow beam .ultrasonic transducer. In the described ink level control in accordanc with the invention, both high and low ink level reference signals are generated to define an acceptable range of in level within the ink fountain. The measured ink level si nal is compared with these reference signals to generate an alarm when the measured ink level falls outside this acceptable range. Enhanced protection is provided by in¬ hibiting the feeding of ink when the ink level drops belo its acceptable low level. This feature prevents ink spil when the fountain is opened for cleaning. It is, therefore, an object of the invention to provide an ink level control which overcomes the previous described disadvantages while enabling an accurate, reliabl BUO_ Λι control of the ink level in an ink fountain of a printing press.These and other advantages and objects of the invention can be understood from the following description of an embodiment described in conjunction with the draw¬ ings.Brief Description of DrawingsFig. 1 is a schematic block diagram of an ink level control in accordance with the invention for use with a printing press; andFig. 2 is an electrical schematic of a simulated ink feed signal generator for use in an ink level control in accordance with the invention.Detailed Description of EmbodimentWith reference to Fig. 1, an ink level control10 for a printing press (not shown) is described. An ink fountain 12 as generally described and shown in the Gegen¬ heimer et al Patent 3,848,529 is illustrated with a foun¬ tain blade 14 and an ink fountain roller 16 converging at a nip 18. The ink fountain 12 may be provided with an agitator 20 which is moved to and fro as described in the Gegenheimer et al patent with a suitable actuator 22. The fountain roller 16 is periodically actuated with a ratchet mechanism (not shown) . Ink 23 is supplied to the fountain 12 from a supply 24 through an automatically controlled ink feed valve 26 and conduit 28. Other ink feed supply elements such as a pump have been deleted for clarity. The ink surface 36 tends to distort from its normal level as shown at 37 depending upon the frequency of operation of the agitator 20, fountain roller 16 and the viscosity of the ink. A more or less permanent quivering and undulated bulge such as 39 extending over the length of the fountain 12 is often encountered. An ink level sensor 30, in the form of an ultra sonic transducer, is disposed at a suitable distance from the ink fountain 12 to direct acoustic pulses along a bea axis 34 transversely onto the surface 36 of the ink 23. The transducer 30 is selected of a type capable of genera ing acoustic pulses and providing an echo signal represen ative of acoustic returns or echoes from the ink surface 36 within the available space of a printing press. The transducer 30 must be capable of operating within the available space above the fountain 12. Since the trans¬ ducer must operate in air, it tends to produce an undampe acoustic pulse followed by undesirable ringing effects an a greater spacing from the ink is needed to allow such trailing acoustic transients to die down. With the print ing press' space limitation, however, the increased spac¬ ing frequently is difficult to accommodate and a high fre quency transducer, capable of operating in the range of about 200 KHz is preferred. Such higher frequency trans¬ ducer 30 enables one to employ remote acoustic ink surfac sensing on printing presses with acceptable accuracies. The high frequency transducer, however, has a narrow beam of the order of about six degrees. Hence, the transducer 30 is also carefully aligned and positioned to sense the various ink surfaces encountered on printing presses. A control network 38 is provided to actuate transducer 30 and respond to the echo signal for control over the ink level in fountain 12. Ultrasonic transducer capable of generating and detecting acoustic pulses are well known and need not be further described. Transducer 30 is controlled with a transceiver40 formed of a digital circuit as may be commonly pur¬ chased. The transceiver 40 responds to pulses, Tx, on line 41 from a timer 42 which may generate these at a hig rate of the order of 100 pulses per second. Each trans- mitter pulse causes the transceiver to deliver a large driving pulse on line 44 to transducer 30 which generates an acoustic pulse towards the ink surface 36. Acoustic_ •fry, returns from ink surface 36 are detected by transducer 30, amplified by transceiver 40 and made available as an echo signal for processing on an output line 46.The echo signal is applied to a gate 48 which is normally enabled by the level on line 50 from an inverter 52 coupled to the timing pulses Tx from timer 42. While pulses Tx are active, gate 48 is disabled. This prevents erroneous responses when transducer 30 generates an acous¬ tic pulse. If desired, a longer lasting inhibition of gate 48 may be obtained by replacing inverter 52 with a pulse network whose output pulse would last while an acoustic return from ink surface 36 could not occur; for example, an inhibiting pulse lasting for slightly less than the round trip transit time of the acoustic energy could be used. The disabling level on line 50 is also applied to reset a flip-flop 54.When gate 48 is enabled and receives an echo signal from transceiver 40, flip-flop 54 is set to provide an echo signal on line 56 to an ink level signal generator 58. The latter is responsive to transmitter pulses Tx on line 41 and the echo signal from flip-flop 54 to measure the time therebetween and produce, on output line 60, an ink level signal representative of the actual ink level in fountain 12. Techniques for measuring the transit time of an acoustic pulse to a reflecting surface are well known in the art. Hence, the measurement of the distance between transducer 30 and ink surface 36 can be carried out with a variety of different ink level signal generators 58. The latter may be an analog or digital circuit capable of pro¬ viding a signal representative of the ink level.Since transducer 30 provides an echo signal at a time which is a function of the spacing of transducer 30 from ink surface 36, the ink level signal is similarly re- lated. However, by placing transducer 30 a fixed known distance from ink fountain 12, the ink level signal on line 60 represents actual ink level in the fountain referenced relative to, for example, the deepest level 5 at nip 18.The ink level signal on line 60 is applied to comparator 62 together with a reference signal represent tive of an operating ink level 59.3 desired to be main¬ tained in fountain 12. This reference signal is obtaine on line 64 from a suitable network 66 and a resulting comparison is produced as an ink feed signal on output 6 of comparator 62 when the ink level, as measured, drops below the operating reference. The comparator 62 is of type which does not present an output as long as the measured ink level is above the operating level. When t ink feed signal occurs on output 68 of comparator 62 it enables a clock 70 which generates ink feed pulses 72 se arated by ink leveling intervals 74 on line 75. The ink pulses 72 are applied to an ink feed relay 76 coupled to operate valve 26 and enable ink to flow into fountain 12. Clock 70 has an interval control network 78 to control the duration of intervals 74 and a pulse width selection network 80 to regulate the widths of pulses 72. The pulse widths are selected to be long enough to keep with the printing press' utilization of ink, but not so long that the fountain would overflow.The intervals 74 must be long enough to allow the ink to level out in between feeds to prevent an over flow, but short enough to keep up with the ink utilizati of the printing press.The interval control network 78 sets the time between successive pulses 72. This interval is made sufficiently long to enable a change in the ink level to be registered in response to a previous ink supply pulse. The duration is a function of viscosity with more viscous inks requiring longer intervals.For a practical application, the pulse widths may be of the order of 1 to 15 seconds separated by inte vals of 15 seconds for an ink having a viscosity of the order of 200 poise. The ink level control 10 maintains ink in the fountain below maximum level 59.5 by applying a high ink level reference signal on line 82 from a reference source 84 to a comparator 86. The high ink level reference sig- nal represents the maximum acceptable ink level 59.5 in the fountain 12 and is compared with the measured ink level signal on line 60 to produce an alarm on comparator output 88 when the ink level exceeds the maximum level 59.5. From time to time an ink wave, such as caused by the action of the agitator 20, generates an acoustic re¬ turn which causes the measured ink level signal on line 60 to temporarily represent an ink level above the maximum level 59.5. In such case comparator 86 may produce an alarm signal on output 88. Since such alarm condition is of short duration, a timer 90 is employed to screen out momentary high ink level detections. Timer 90 is of a type whereby the high ink level alarm on line 88 must per¬ sist for a minimum time period to cause a high ihk level alarm on output 92 to activate a high level relay 93. The relay may be used to sound an audible alarm 94.The ink level in fountain 12 is normally kept at or above operating level 59.3. If, notwithstanding such control, the ink level drops below the operating level 59.3 and also below minimum level 59.2, the condition is identified as a malfunction with a minimum level control 95.The measured ink level signal on line 60 and a low ink level reference signal on line 96, representative of minimum level 59.2 and generated by a source 98, are compared by a comparator 100. If the measured ink level drops below minimum 59.2, a low ink level alarm signal is produced on comparator output 102.Since a low ink level alarm is construed as a malfunction of the system, such as may occur if the ink fountain is in an open unused condition, the comparator output 102 is applied to an inhibit input of comparator 62 BURt0MP1 to inhibit it from generating an ink feed signal on line 68. Comparator output 102 is also applied to a relay 104 to operate such devices as appear necessary to respond to such low ink level condition since the low level may also be due to valve 26 being stuck or the ink supply being de pleted. Relay 104 may, for example, sound an audible alarm 106.The use of ultrasonic transducer 30 provides th advantage of remote sensing of the ink level. However, from time to time the ink surface 36 is not level so that acoustic returns are reflected in the direction of arrow 35 instead of back onto transducer 30. As a result, an echo may be lost and no echo signal produced on line 56. In order to avoid a misinterpretation of such echo loss a an excessively low ink level, the loss of echo signal is detected with a network 110 and an appropriate ink level signal is simulated and provided on line 60.Echo loss detector 110 includes a pulse network 112 which sets a flip-flop 114 in the event an echo signa fails to occur on line 56 within a certain time period following a transmitter pulse Tx. If an echo signal does occur, the setting pulse from pulse network 112 is ineffe tive since the echo signal on line 56 from flip-flop 54 i applied to maintain flip-flop.114 in its reset state. In the event no echo is detected, the reset level on line 56 to flip-flop 114 is not present and the output pulse on line 116 from pulse network 112 sets flip flop 114 to provide an echo loss signal on flip-flop outp 118. With the generation of an echo loss signal on line 118, an echo simulator circuit 120 is activated to provide a simulated ink level signal on line 122 represen ative of an ink level 59.4 between the operating level 59 and maximum level 59.5. The ink level signal is applied network 58 and appears on line 60 as long as echoes are lost.- As soon as an echo signal again is produced, flip- flop 114 is reset and the simulated ink level signal onIJUO _• _. I ?N line 118 deactivated.In the event an echo loss condition persists for an excessive time period, a malfunction signal is produced with a timer 124 actuated by the echo loss signal on line 5 118. Timer 124 generates an alarm signal on line 126 for actuation of an appropriate alarm 128.Fig. 2 illustrates an analog form of echo simu¬ lator 120 for generating a simulated ink level signal. The simulator operates with an ink level signal generator10 58 of an analog type whereby the average voltage from flip-flop 54 (proportional to ink level) is stored in a capacitor 132.When an echo loss signal occurs on line 118, it closes a transistor switch 134 having a simulated refer-15 ence level signal from a source 136 coupled to a power electrode 138 such as the collector. The other- power electrode 140, the emitter, is coupled to capacitor 132 to clamp its voltage to the simulated reference level from source 136. Hence, as long as an echo loss condition per-20 sists, a simulated ink level signal is provided on line 60. A particular advantage of capacitor 132 involves its smoothing effect upon the ink level signal. Such smoothing is desirable in view of the occasional loss or changes in the arrival time of an echo signal due to the25 vibratory and disturbed nature of the ink surface 36. This smoothing is done over a time period sufficient to average a desired number of echo signals. A time constant associated with the charging, of capacitor 132 may be of the order of about a third of a second.30 The ink level control in accordance with the invention can be obtained with a digital network. For example, a microprocessor may be programmed to respond to the transceiver output 46 and transmitter pulses, Tx, to provide a digital echo signal. One method in which this35 can be done is to enable an internal microprocessor clock to enter pulses into a register and terminate this when the transceiver generates an echo signal. The accumulated* count in the register represents the two-way travel time of an ultrasonic pulse from transducer 30 to ink surface 36. The actual distance is directly proportional to the travel time and can be derived using a value of the speed of sound in air.The distance value effectively represents the measured ink level by virtue of the known distance betwee the transducer and the bottom level 59.2 of the ink foun¬ tain. The distance value is thus converted to a measured ink signal within the microprocessor and stored in a suit able memory location. A suitable averaging technique may be employed to smooth out the effect of ink level surface variations. The number of travel time or distance measur ments to be averaged depends upon the travel speed of the agitator 20 and the size and frequency of the vibrations of the ink surface 36. In a pulse echo ink level control which generates of the order of about 100 echo pulses per second, the averaging of about 50 measured travel times can be used. The stored ink level signal is then compared with various previously stored digital values for the hig low and operating levels to provide an ink feed signal to the ink feed valve 26. An echo loss can be detected by comparison with a particularly low ink level reference value such as 59.1. The digital form of ink level contro 10 may thus take the form of a programmed microprocessor or with discrete digital circuits as may appear desirable For purposes of illustration, with the control as shown i Fig. 1, a digital form of the measured ink level signal such as developed either by generator 58, or its digital counterpart, is stored in a memory such as represented by storage network 57. This storage may be a location in a microprocessor memory or a particular output register for subsequent comparison with the reference signals. The stored ink level signal is retained until replaced as a result of a new measurement with an echo signal.When a loss of echo signals is sensed, such as-^UO^ with detector 110, the newly measured ink level will appear as an excessively low ink level and should not be used. Therefore, the output on line 118 is applied to network 57 to prevent replacement of the previously stored digital measured ink level signal, Such effect may, for example,, be obtained by blocking the input to register 57 with suitable logic gates, Hence { when an echo loss occurs r a previously measured ink level signal is used to simulate the current ink levels. This condi- tion persists until an echo signal is again detected.It may be preferred to simulate a digital ink level measurement of a known ink level to avoid maintain¬ ing an ink level signal which demands a feed of ink. In such case the detection of an echo loss on line 118 is used to replace the digital signal in storage network 57 with one representative of a predetermined ink level to avoid ink fountain overflows as may occur when the previ¬ ous ink level measurement sensed a low ink level. Such digital simulated predetermined ink level signal may be generated as soon as an echo loss is detected or may, for example, be obtained from a digital form of the simulated reference source 136 as shown in Fig. 2 such as can be stored in a memory location of a microprocessor.In some cases it may be convenient to employ the signal on the output 126 from timer 124 directly to an in¬ hibit input 144 of clock 70. This would automatically inhibit the feed of ink in case of an extended period over which an echo loss may arise. In such case, care must be taken to avoid a momentary erroneous occurrence of an ink level signal indicating a need for ink feed as•soon as echoes are sensed again.The echo loss detector 110 may be conveniently employed to align the ultrasonic transducer 30 onto ink surface 36. This is done by mounting transducer 30 for pivoting in transverse planes which are also normal to ink surface 36. The transducer' 30 is then pivoted until the echo is lost as observed by detecting a visual ala energized by detector 110. The middle of the pivot range for each plane is then selected as the aligned position o transducer 30.In the embodiment shown in Fig. 1 the described alignment procedure may also be carried out by observing a light source 53, such as an LED, driven by the reset output 55 of flip-flop 54. During normal operations the output 55 will be off most of the time and hence a very dim LED output is obtained as a sensing of the proper operation of the ink level control. When an echo is lost however, the reset output 55 will be continuously on and as a result the LED output significantly brighter. When operational functions of the flip-flop 54 and related seg ments of control 10 are porvided inside a microprocessor alignment of transducer 30 can be carried out by monitor¬ ing alarm 128.Having thus described a printing press ink leve control in accordance with the invention, its advantages can be appreciated. The level of ink can be precisely controlled without direct contact with the ink and while the ink surface is disturbed by an agitator. Variations from the described embodiment may occur to one skilled in the art. For example, the echo loss simulator network ma be in digital form to accommodate a digital ink level sig nal generator. Also, a plurality of ink controls may be used. The scope of the invention, therefore, should be determined by the following claims.^fr. | C L A I M S1. An apparatus for automatically controlling the level of ink in an ink fountain used in a printing press by reg¬ ulating the feed of ink from a supply through a valve to the fountain comprising ultrasonic ink level sensing means remotely spaced from the ink fountain for directing ultrasonic pul¬ ses at the ink fountain to generate an echo signal repre¬ sentative of ultrasonic returns from the surface of the ink; means responsive to the echo signal for gener¬ ating a measured ink level signal indicative of the oper¬ ating level of ink in the ink fountain; means for producing an operating ink level reference signal representative of a desired ink level in the fountain; means for comparing the measured ink level signal with the operating ink level reference signal to generate an ink feed signal when the ink level in the fountain drops below the operating level; means responsive to the ink feed signal for generating ink feed pulses spaced by intervals of a pre¬ determined duration selected commensurate with the time period needed to enable ink supplied during a preceding pulse to register a change in the measured ink level sig- nal and enabling the flow of ink through said valve to the ink fountain during said ink feed pulses; means for detecting when an echo signal fails to be generated in response to an ultrasonic pulse directed at the ink fountain and producing an echo loss signal indicative thereof; and means for registering an echo loss alarm in response to said echo loss signal. 2. The ink level control apparatus as claimed in Clai1 wherein said means for registering the echo loss alarm further includes means for delaying registration of said echo loss alarm until said echo loss signal has persisted for a predetermined time selected commensurate with normal op erating conditions.3. The ink level control apparatus as claimed in Clai2 and further including means for effectively inhibiting said ink fee after said predetermined time while said echo loss signal persists.4. The ink level control apparatus as claimed in Clai 1 and further including means responsive to the echo loss signal for establishing a simulated measured ink level signal indica tive of an acceptable ink level in the fountain while sai echo loss signal is active.5. The ink level control apparatus as claimed in Clai 4 wherein said means for generating the measure ink level signal further includes means producing a volt¬ age whose magnitude is representative of the ink level in the fountain; and wherein said means for establishing said simu lated measured ink level signal further includes means fo clamping said voltage to a magnitude representative of an acceptable ink level in the fountain when said echo loss occurs. BUO ι A £ ?N 6. The ink level control apparatus as claimed in Claim 4 wherein said means for generating the measured ink level signal further includes digital storage means for storing a digital signal representative of the ink level in the fountain as the measured ink level signal; and wherein said means for establishing a simulat¬ ed ink level signal further includes means for retaining a previously generated stored digital signal as represent¬ ative of the ink level in the fountain while an echo loss signal occurs.7. An apparatus for automatically controlling the level of ink in an ink fountain used in a printing press by reg- ulating the feed of ink from a supply through a valve to the fountain comprising ultrasonic ink level sensing means remotely spaced from the ink fountain for directing ultrasonic pul¬ ses at the ink fountain to generate an echo signal repre- sentative of ultrasonic returns from the surface of the ink; means responsive to the echo signal for gener¬ ating a measured ink level signal indicative of the operat¬ ing level of ink in the ink fountain; means for producing an operating ink level reference signal representative of a desired ink level in the fountain; first comparing means for comparing the meas¬ ured ink level signal with the operating ink level refer- ence signal to generate an ink feed signal when the ink level in the fountain drops below the operating level; means responsive to the ink feed signal for generating ink feed pulses spaced by intervals of a pre¬ determined duration selected commensurate with the time period needed to enable ink supplied during a preceding pulse to register a change in the measured ink level sig¬ nal and enabling the flow of ink through said valve ink fountain during said ink feed pulses; means for producing a low ink level referenc signal representative of a minimum acceptable ink level the fountain; second comparing means for comparing the mea ured ink level signal with the low ink level reference signal to generate a low ink level alarm signal when the ink level in the fountain drops below the minimum accept able ink level; and means responsive to the low ink level alarm signal for effectively inhibiting the effect of the ink feed signal to disable further supply of ink and registe an alarm condition representative of said low ink level.8. The ink level control apparatus as claimed in Clai 7 wherein said means for effectively inhibiting the effec of the ink feed signal is coupled to said first comparin means for disablement thereof upon occurrence of ink lev below said minimum acceptable level in the ink fountain.9. The ink level control apparatus as claimed in Clai 7 and further including means for producing a high ink level referenc signal representative of a maximum acceptable ink level i the fountain; third comparing means for comparing the meas- ured ink level signal with the high ink level reference signal to generate a high ink level alarm signal when th ink level in the fountain exceeds the maximum acceptable level for a predetermined time period.10. The ink level control apparatus as claimed in Clai 9 wherein said means for generating the high ink level alarm signal further includes timer means effectively coupled to the outpu of the third comparing means for generating said high ink level alarm signal after said high ink level in the foun- tain has persisted for a predetermined minimum time periofry, 11. An apparatus for automatically controlling the level of ink in an ink fountain used in a printing press by regulating the feed of ink from a supply comprising ultrasonic ink level sensing means remotely spaced from the ink fountain for directing ultrasonic pulses at the ink fountain and generate echo signals rep¬ resentative of ultrasonic reflections from the surface of the ink; means responsive to the echo signals for generating a measured ink level signal indicative of the level of ink in the fountain; means for producing an operating ink level reference signal representative of a desired ink level in the fountain; means for comparing the measured ink level signal with the operating ink level reference signal to generate an ink feed signal when the ink level in the fountain drops below the desired ink level; means for generating high and low ink level reference signals respectively representative of range limits of acceptable ink- levels in the fountain; means for comparing the high and low ink level reference signals to the measured ink level signal and generate respectively high and low ink level alarm signals when the ink level in the fountain is no longer within the acceptable range limits; and means responsive to the ink feed signal for generating ink feed pulses separated by ink leveling inter¬ vals, said intervals being selected of sufficient duration to enable ink supplied during a previous pulse to estab¬ lish a new ink level. 12. The ink level control apparatus as claimed in Clai11 and further including means for detecting a loss of echo signals an generate an acho loss signal indicative thereof; and means actuated by the echo loss signal for pr ducing a simulated ink level signal representative of an ink level within the acceptable range limits.13. The ink level control apparatus as claimed in Clai12 and further including means for generating an alarm signal when said echo loss is active for a predetermined time.14. An apparatus for automatically controlling the lev of ink in an ink fountain used in a printing press by reg ulating the feed of ink from a supply through a valve to the fountain comprising ultrasonic ink level sensing means remotely spaced from the ink fountain for directing ultrasonic pul ses at the ink fountain to generate an echo signal repre¬ sentative of ultrasonic returns from the surface of the i means responsive to the echo signal for gener ating a measured ink level signal averaged over a desired number of echo signals to smooth out effects from varia¬ tions in the measured ink level signal as a result of sur face movements thereof; - means for producing an operating ink level reference signal representative of a desired ink level in the fountain; means for comparing the averaged measured ink level signal with the operating ink level reference signa to generate an ink feed signal when the ink level in the fountain drops below the operating level.•B^ 15. The ink level control apparatus as claimed in Claim 14 and further including means for detecting when an echo signal fails to be generated by the ultrasonic ink level sensing means in response to an ultrasonic pulse directed at the ink fountain and producing an echo loss signal indicative thereof; and means for simulating a measured ink level sig¬ nal in response to the echo loss signal and of a magnitude selected to prevent overflow of ink from the ink fountain.16. In an apparatus for automatically controlling the level of ink in an ink fountain used in a printing press by regulating the feed of ink from a supply through a valve to the fountain, the improvement comprising ultrasonic transducer means remotely spaced from the ink surface and selected to direct ultrasonic pulses at the ink fountain and generate an echo signal representative of ultrasonic returns from the surface of the ink; means for detecting when an echo signal fails to be generated by the ultrasonic transducer means in re¬ sponse to an ultrasonic pulse directed at the ink fountain and producing an echo loss signal indicative thereof; and means for registering an echo loss alarm in response to said echo loss signal to indicate a malfunc¬ tion.17. The improved ink level control as claimed in Claim 16 wherein said registering means further includes means for delaying registration of said echo loss alarm until said echo loss signal has persisted for a predetermined time selected commensurate with normal ink operating conditions. BU AOWPI^SNATIO | BALDWIN GEGENHEIMER CORP | MACPHEE J; RAALTE P VAN |
WO-1979000963-A1 | 1,979,000,963 | WO | A1 | XX | 19,791,115 | 1,979 | 20,090,507 | new | G02C13 | G02C7 | C11D3, C11D7, C12N9, G02C7, G02C13 | C11D 3/00B16, C11D 3/386D | METHODS AND MATERIALS FOR CLEANING SOFT CONTACT LENSES | A cleaning solution for soft contact lenses is described. The solution differs from previously known solutions in that it includes a lipolytic enzyme together with a buffering substance, such as a phosphate. The cleaning solution removes any lipids present on the surface of the lens by splitting them into fatty acids and esters for removal by subsequent rinsing and, optionally, boiling in physiological saline solution. A supplementary cleaning solution comprises, in addition to the lipolytic enzyme, a proteolytic enzyme, such as papain or bromelain, such solution providing for complete removal of all deposits from the surface of the lens. The solution of the invention is preferably hypertonic and it is applied either by using a droplet technique or by introducing the lens fully into the solution. | TITLE OF INVENTION;METHODS AND MATERIALS FOR CLEANING SOFT CONTACT LENSES.TECHNICAL FIELD:The present invention relates to methods and materials for removing from soft contact lenses deposits that are formed during use. Such deposits contain mainly Albumin, Globulins and Lipids.BACKGROUND ART:Deposits that occur during use of soft contact lenses generally result in an opaque film, yellow dis¬ coloration, white spots and thread-like configurations on the lenses. Investigations carried out have shown that these deposits can consist of Albumin, Ig 7-Globulin, Lysozyme and lipoproteins. The deposits are often largely composed of Lipids and denatured Albumin, which aredeposited on the lenses from the tear fluid as a result of the saline solution with which the lenses are impregnated being exchanged' for the tear fluid. The drying-out of a lens, for instance through its use in a dry environment and by air flowing past it, etc. causes some Albumin to be denatured and deposited on the lens. Even when contact lenses are sterilized by boiling, Albumin is denatured which gives rise to • apolar interior groups of Lipids. Other causes too, such as for example continuous use, cause Albumin and Lipids to be deposited on contact lenses in fairly large quantities. One method of cleaning contact lenses is already known which comprises the steps of dissolving in water a proteolytic enzyme in tablet form and then placing the lenses to be cleaned in the solution for a period of at least two hours. This process has been regarded as complicated by the wearers of contact lenses so that cleaning has not always been carried out as regularly as is required and this has resulted in lenses finally acquiring such a coating that the lenses have become unusable. Moreover, the prior art using only proteolytic enzymes does not provide for complete removal of the deposits formed in that deposits of lipid origin remain substantially unaffected by the solutions of the prior art.SUMMARY OF THE INVENTION:An object of the present invention is to provide cleaning solutions and methods for cleaning soft contact lenses which, on the one hand are simple for the contact lens wearer to use and which also provide an improved cleaning effect.It is another object to provide cleaning liquids which prevent a general build-up of proteins and lipids. Yet another object of the present invention is to provide solid compositions of matter to be dissolved in an aqueous vehicle to form soft contact lens cleaning solutions, preferably of a hypertonic character. According to one aspect of the invention an enzyme ■ containing cleaning liquid for soft contact lenses con¬ sists of a solution containing a lipolytic enzyme (mainly for reducing the lipids) and, optionally, a proteolytic enzyme, such as papain or bromelain, (for reducing the Albumin deposits) and, additionally, a buffering agent, such as a phosphate. Such cleaning liquid is preferably hypertonic to its nature, i.e. its osmotic pressure exceeds that of a physiological solution, so that in treatment with the solution some dewatering of the lens takes place, which seems to be beneficial to the cleaning effect. During after-treatment with an isotonic solution, for example a saline solution, the lens reversibly again takes up water to revert to its original state.A pack for cleaning soft contact lenses comprises a volume of a solution containing Papain or Bromelain and a Lipolytic Enzyme, a device for forming droplets of the solution for depositing same on the surface of a soft contact lens and a volume of a sterile isotonic physiological saline solution in which the lens can be rinsed and subsequently boiled.A method of cleaning a soft contact lens in accordance with the invention to remove deposits on the surface of the lens by enzymatic action comprises the steps of placing at least one drop of a solution con¬ taining Papain or Bromelain and in addition a Lipolytic Enzyme, on the contact lens which is to be cleaned to reduce both Albumin and Lipids present to water soluble peptones, fatty acids and esters, and subsequently removing the resulting products by rinsing and boiling in a physiological saline solution.Preferably the enzyme activity in the cleaning solution is of the order of 100 tyrosine units per ug of protein. The fluid activity is allowed to occur for a period of the order of 15 minutes.Preferably the physiological saline solution has a particle size below 0.2 microns, and is isotonic, has a pH-value of 7*0 with a buffer capacity of 6-8 and is also sterile.A preferred enzyme solution for cleaning the lens consists of Bromelain, Mannitol, Sorbitol, Ethylenedia- minetetraacetic acid, Sodium Metabisulphite, and a lipolytic enzyme. A preferred cleaning solution may consist of: Purified fruit bromelain 50-500 g, e.g. about 100 g.Sorbitol 100-1000 g, 11- 500 g.Mannitol 10-100 g, 50 g.Sodium hydrogen sulphite 8-12 g, 10 g.Ethylenediaminetetraacetic acid disodium salt 0.8-1.2 g, 1 g. Potassium sorbate 10-1000 mg, ft 100 mg. diluted to 1 litre aqua dest., together with Lipase from cand. cylindracae, preferably in an amount corresponding to about 50000 units, in 1000 ml. 0.1 M Phosphate buffer in an aqueous polymer complex.An alternative cleaning solution (which comprises another aspect of the invention) which may be used to clean a soft contact lens consists of a solution of Lipase and a phosphate buffer.When a proteolytic enzyme and a lipolytic enzyme are used In combination it is preferred in order to avoid undue interaction between the enzymes to include in the solution a so-called aqueous polymer complex , which is conventional in the art and have for a purpose to bind the lipolytic enzymes so that it will not be unduly destroyed by the proteolytic enzyme. The nature of this polymer complex is not critical and any commercial product may be used, such as polyethylene glycol , polyvinyl alcohol, polyvinyl pyrrolidone and the like. As a fully non-limiting example one may mention the polymer complex K-ollodorf 25 or 30 from BASF, West Germany.In order to obtain a fully understanding of the invention, its background and its underlying problems, some further explanation will be given below.The polymers used in the manufacturing of soft contact lenses at the present time, PMMA, HEMA and PvP all have a common factor, that is, they are lipid and protein retensive. New materials have been introduced 0MP1 such as silicone, even in this material there is lipid retention. At the present time it does not seem possible to present a material for the manufacturing of soft contact lenses that does not present this problem. This problem of fatty deposits from tear fluids has been demonstrated in numerous investigations. The insi¬ dious, relentless accumulation of fatty deposits on and in the matrix of the lens material can appear after a short period of time, it seems that the amount of lipids in tear fluid varies from one person to the next.The lipid deposits appear either as yellowish tinting of the lens or as a whitish haze.Chemically the deposits are composed of phospho- lipids, probably in the form of lecitin, forming together with the protein a lecitoprotein, (lecitin on exposure to heat and light tends to autooxidise or decompose into yellowish substances) or cholesterol and fat esters which are white in colour. Plaques or what one might call lesions also appear on the lenses after a period of time. Typically the -plaque consists of a central core of lipid lying free on the polymer and protruding into the material matric causing a sand grain sensation when the lens lies in the eye.Unfortunately, we have only theories to explain how fatty substances in the tear fluid are transformed into obstructive plaques. However, these plaques start from the same observation - an excess of lipids - and in particular cholesterol and lecitin.Based on these observations it is therefore quite apparent that a method for cleaning soft contact lenses presently and in the future must be one that can remove the lipid and protein deposits formed in the soft contact lens material during wearing.OMPI Due to the fact that new materials are being investigated it is necessary that the cleaning method must be compatible with these materials. An enzymatic method whereby a lipase is used is without doubt the most gentle method and probably the most efficient for removing fatty deposits from soft contact lenses..It is also evident that the greater the water content of the polymer the greater the binding of protein and lipids, this binding tends to be normally a surface adsorption but in those polymers that are combined with copolymers of certain types there is a possibility that a covalent binding can occur.This type of binding is naturally more difficult to separate than an ordinary surface adsorption. It is, however, possible with the use of lipase in combination with a tenside; the tenside in this case increases the water/oil interphase and allows the enzyme to react upon the lipids.With regard to the enzymes used in the liquid or solution according to the invention any lypolitic enzyme hydrolyzing the lipids to yield fatty acids and -glycerol are useful. A preferred variety is lipase derived from cand. cylindracae, suitably prepared by lyophilization. As a proteolytic enzyme any protein-di- gesting enzyme is useful, preferred examples being bromelain and papain. When usingin combination both alipolytic enzyme and a proteolytic enzyme, the latter being papain, it will be noted that the beneficial effect of free sulfhydryl groups on the activity of papain will be satisfied by the presence of the lipase containing sulfhydryl groups. Thus, such combination of enzymes is particularly preferred, especially when used in solutions of a hypertonic character. EXAMPLES:The invention will now be further described by non-limiting examples.Example I. A soft contact lens cleaning fluid (known as PROLEN) is made up as follows:-Purified fruit bromelain 100 gSorbitol 500 gMannitol 50 g 0 Sodium hydrogen sulphite 10 g Ethylenediaminetetraacetic acid disodium salt 1 gPotassium sorbate 100 mg Dilute to 1 litre aqua dest.Then add:-15 Lipase from cand. cylindracae 50000 units in 1000 ml. 0.1 M Phosphate buffer in an aqueous polymer complex.Example II.A second soft contact lens cleaning fluid (known as LIPREN) is made up as follows:- 20 Lipase derived from cand. cylindracae, lyophilised 100 units. - 0.1 M. phosphate buffer 10 ml.Methods of use PROLENA few drops (0.3 ml) of the fluid are placed on a 25 lens and left on the lens for 15 minutes. The lens is then rinsed in a saline solution and thereafter boiled in the saline solution for 20 minutes. Finally the lens is rinsed once more in the saline solution before rein¬ serting.30. LIPREN(a) For regular periodic cleaning.A freeze dried lipase is reconstituted with a phosphate buffer (0.1 ___)• The lenses are placed in this solution and allowed to remain in the solution for35 30 minutes.OKPI■■ fe After this time the lenses are removed and rinsed in a saline solution and then boiled in the saline solution for 20 minutes. After boiling the lenses they are once again rinsed in saline solution before rein- serting.(b) For lenses that have not previously been treated with Lipren and have visual deposits or are dis¬ coloured.A freeze dried Lipase is reconstituted with a phosphate buffer (0.1 M). The lenses are placed in the fluid and allowed to remain in the fluid for 8-10 hours. The lenses are removed and rinsed in dest. water. The lenses are then heated in a saline solution to θ°C for 30 minutes. The lenses are then rinsed in dest.water and boiled in saline solution for 30 minutes.Finally the lenses are rinsed in saline solution before reinserting.The cleaning of soft contact lenses using cleaning liquids of the invention.After use a lens is usually coated with deposits of protein, lipoproteins and lipids. In accordance with one aspect of the invention the lens is treated with a preparation having a high enzymatic effect which contains a stabilised protease and a high activity lipase. Drops of the preparation are placed on the lens in accordance with the invention and it is left for the preparation to take effect, for 15 minutes.This cleaning preparation is, as described above, preferably formed from Bromelain, Mannitol, Sorbitol, Ethylenedia inetetraacetic acid, Sodium Metabisulphate and lipolytic enzyme.Complete removal of lipids from the lens is achieved by using a stabilised enzyme in fluid form and this may be applied either separately or as a second step. This is typically dripped onto the contact lens so as to remove any lipid deposits.The stabilised enzyme in fluid form is, as described above, preferably a lipase with a phosphate buffer. A further step in the cleaning operation involves rinsing the contact lens in a physiological saline solution and then boiling the lens in the same or a similar solution.The saline solution should be particle-free (i.e. have a particle size below 0.2 micron), should be isotonic, should have a pH-value of 7*0 and a buffer capacity of β-8 and should also be sterile. The pH-value which is indicated is that value which will avoid smarting when the lens is subsequently inserted. An incorrect pH-value will cause smarting to occur. An incorrect pH-value will also cause the protein in the tear fluid to become denatured spontaneously which is not, of course, desirable.In order to fulfil the conditions imposed as to purity and sterility, the solution is preferably packed in a disposable pack and is sterilised by means of Gamma radiation.Report of experiments to determine effectiveness of invention. With a view to determining the cleansing effect of the solutions and methods proposed by the invention, investigations were carried out as follows. For protein determination, the method according to Lowry as modified by Wedler was used. For determining the lipid quantity present, the method according to Boyer et al was used.Analysis of tear fluid according to several different sources shows that the fluid consists of Lysozyme, Ig 7-globulin, 1-lipoprotein, small amounts of carbohydrates and phospholipids. A similar solution was therefore prepared from the following:- 7-chymo- trypsin, serum albumin, lysozyme, bovine mucin, globulin II, β-globulin III, globulin and β-lipoprotein in 0.9 NaCl solution. Lenses were placed in this prepared solution and left over night. Control lenses were kept in a sterile saline solution instead of the prepared solution. At the end of the period of storage the lenses were divided into four groups:-Group 1. The lenses in this first group were rinsed and then boiled in a sterile saline solution.Group 2. The lenses in the second group were rinsed in a cleaning solution and then stored in a saline solution containing preservatives.Group 3- The lenses in Group 3 were treated with an enzyme solution and subsequently rinsed and boiled.Group 4. The lenses from the saline solution were treated in the same way.After treatment the protein and lipid content of each of the four groups was found to be as follows:- Group 1 - Protein content 3-8 Ug per lens. Total lipid content100-250 pg per lens. Group 2 - Protein content 1-4 pg per lens. Lipid content 60-120 pg per lens.Group 3 - Protein content 0-0.5 pg per lens. Lipid content0-30 pg per lens. Group 4 - Protein content 0.02 pg per lens. Lipid content0 ug per lens. The invention allows soft contact lenses to be cleaned rapidly and effectively and in general the cleaning operation should be carried out daily. However, where lenses are worn day and night, the intervalOMPI. between cleanings may be extended to every other or even every third day.The invention therefore provides for a simpler cleaning process than the known technique which requires the dissolving of tablets in water and also provides for a shorter cleaning period than hitherto. What is more important, however, is that the invention allows a more complete cleaning of the contact lens on account of the higher enzymatic activity. Unlike previously known cleaning preparations, the method according to the present invention is also designed to be used daily on the one hand for cleaning the lenses and on the other hand as a preventative measure to present the build-up of larger deposits of protein and lipids which after a time are difficult to remove and affect the properties of the lens.The types of enzymes which can be utilised may be Papain or Bromelain in each case together with a lipolytic enzyme. Cysteine and Polysaccharides may be used as substrate materials.Enzymatic activity should be of the order of 100 tyrosine units per pg of protein (substrate). By splitting the albumin into water-soluble peptones by enzymatic action, the latter can be rinsed or boiled away using a physiological saline isotonic solution.The invention provides a stable liquid cleaning agent for cleaning soft contact lenses which can be stored under normal environmental conditions without loss of enzymatic activity thereby obviating the need to dissolve a tablet or quantity of powder in water so as to produce the cleaning solution for the lens. In this way just sufficient quantity of the cleaning liquid need be used to cover the surface of the lens and it is with this in mind that the invention provides for the application of the cleaning liquid by means of droplet applicator or the like.Typically the PROLEN solution described above is used as a regular daily cleaning agent. This will remove most of the deposits normally found on the lens but will not completely remove the Lipid deposits. The steady build-up of Lipids is conveniently removed by periodically (e.g. monthly) cleaning the lens in LIPREN as described above. The Lipase in a phosphate buffer forming the LIPREN effectively removes the Lipid build-up. | CLAIMS :1. An enzyme containing liquid for cleaning soft contact lenses, characterized by consisting of a solution containing a lipolytic enzyme and a phosphate buffer.2. A liquid according to claim 1, characterized in that the Lipase is derived from cand. cylindracae, lyophilised.3. A liquid according to claim 2, characterized in that there are 100 units of the Lipase in 10 ml of 0.1M phosphate buffer.4. A liquid according to any of the preceding claims, characterized by containing additionally a proteolytic enzyme.5. A liquid according to claim 4, characterized in that the proteolytic enzyme is Papain or Bromelain.6. A liquid according to claim \z>, characterized by consisting ofPurified fruit bromelain 50-500 g, e.g. about 100 g.Sorbitol 100-1000 g, 500 g.- Mannitol 10-100 g, 50 g.Sodium hydrogen sulphite _ 8-12 g, 10 g.Ethylenediaminetetraacetic acid disodium salt 0.8-1.2 g, 1 g.Potassium sorbate 10-1000 mg, e.g. lOOmg. diluted to 1 litre aqua dest., together with Lipase from cand. cylindracae, preferably in an amount corre¬ sponding to about 50000 units, in 1000 ml. 0.1 M Phosphate buffer in an aqueous polymer complex.7. A liquid according to any of the preceding claims, characterized in that it is hypertonic.8. A method of cleaning a soft contact lens by removing deposits from the surface of the lens by enzymatic action, characterized by the steps ofOMP1 a) placing at least one drop of a solution containing a lipolytic enzyme and in addition, optionally, a proteolytic enzyme, such as Papain or Bromelain, on the surface of the lens which is to be cleaned, to reduce both the Albumin and Lipids present on the surface to water soluble peptones, and fatty acids and esters and b) subsequently removing the resulting products by rinsing and boiling the lens in a physiological saline solution.9. A method as claimed in claim 8, characterized in that the enzymatic activity of the said solution is of the order of 100 tyrosine units per pg of protein.10. A method as claimed in claim 8 or 9, characterized in that the said at least one drop of solution containing a lipolytic enzyme and, optionally a proteolytic enzyme is left on the surface of the lens to be cleaned for a period of about 15 minutes.11. A method as claimed in any one of claims 8 to 10, characterized in that the physiological saline solution has a particle size below about 0.2 micron, is isotonic, has a pH-value of about 7«0 and a buffer capacity of 6-8 and is also sterile.12. A method as claimed in any one of claims 8 to 11, characterized in that the enzyme solution which is applied to the lens consists of Bromelain, Mannitol, Sorbitol, Ethylenediaminetetraacetic acid, SodiumMetabisulphite and a Lipase.13. A method as claimed in any of claims 8 to 11, characterized in that the enzyme solution consists of: Purified fruit bromelain 50-500 g, e.g. about 100 g.Sorbitol 100-1000 g, 500 g.Mannitol 10-100 g, 50 g.Sodium hydrogen sulphite 8-12 g, . 10 g.Ethylenediaminetetraacetic acid disodium salt 0.8-1.2 g, 1 g.Potassium sorbate 10-1000 mg, 11 100 mg. diluted to 1 litre aqua dest., together with Lipase from cand. cylindracae, preferably in an amount corre¬ sponding to about 50000 units, in 1000 ml. 0.1 M Phosphate buffer in an aqueous polymer complex.14. A method of cleaning a soft contact lens, characterized by comprising the steps of placing the lens in contact with a solution as claimed in any of claims 1-6 for a first specified period of time, rinsing it in a saline solution, removing it and boiling it for a second specified period of time in a saline solution and thereafter rinsing it again in a saline solution.15. A method as claimed in claim 14, charact¬ erized in that the first specified period of time is 30 minutes and the second specified period of time is 20 minutes.16. A method of cleaning a soft contact lens, characterized by comprising the steps of placing the lens in contact with a solution as claimed in any of claims 1-6 for a specified period of time, removing it from the solution and rinsing it in dest. water, heating it in a saline solution to a given temperature for a second specified period of time, subsequently rinsing it in dest. water and thereafter boiling it in saline solution for a third specified period of time and rinsing it in saline solution.17. A method as claimed in claim 16, charact¬ erized in that the first specified period of time is 8 to 10 hours, the second specified period of time is 30 minutes, the given temperature is 4θ°C and the third specified period of time is also 30 minutes. l8. Dry composition of matter, characterized by comprising a lipolytic enzyme, buffer and additional substances so as to form, when dissolved in water, a hypertonic soft contact lens cleaning liquid.19* Composition according to claim 18, charact¬ erized by further comprising a proteolytic enzyme.20. Composition according to claim 19^ charact¬ erized by comprising Bromelain, Mannitol, Sorbitol, Ethylenediaminetetraacetic acid, Sodium Metabisulphite and a Lipase.21. Composition according to any of claims l8-20, characterized by comprising as a buffer a phosphate buffer.TB/On | BEDDING P | BEDDING P |
WO-1979000979-A1 | 1,979,000,979 | WO | A1 | XX | 19,791,129 | 1,979 | 20,090,507 | new | F02B3 | F02M39 | F02B1, F02D35, F02D41, F02P5 | F02D 41/06, F02D 41/06D, F02D 41/06D2, F02D 41/18, F02P 5/155D, R02B 1/04 | ELECTRONIC ENGINE CONTROL | An electronic controller (2) for an internal combustion engine (22) provides a ratio control signal corresponding to a respective air/fuel ratio, and responds to an air flow signal, a fuel flow signal and the ratio control signal to control fuel flow as to make the ratio of air flow to fuel flow substantially equal to said respective air/fuel ratio. The ratio control signal is developed from a base run ratio control signal as modified in response to various parameters such as engine temperature, manifold pressure, idle, manifold vacuum, fuel temperature, wide open throttle, engine speed, and start. The controller (2) also provides a speed-up circuit (5) for promptly responding to change in air flow and dynamic braking for the fuel metering pump (52). The pump speed circuit (7) includes a range extender (164). The controller (2) further provides a timing advance control signal in response to air/fuel ratio and various engine parameters such as engine speed, manifold pressure, throttle position, engine temperature, air temperature, air/fuel ratio, and start. | ELE CTRONIC ENGINE CONTROLThis invention relates to engine controls and more particularly to the control of fuel flow and igni¬ tion timing in connection with a spark ignited internal combustion engine. Still more specifically, this inven- tion relates to the control of fuel flow and spark advance in response to a number of sensed engine conditions.It is well known to control fuel flow in an internal combustion engine, especially to maintain an appropriate air/fuel ratio, as is disclosed in Priegel United States Patent No. 3,817,225 issued June 18, 1974, for Electronic Carburetion System for Low Exhaust Emissions of Internal Combustion Engines. Priegel dis¬ closes a system wherein the rate of air flow and certain other parameters are measured and used to control the drive of a positive displacement metering pump to supply fuel at an appropriate air/fuel ratio.In such systems it is known to use an air flow transducer like that disclosed in Chapin United States Patent No. 4,089,215 issued May 16, 1978, for Air Flow Transducer. The air flow as detected by such transducer is used in connection with an electronic control system for controlling the flow of fuel to maintain an appropriate air/fuel ratio. In connection with such control it is known to utilize a fuel supply system as disclosed in Chapin and Merrick United States Patent No. 4,112,901 issued September 12, 1978, for Fuel System with Metering . Pump for Internal Combustion Engines. It is also known to utilize such fuel supply systems to supply fuel to carburetor like .that shown in Chapin United States Pat No. 4,087,491 issued May 2, 1978, for Carburetor with Hollow Air Control Valve.** The present invention is d ected to an improved electronic controller, particular one that may be used with the air flow transducer of United States Patent No. 4,089,215 for controlling a fuel supply system like that disclosed in United State Patent No. 4,112,901. The controller of the present invention is r ponsive not only to rate of air flow and rate of fuel flow, but also to barometric pressure, manifold pressu air temperature, throttle position, fuel temperature, engine temperature, the use of accessories, start cond tion, and engine position (and hence, indirectly, engi speed) for supplying fuel at an appropriate rate. It well known to utilize microprocessors or computers res ponsive to various engine conditions to provide fuel control. One such system is shown in Moyer et al. Uni States Patent No. 3,969,614, issued July 13, 1976, for Method and Apparatus for Engine Control. The present invention also utilizes the elect controller for controlling ignition timing. Conventional centrifugal means dependent upon engine speed and mean responsive to manifold vacuum have been used to advanc the spark. Comparable spark advance has been achieved electronically. One such electronic controller is dis closed in the aforesaid Moyer et al. Patent No. 3,969, Another timing control is shown in Crall et al. United States Patent No. 3,978,833 issued September 7, 1976, Engine Control Circuit for Providing a Programmed Con Function. Like the present invention, certain of the c trollers of the prior art have been used to provide wh might be called the best performance. However, what-BUO best depends upon a number of competing factors, such as economy, ecology and drivability, the latter two being particularly subjective. In any event, in accordance with the present invention fuel flow and ignition timing are controlled in a manner to provide different relation¬ ships to the engine conditions than have been found in the controls of the prior art.Thus, a primary aspect of the present invention is to provide an improved electronic control of fuel flow and ignition timing as to optimize fuel economy, exhaust emission, drivability, and more particularly the relation¬ ships among the three. More specific aspects and advantages of the present invention will become apparent from considera¬ tion of the following- detailed description, particularly when taken in connection with the appended drawings in which: FIGURE 1 is a diagrammatic illustration of a con¬ trolled air/fuel system and ignition timing system for an internal combustion engine utilizing the controller of the present invention; FIGURE 2 is a diagrammatic illustration of a pre¬ ferred form of the controller 2 of the present invention showing the relationships among the respective control circuits;FIGURE 3 is a schematic diagram of the pressure signal circuits 3 of the controller 2;FIGURE 4 is a schematic diagram of a mass flow converter 4 for combining the air flow signal, the baro¬ metric pressure signal and the air temperature signal to provide a measure of mass flow in the controller 2; FIGURE 5 is a schematic diagram of a speed-up circuit 5 for correcting the mass flow signal from the mass flow converter 4 for inertia lag;FIGURE 6 is a'schematic diagram of an accelerator pump circuit 6 for providing additional fuel flow upon acceleration in the controller 2; -4-FIGURE 7 is a schematic diagram of pump drive circuitry 7 of the controller 2 for driving a metering providing fuel for the engine in response to a signal d pendent upon air flow; FIGURES 8 and 9 are schematic diagrams of respecti parts I and II of ratio control circuitry 8 and 9 for p viding a ratio control signal for determining the air/f ratio to be maintained by the pump driver circuitry 7;FIGURE 10 is a schematic diagram of throttle by control circuitry 10 in the controller 2;FIGURE 11 is a schematic diagram of the ignit timing control circuitry 11 in the controller 2;FIGURES 12 and 13 are schematic diagrams of respective parts I and II of timing advance circuitry 12 and 13 for providing a timing advance control signal the timing control circuit 11; andFIGURE 14 is a graphical illustration of the respective timing advance control characteristics provi by the timing advance circuitry 12 and 13. The present invention is useful in internal c bustion engines having air/fuel control systems wherein fuel is supplied in metered amounts providing a particu desired ratio of air to fuel for engine operation. In systems, air flow to the intake manifold of the engine controlled and measured, and air flow rate, usually in c junction with other parameters, is used to develop a co trol signal used for providing fuel at the desired aix/f ratio. In FIGURE 1 there is illustrated very generally a control system for supplying an appropriate mixture o air and fuel to the intake manifold 20 of an internal c bustion engine 22 and for supplying ignition sparks at appropriate times to the respective combustion chambers the engine 22. The engine 22 may be a multi-cylinder s ignited reciprocating engine, specifically one burning gasoline. The engine 22 may have a conventional igniti system 24 which includes the usual spark coil, spark plugs, distributor and associated components.The system of FIGURE 1 includes a carburetor 30 which, as shown, is preferably conical. As a principal function of the carburetor 30 is to control the rate of flow of air to an intake manifold of an engine, the conical carburetor 30 is sometimes referred to as a conical throttle. The opening of the conical throttle 30 is controlled by a throttle rod 32 which may be connected, for example, to a conventional automobile accelerator pedal. The throttle rod 32 may be connected through a crank 34, a shaft 35 and gears 36 to control the throttle opening and hence the rate of flow of air into the intake manifold 20. As this is the principal air flow and as the throttle 30 is the throttle by which the operator controls engine speed, the throttle 30 may also be referred to as the main throttle. The throttle 30 is enclosed in a hous¬ ing 38 which fits over the intake manifold 20 of the internal combustion engine 22. The throttle control linkage passes through the housing 38 at the shaft 35. The conical throttle 30 and its manner of operation may be as described in the aforesaid United States Patent No. 4,087,491.All air flowing into the intake manifold flows through the housing 38, flowing into .the.housing through a filter 42 and an air flow transducer 44. The air- flow transducer 44 measures the rate of air flow into, and hence out of, the housing 38 by producing a systematically related electrical signal AIR FLOW on a conductor 46 which goes to the controller 2. More particularly, the air flow transducer 44 and its manner of operation may be as des¬ cribed in the aforesaid United States Patent No.4,089,215. Such transducer comprises a rotor driven by the entering air to produce a signal AIR FLOW formed as pulses occur- ring at a rate indicative of volumetric rate of air flow. The controller 2 receives other signals from other sensors as described below and utilizes the various signals to provide appropriate fuel pump power PUMP on a conductor 50 to a metering pump 52. The metering pump 52 is supplied with fuel throu a conduit 53 by a supply pump 54 from a fuel tank 56, wit any excess fuel being returned to the fuel tank 56 through a return conduit 58. A pressure regulator valve 59 main¬ tains a predetermined reference pressure at the intake o the metering pump 52. The metering pump 52 supplies fuel to the carburetor 30 through a conduit 60 and an equaliz valve 62. A feedback signal PUMP TACH indicative of pum speed is developed by a pump tachometer 64 coupled to the metering pump 52 to move therewith. The PUMP TACH signal is a series of periodic pulses occurring at a rate propo tional to pump speed. The metering pump 42 is a positive displacement pump so that the PUMP TACH signal is indicativ of rate of fuel flow. The PUMP TACH signal is fed back ove a conductor 65 to the controller 2 which utilizes the feed back signal to assure that the metering pump 52 operate at the desired speed. Reference pressure is applied to the equalizer valve 62 through a conduit 66. Such fuel suppl system and its manner of operation may be as described i the aforesaid United States Patent No. 4,112,901. Also illustrated generally in FIGURE 1 is a bypa throttle 68 which operates as an auxiliary air control fo admitting a controlled additional amount of air into the intake manifold 20, as may be called for by a signal B.P. SOL developed in the controller 2 and applied to the bypass throttle 68 over a conductor 70, as described in greater detail in Chapin and Merrick Patent No. 4,108,127, issued August 22, 1978, for Modulated Throttle Bypass. Reference will now be made to the other sensors illustrated in FIGURE 1. A barometric pressure transducer 72 is disposed within the housing 38 and measures the ambient air pressure by producing an output signal BARO PRESS indicative of barometric pressure transmitted to the controller 2 over a conductor 74.An air temperature sensor 76 is also disposed within the housing 38 to measure ambient air temperature. Such sensor may provide an output signal Rt in the form of a resistance magnitude dependent upon temperature. The out¬ put signal is coupled to the controller 48 over a conductor 78. Fuel temperature is sensed by a fuel temperature sensor 80 disposed within the metering pump 52. The fuel temperature sensor may comprise a temperature sensitive diode which produces a fuel temperature signal FTC on a conductor 82 connected to the controller 2. A throttle, position sensor 84 is coupled to the shaft35 and produces a throttle position signal TFV on a conductor 86 extending to the controller 2. The throttle position sensor may comprise a transformer with a movable core and a split secondary winding. The core is moved by the shaft 35 to produce an imbalance in the secondary winding. The imbalance is then detected by a conventional circuit which produces an analog signal TPV indicative of throttle position.A wide open throttle sensor 88 is also coupled to the shaft 35. The wide open throttle sensor may be in the form of a limit switch which is closed when the throttle is moved to its extreme wide open condition. The closing of the switch applies a signal WOT to a conductor 90 connected to the controller 2. For the controller 2 described below, the signal WOT indicative of wide open throttle is a ground condition, the conductor 90 being otherwise at a positive potential.An engine temperature sensor 92 may comprise a temperature sensitive diode disposed in the engine coolant. This transducer produces an engine temperature signal ETS on a conductor 93 connected to the controller 2.Manifold pressure is sensed by a manifold pressur sensor 94 coupled to the manifold 20. The manifold pres sure sensor 94 may operate in the fashion of the barometri pressure sensor 72 to provide a manifold pressure signal MANIF PRESS on a conductor 95 connected to the controlle 2.An accessories sensor 96 may be used to indica whether or not certain accessories are being used as may load the engine, most notably an air conditioner. The detector may comprise a connection to the switch turning the air conditioner on and thus apply an appropriate sign ACC to a conductor 98 connected to the controller 2.Similarly, a start condition may be sensed by start sensor 100 which may comprise a connection to the switch starting the starting motor and thus develop a signal 12V ST on a conductor 102 connected to the contro ler 2.In order to determine the speed and position o the engine, a run pickup 104 is coupled to the distribut of the ignition system 24. The run pickup 104 may com¬ prise an electromagnetic pickup sensing the interruption of a magnetic field at a particular time in the distribu tor cycle, such as for example, 60° before top dead cent for each cylinder. An output signal RUN pickup in the form of periodic pulses is applied over a conductor 106 the controller 2 where it may be used to develop a signa indicative of engine speed. The signal may also be used in timing. Similarly, a start pickup 108 may be used to develop a signal START PICKUP useful in providing timing during a starting condition. Such signal may, for examp produce a pulse at 10° before top dead center over a con ductor 110 connected to the controller 2.To complete the description of the system illu trated in FIGURE 1, the controller 2 produces a timing signal IGNITION PULSE in response to the sensed conditions and applies this, signal over a conductor 112 to the ignition system 24.It should be noted that each of the conductors referred to that are shown as single lines in FIGURE 1 may in fact comprise a pair or more of conductors to provide the necessary paths for completion of the respective signal circuits. The completion of the conductors to the control¬ ler 2 are not all shown in order to avoid the confusion of multiple lines. In point of fact, each of the arrowheads extending from the respective sensors indicates the con¬ nection of the respective conductor to the controller 2. Similarly, in the remaining figures the respective conductors are shown at the input to the controller 2. Where the same signal is applied to different parts of the controller, the same number will be used to identify collectively the conductors over which the signal is applied.FIGURE 2 is a diagrammatic illustration of the entire controller 2 showing the connections from the res- pective sensors and showing the interconnections between the various component circuits illustrated in FIGURES 3 through 14.In FIGURE 3 are illustrated the pressure circuits 3. These circuits include a barometric pressure circuit 114 which receives the barometric pressure signal BARO PRESS from the barometric pressure transducer .72 over the conductor 74 and produces on a conductor 116 an analog signal BTV systematically related to barometric pressure. The barometric pressure circuit 114 is essentially an amplifier with an output circuit to provide a signal of appropriate magnitude at an appropriate impedance level. Similarly, a manifold pressure circuit 118 receives the manifold pressure signal MANIF PRESS from the transducer 94 over a conductor 95 and produces a systematically re- lated manifold pressure signal MPV, an analog signal corresponding to the manifold pressure. The signal MPV applied to a conductor 12Q. The pressure circuits 3 al include a manifold vacuum circuit 122 which is essentia a subtraction circuit providing a manifold vacuum signa MVV on a conductor 124 that is the difference between t barometric pressure signal BPV and the manifold pressur signal MPV. The signal MW is therefore indicative of magnitude of the vacuum in the manifold, that is, the n gative pressure below barometric that exists in the int manifold 20.The mass flow converter 4, as shown in FIGURE combines the barometric pressure signal BPV with the ai temperature signal Rt to produce a signal ADV indicativ of air density and utilizes this signal to modify the a flow signal AIR FLOW, which is indicative of volumetric rate of flow of air, to produce a signal MFV indicative of mass rate of flow of air.As shown in FIGURE 4, the mass flow converter includes a multiplier circuit 126 to which the barometr pressure signal BPV is applied on the conductor 116 and the air temperature signal Rt is applied over the conduct 78, or in this instance, more properly between conductor 78, one of which is grounded. The signal BPV is applie to the + terminal of an amplifier N4-5, 6, 7 through a resistor R39. Resistors R39 and R34 form a voltage divi placing the signal at the + terminal in the appropriate scale range. The output of the amplifier N4-5, 6, 7 at pin 7 is applied through a transistor Q6 to an output c ductor 128. A resistor R36 and the resistance Rt represent air temperature form a voltage divider providing the input to the - terminal of the amplifier N4-5, 6, 7 through a resistor R35. The air temperature sensor 76 a negative temperature coefficient of resistance, where BU -li¬the resistance of the air temperature signal Rt increases as temperature goes down. This, thus, introduces a multiplying factor into the amplifier N4-5, 6, 7, causing the output on the conductor 128 to go up as temperature goes down. This, of course, is the relationship between air density and temperature, and the output signal ADV on the conductor 128 is thus representative of air density provided the various circuit elements are of the appropriate magnitude. More particularly, the resistance of the re- sistor R36 is selected relative to the resistance of Rt, the resistance of the air temperature sensor 76, to make the response approximately linear over the desired range. For example, the resistance of the resistor R26 may bemade equal to the resistance of the signal Rt at 25°C. As shown in FIGURE 4, the mass flow converter 4 includes a signal conditioning circuit 130 which receives the air flow signal AIR FLOW on the conductor 46. The air flow signal AIR FLOW is typically in the form of periodic pulses having positive and negative components occasioned by the building up and collapsing of the magnetic field in the air flow detector. The signal conditioning circuit 130 operates to convert the input signals into a series of corresponding pulses of uniform magnitude and duration. More particularly, transistors Ql and Q2 cause a signal to be developed across a resistor R4 that corresponds to the • air flow signal AIR FLOW. The AC component of this signal is applied through a capacitor C5 and a resistor R5 to a Schmitt trigger circuit that produces corresponding square wave pulses at Nl-7. These square wave pulses are applied to pin 3 of a one-shot multivibrator N2. At the same time the pulses are inverted by an inverter Nl-1, 2, 3 and applied to the same pin 3. This amounts to doubling the number of triggering pulses applied to the multivibrator N2. The multivibrator N2 thus produces output pulses of uniform duration and magnitude at pin 12 which pulses are at twice the frequency of the input pulses at the • conductor 46. These pulses are thus at a frequency corresponding to volumetric rate of air flow.The multivibrator output pulses are applied over a conductor 136 to a multiplying circuit 138. These pulse act to turn on a transistor Q3 and turn off a transistor Q4 for the duration of each pulse. Thus, during each puls the air density signal ADV is applied through the transisto *Q3 to charge a capacitor C2 through a resistor R23. When the pulse is off, the transistor Q3 is non-conductive, an the transistor Q4 conducts, permitting the capacitor C12 to discharge through the resistor R23. The resistor R23 and capacitor C12 thus act as an integrating circuit, the average voltage developed on the capacitor C12 being pro- portional to the magnitude of the air density signal ADV times the proportion of time that the capacitor is charge by virtue of the pulses from the.multivibrator N2. That is, the integrated value is the product of pulse width, 'pulse height and pulse rate, pulse width being the duration of the multivibrator pulse (a constant) , pulse height being pro¬ portional to the air density, and pulse rate being proportional to the rate of occurrence of the multivibrator pulses which is'in turn proportional to volumetric rate of air flow.. Thus, the signal developed on the capacitor C12 is proportional to the product of air density and the volumetric rate of air flow. As. density times volume is mass, the integrated signal is thus proportional to mass rate of flow. The integrated signal is applied to an amplifier 142 wherein a potentiometer Al adjusts the factor of proportionality. The amplifier output is applied through a filter 144 to develop on a conductor 146 a corresponding signal MFV corresponding to the mass rate of flow of air.The signal MFV indicative, of mass, rate of flow i§ applied to the speed-up circuit 5 which acts to overcomeO PI the sluggishness of the air flow transducer 44.- In this case, the speed-up circuit 5 essentially takes the deriv¬ ative of the applied signal MFV and after a gain adjustment effected by a potentiometer A4, the derivative is added to the signal MFV at a terminal N3-10. The combined signal is then amplified arid appears at the terminal N3-8 as a signal AFV which represents a compensated mass rate of air flow signal more accurately representative of the true mass rate of flow. That is, the mass rate of air flow as measured is necessarily a delayed measurement because the inertia of the measuring instrument precludes its instantaneous response to the changes in rate of air flow through the transducer and coupling of the transducer to the air flow is imperfect. The speed-up circuit 5 notes a change in rate of flow by noting the magnitude of the derivative or rate of change of the mass flow signal MFV. When there is a relatively fast rate of change, this indicates that there will be substantially further future change, until the transducer reaches its stable condition , truly indicative of rate of air flow. Thus, by adding a signal related to the rate of change either positively or negatively, the combined air flow signal AFV is more re¬ presentative of the stable condition and hence more representative of the true rate of air flow. In the circuit illustrated, the mass flow signalMFV is applied across a voltage divider formed by resistors R42 and R43. The portion of the signal appearing across the resistor R43 is applied to an amplifier N3-5, 6, 7 to con¬ trol a transistor Q13 to provide current flow through the transistor Q13 as to maintain the voltage drop across a resistor R44 equal to that across the resistor R43. This current flows through a diode string D10-D11-D12-D13. This causes a potential drop across the diode string that varies with current flow, but non-linearly as diode impedance varies inversely with current. For this reason changes in the mass flow signal MFV make smaller changes in the voltage drop across the diode string when the mass flow signal is highe The change in signal across the diode string is applied through a capacitor C21 and amplified by an aπplifier N3-12 13, 14 to produce a signal at the terminal N3-14 proportion to the change in potential across the diode string. A potentiometer A4 and a resistor R53 are connected in seri from the terminal N3-14 and the 6-volt power supply. Th 6 volt supply permits positive and negative swings to th differential signal. The setting of the potentiometer A determines the gain of the amplifier 'N3-12, 13, 14. The differential signal at the terminal N3-14 is applied through a resistor R52 to add to the mass flow signal MFV. The summed signals are applied through an amplifier N3-8, 9, 10 to produce compensated air flow signal AFV on a con¬ ductor.148. The 6-volt supply is connected to the input terminal N3-9 through a resistor R55 and a potentiometer A5 to offset the effect of the connection of the 6 volt power supply to the amplifier N3-12, 13, 14. The effect of the non-linear current-voltage characteristic of the diodes D10-D11-D12-D13 is to reduc the effect of the speed-up circuit 5 at high rates of ai flow where the air flow transducer 44 is better coupled the air stream than at low rates of flow. Thus, a step function at high rates of flow, as indicated by a high mass flow signal MFV, makes a relatively small change in the compensation signal as developed at the terπLnal N-3-14 This makes the compensation greatest where it is most needed. The 11 volt power supply is momentarily applie through a capacitor C19 when the controller 2 is first turned on. This momentarily causes a transistor Q4 to con duct to disable the speed-up circuit 5 at the start.It is well known that a gasoline engine function better upon accelerating if the air-fuel mixture is enriched. lϊΛJRO It is therefore conventional to provide an accelerator pump operating upon depression of the accelerator pedal to squirt a small additional amount of gasoline into the carburetor upon change of accelerator pedal position in the direction of further opening of the throttle. This function is achieved in the present invention by operation of the accelerator pump circuit 6 illustrated in FIGURE 6. The throttle position signal TPV is applied over the con¬ ductor 86 to the accelerator pump circuit 6. The pump circuit 6 comprises a long time constant pump circuit 150 and a short time constant pump circuit 152. In the long time constant pump circuit 150, any change in throttle position signal TPV charges capacitors C12 and C13 which are then discharged through a potentiometer Al connected as a variable resistor and a resistor R18, with a time constant determined by the position of the potentiαneter Al. A portion of this signal is picked off a potentiometer A2 which determines the amplitude of the signal. This signal is amplified by an amplifier N2-5, 6, 7 to produce at a resistor R26 a signal of amplitude dependent upon the change in throttle position signal TPV with a time constant dependent upon the settingg of the potentiometer Al. An amplifier N2-1, 2, 3 is connected to assure that the signal not go negative. A transistor Q2 and the connections thereto, particularly the voltage momentarily applied through a capacitor C14 when the system is first turned on, disables the circuit momentarily to give time for the capacitors C12 and C13 to become charged initially by the throttle position signal TPV. An RPM limit circuit 154 acts to limit the amplitude of the output signal from the long time oonstant pump circuit 150 to an upper limit dependent upon the engine speed. As will be described in greater detail in connection with FIGURE 11, a signal RPMV indicative of engine, speed is developed on a conductor 156 in response to the run pickup signal RUN PICKUP, applied over the conductor 106 from th run pickup sensor 104. The RPM limit circuit 154 assures that the signal at N2-13 not rise above the engine speed signal RPMV. This provides an upper limit to the amplitude of the signal developed on the capacitorsC12 and C13 and limits the amplitude to a smaller voltag at lower speeds.The short time constant accelerator pump circui 152 is similar to the pump circuit 150 except that it operates with a shorter time constant as determined by t setting of a potentiometer A7 and provides a signal of different amplitude as determined by the setting of a potentiometer A6. The output of the short time constant accelerator pump circuit 152 is applied through a resist -R27 to a summing amplifier N4-5, 6, 7 to which the outpu of the long time constant accelerator pump circuit 150 is also applied. The outputs of the long time constant accelerator pump circuit 150 and the short time constant accelerator pump circuit 152 are summed in the summing amplifier N4-5, 6, 7, and the summed output is added to t compensated mass air flow signal AFV applied over the co ductor 148 through a summing resistor R37. These signals are summed in a summing amplifier N4-1, 2, 3, and the summed output is applied through a resistor R41 to an output conductor 157 as the fuel control signal FCV.A transistor Ql responds to negative signals applied to the capacitors C12 and C13 by groundingthe fue control signal FCV in the event of negative accelerator motion, that is, when the accelerator pedal is lifted. This reduces the fuel flow more than would normally be t case upon raising the accelerator pedal and acts to dispose of excess fuel already in the fuel system. This eliminates a so-called CO spike in the exhaust emissions. Such spike is occasioned by the fact that the. fuel feed system contains some fuel accumulated in the system follo BU O ing the metering fuel pump. This- fuel is £n excess of the desirable amount for proper burning of the fuel when the throttle is being closed, reducing the amount of air. To offset this somewhat and to reduce the excess fuelpromptly, the fuel control signal FCV is momentarily depressed. An amplifier N4-12, 13, 14 and a diode D5 keep the output of the short time constant pump circuit 152 from going negative.It has been discovered that cold engines willrun more smoothly upon sudden accelerations if more fuel is added by the accelerator pump action than would be desirable when the engine is hot. .A signal CLD indicative of a cold engine is applied to the accelerator pump circuits 6 over a conductor 158. As will be described in greater detail below, the cold signal CLD is derived from the engine tem¬ perature signal ETS applied to the controller 2 on the conductor 93. In the accelerator pump circuit 6., the cold signal CLD is applied to a transistor Q3 to change the gain of the long time constant accelerator pump circuit 150 to increase the gain when the engine is cold.The fuel control signal FCV is in a sense the primary control voltage for the pump driver circuit 7. As shown in FIGURE 7, the pump driver circuit 7 is essentially a circuit wherein the fuel control signal FCV applied on the conductor 157 is compared to the pump speed signal POMPTACH applied on the. conductor 65, and the metering pump 52 s driven at such speed by the power applied at the conductor 50 as to place the fuel control signal and the pump speed signal in appropriate ratio as determined by a ratio control signal RCV applied on a conductor 160. The ratio control signal RCV is developed in the ratio control circuits 8 and 9 as illustrated in FIGURES 8 and 9 and discussed further below. Because the pump 52 is a positive displacement pump, pump speed is a measure of rate of flow of fuel. Thus, the pump driver circuit 7 causes the metering pump 50 to operate at such speed as to maintain the ratio of air flow (as indicated by the fuel control signal FCV) to fuel flow (as indicat by the PUMP TACH signal on the conductor 65) at the ap¬ propriate magnitude as demanded by the ratio control sign RCV on the conductor 160. Actually, of course, under co ditions of acceleration the accelerator pump circuit 6 causes the fuel control signal FCV to be somewhat differen from the actual air flow signal AFV. Even so, one may broadly construe the pump driver circuit 7 as maintainin fuel flow at an appropriate air/fuel ratio.The fuel control signal FCV is applied on the conductor 157 through a follower circuit 162 and thence through a pump range extender circuit 164 to the + input terminal of a differential amplifier 165. The pump speed signal PUMP TACH is applied ove the conductor 65 to a signal conditioning circuit 166 which operates substantially like the signal conditionin circuit 130 described above in connection with FIGURE 4. That is, the pump speed signal PUMP TACH is in much the same form as the air flow signal AIR FLOW and the signal conditioning circuit 166 operates to convert the input signals into a series of corresponding pulses of uniform magnitude and duration at the terminal 12 of a one-shot multivibrator N5. As before, the output pulse rate is twice the input pulse rate, at least under some conditions.The output of the signal conditioning circuit 166 is applied to a multiplier circuit 168 which operate much like the multiplier circuit 138 described in connec tion with FIGURE 4. In this case the other input is the ratio control signal RCV applied over the conductor 160. The output of the multiplier circuit 168 is by way of an integrating circuit comprising a resistor R21 and a capacitor C5 which operates to produce on the capacitor C5 a signal proportional to the product of the ratio con trol voltage and the pump speed. This combined signal is applied to the - input terminal of the differential ampli¬ fier 165. The amplifier 165 thereupon acts to compare the fuel control signal FCV with the fraction of the fuel flow signal as demanded by the ratio control signal RCV.'. The pump range extender circuit 164 is to permit relatively accurate fuel metering over a relatively wide • range of speeds. The control range is limited by the permissible length of output pulses from the multivibrator N5. If the pulses are very short, the signals are too small for accuracy. On the other hand, if the pulses are made relatively long, then the pump speed may be so great that the pulses occur so.rapidly that the pulses actually overlap, making further control impossible as the signal can be no greater than fully on. To alleviate this diffi¬ culty, the pump range extender circuit 164 cuts the effective pulse rate in half at high metering pump speeds.As shown in FIGURE 7, the pump range extender circuit 164 receives the fuel control signal FCV from the follower circuit 162 and the ratio control signal RCV from the conductor 160. Effectively, a differential amplifier N3- 5, 6, 7 compares the fuel control signal FCV with a portion of the ratio control signal RCV and develops a range control signal on a conductor 170 indicating which is the larger. As the ratio control signal RCV is a measure of the desired ratio between air flow (as represented by the fuel control signal FCV) and fuel flow (as indicated by the PUMP TACH signal) , the ratio control signal is itself determinative of an air flow at which the pump speed exceeds some limit. That is, for any pump speed limit where it is desired to activate the pump range extender circuit 164, the ratio control signal RCV relates this limit to air flow. The relative resistances of resistors R5 and R7 set the corres¬ ponding air flow limit for switching in the range extender circuit 164. Thus, whenever the fuel control signal FCV is larger than the control level, as would indicate a demand for a relatively high pump speed, the range contr signal is low, and whenever the fuel control signal is smaller, as would indicate a demand for a relatively low pump speed, the range control signal is high. The range control signal on the conductor 170 is applied to the in verter N4-1, 2, 3 to turn the inverter off when the rang control signal is low. This halves the number of output pulses from the multivibrator N5, permitting twice as ma pulses and hence twice the pump speed before the range o the multivibrator control is reached. This permits use a longer period for the multivibrator and hence more ac¬ curate control at the lower speeds. The result of thus extending the range of the multivibrator is to reduce th output signal to the - terminal of the amplifier 165 by -factor of 2. To compensate for this, a high signal on the conductor 170 is applied through a transistor Q2 to turn on a transistor Ql which acts to shunt a resistor R9 in a voltage divider comprising resistors R9 and R10 of equal resistance. This means that the shunting of the resistor R9 cuts in half the gain of an amplifier N2-5, 6, 7. Thus, the + input to the amplifier 165 is cut in half at the same time that the input to the - terminal is halved. The differential amplifier 165 thus produces a pump control signal on a conductor 172 indicative of whether the pump speed is above or below the desired spee The pump control signal is applied through a switching circuit 173 to a power amplifier 174. This switching circuit 173 is normally in the condition wherein a tran- sistor Q4 is on and a transistor Q3 is off. This couples the conductor 172 to the power amplifier 174. When the pump control signal on the conductor 172 is greater than reference potential on a conductor 176, a transistor Q5 is turned on, which in turn turns on a transistor Q8, which in turn turns on a driving transistor QPD which supplies the driving current PUMP for the pump 52 over the conductor 50. The pump 52 is then driven to make it travel at such speed that the pump speed signal PUMP TACH produces a feedback signal at the - terminal of the differential amplifier 165 as equals the fuel control signal as applied to the + terminal of the comparator. Because the pump 52 is positively driven, it is promptly speeded up when fuel demand increases to follow demand accurately. Should the fuel demand decrease, it is important that the fuel flow be shut down promptly in order that the fuel flow may also accurately and quickly follow the fuel demand when it decreases. This is achieved by' the application of the pump control signal on the conductor172 to render conductive a transistor Q6 whenever the control signal drops below the reference potential on the conductor 176. Conduction by the transis-tor Q6 turns on transistors Q9 and Q10 which thereby shunts the pump circuit causing the motor to act as a generator and thereby remove energy from the motor. This acts as a dynamic brake, causing the motor to slow down more promptly than were it merely to coast.The effect of fuel temperature has so far been ignored. As fuel expands with temperature, the mass of fuel indicated by the pump speed signal varies with the temperature of the fuel. That is, at cold temperatures, a greater mass of fuel will occupy the same space. Thus, a fuel density circuit 178 is utilized to correct the pump tachometer signal for changes in fuel density. The density is sensed by the fuel temperature sensor 80, which may be a diode having a negative temperature coefficient of resistance. This produces a fuel temperature signal FTC at the conductor 82 in the form of a resistance which rises as temperature goes down. A voltage divider ccmpris- ing resistors R63 and R64 sets an operating level to match the resistance of the fuel temperature sensor at some nominal temperature, such as 25°C. This signal is appli through a follower circuit N6-5, 6, 7 to a conductor 180 This establishes the operating reference level. The gai of the circuit is determined by the setting of a poten¬ tiometer Al connected between the conductor 180 and a resistor R66 connected to the conductor 82. The signal at the tap of the potentiometer Al is the sum of the re¬ ference level, and a portion of the signal developed acro the fuel temperature sensor 80. It is thus a measure of fuel temperature. Such signal is applied to an amplifi N6-1, 2 , 3, the output of which is applied to pin 7 of the multivibrator N5. This modifies the time constant of the multivibrator to provide longer pulses when the fu is colder and hence more dense and shorter pulses when the fuel is warmer. This compensates for changes in the density of the fuel.An optional feature is the connection of a transistor Q14 to N5-2 and 4 and the circuit for turning the transistor Q14 on. The transistor Q14 is turned on by a signal ALCOHOL applied to a conductor 182. When the transistor Q14 is turned on the time constant of the multivibrator is changed. This permits an alternative setup to the signal conditioning circuit 166 whereby pulses of different length may be produced when a dif¬ ferent fuel is used, as for example, alcohol. Thus, whe such fuel is used in lieu of the regular fuel, a signal may be applied to the conductor 182 to modify the time constant of the multivibrator N5 accordingly. The purpose of the switch circuit 173 is to shut-off the metering pump 52 when the engine is not runni More particularly, the circuit 173 is designed to turn off the pump 52 when the engine speed signal RPMV, as applied to the conductor 156, indicates that the engine is turning at less than idle speed and hence is not running This acts to prevent flooding of the engine if the ignition switch is left on while the engine is stopped. The level indicative of idle is determined by the resistance of a resistor R17 connected in a voltage divider including a resistor R16. The engine speed signal is applied from the conductor 156 to the + terminal of a comparator Nl- 5, 6, 7.. When this signal falls below the reference on the resistor R17, the output signal at Nl-7 turns off the transistor Q4, thus turning off the power amplifier 174. At the same time, this signal turns on a transistor Q3 which thereby short-circuits the output of the differen¬ tial amplifier 165 to assure discharge of the output capacitor C4 when the engine is not running. This prevents accumulation of a charge on the capacitor C4 and hence the presence of a control signal demanding fuel at the time the transistor Q4 is first turned on. This prevents an undesirable transient upon starting.In respect to starting, it is of course impor¬ tant to override the turning off of the transistor Q4 when one wishes to start the engine. This is achieved by applying the start, signal 12V ST to the conductor 102 to override the engine speed signal RPMV at the input to the comparator Nl-5, 6, 7 and thus assure turning on of the transistor Q4 and turning off of the transistor Q3 upon starting the engine.The ratio control circuits 8 and 9 as shown in FIGURES 8 and 9, respectively, develop the signal RCV corresponding to a desired air to fuel ratio. There is circuitry for developing a basic run ratio signal for the normal steady state condition with various other cir¬ cuits for making adjustments in such signal for various transient conditions such as to provide enrichment during idle, when starting, and when cold and for certain condi¬ tions where extra power is required for drivability irrespective of economy or ecology. Many of these adjust- ents are somewhat empirical, based upon a particular engine and the vehicle it is propelling. As indicated above,, the circuitry is .to provide suitable optimization of economy, ecology and drivability and suitable trade- offs among the three. In general, the circuit illustrat is suitable particularly for a so-called lean-burn engine That is one in which the air to fuel ratio is well above the stoichiometric ratio, with substantially more air *than is needed for combustion. The basic run ratio is determined by a run rat circuit 184 which is essentially a potentiometer connect between a conductor 186 and ground. The adjustment of a potentiometer KP determines the run ratio which may, for example, be set to be 20:1. The conductor 186 is at a reference potential of 6 volts under steady state conditions when the engine is hot. It is varied pursuan to a temperature control signal ENR V applied to the con ductor 186 from circuitry shown in FIGURE 9 and discusse further below. The signal picked off the potentiometer is applied through a resistor R18 to a conductor 188, when it passes through a buffer amplifier 190 to become the ratio control signal RCV on the conductor 160.Referring now to FIGURE 9, the signal ENR V applied to the run ratio control circuit is developed by a cold enrichment circuit 192. The input to this cold enrichment circuit 192 is the engine temperature ETS ap¬ plied to the conductor 93. This signal is basically a resistance signal created by the negative temperature coefficient of resistance of a diode comprising the tem- perature sensor 80 placed in the coolant of the engine. A voltage is developed on this sensor 80 by way of a 6- volt power supply and a resistor R10, the resistances of the sensor 80 and the resistor R10 forming a voltage divider. The resistor R10 determines the range of signa levels on the conductor 93 as the resistance of the sensor 80 changes with temperature.Basically, the cold enrichment circuit 192 operates by comparison of the engine temperature signal ETS with a reference potential developed on a conductor 194. In the circuit illustrated in FIGURE 9, this refer¬ ence potential is 0.6 volts as developed by a reference potential circuit 196. When the signal ETS is below 0.6 volts, the engine may be considered to be warmed up. The resistor R10 determines the temperature at which the signal reaches such level, which may, for example, cor¬ respond to 180°F. A potentiometer A2 provides a tap that may be adjusted to select a desired portion of the dif¬ ference between the engine temperature signal ETS and the reference potential on the conductor 194. This sets the slope of the characteristic curve and determines the rate at which the signal ENR V on the conductor 186 varies with engine temperature. The signal at the tap of the potentiometer A2 is compared with the reference potential on the conductor 194 in a comparator comprising Nl-1, 2, 3.When the engine is warmed up, the signal picked off at the tap is less than 0.6 volts, and the output of the comparator keeps a transistor Q6 turned off. This allows the 6-volt power supply signal to be applied through a resistor R18 to a follower circuit N3-5, 6, 7 to the conductor 186. On the other hand, when the signal at the tap rises above the reference level the transistor Q6 is caused to conduct through resistors R18, R19 and R20, thereby reducing the input to the follower N3-.5, 6, 7 in proportion to the signal difference between the signal on the tap of the potentiometer A2 and the reference potential 0.6 volts.In general, the slope of the characteristic curve is set to provide for drivability when the engine is cold. This is a relatively short period of time, yet it is critical in car operation as it is important that one be able to start one's car without stalling and with out uneven drivability that would be annoying, if not entirely unsafe. On the other hand, as the engine warms up past the critical region, but before it is fully warm up to its operating temperature, it becomes more importa to meet emissions requirements. To this end, an auxilia reference potential circuit 198 provides an auxiliary reference potential on a conductor 200. The auxiliary reference potential on the conductor 200 is made slightl higher than the reference potential on the conductor 194 as, for example, about 0.65 volts. This is set by the position of a potentiometer A4 to correspond to some par ticular engine temperature, for example, 75°F. It is the nature of the reference potential circuits 196 and 198 that the potential at their outputs cannot go above the selected reference potentials, while .permitting the voltage to go below such values. This means that when t engine is very cold, that is, below the temperature cor- responding to the reference set by the potentiometer A4 current flows through the transistor Qβ and flows partly through a resistor R22 as well as through the resistor 2 The enrichment signal ENR V therefore varies with engine temperature according to a temperature characteristic having a slope that is relatively steep, assuring substa tial enrichment. Once, however, the engine temperature rises above the temperature corresponding to the setting of .the potentiometer A4, current ceases to flow through the resistor R22 to the conductor 200. Thereafter the enrichment voltage varies as a somewhat different functi of engine temperature with a flatter slope, until the temperature rises to the temperature corresponding to 0. volts on the conductor 194, which may be considered oper ating temperature. At that temperature, the transistor Q6 ceases to conduct and the enrichment signal ENR V is at the 6-volt reference level.As mentioned above, one of the more difficult times in operation of an internal combustion is at the start. It is helpful under start conditions to provide additional, fuel flow to assure starting. In the circuit of FIGURE 9, this is achieved by a cold start enrichment circuit 202. This circuit is activated by application of a starting signal 12V ST on the conductor 102. This enables a transistor Q4 to apply the engine temperature signal ETS to the cold start enrichment circuit 202. This circuit 202 operates much as the cold enrichment circuit 192 to draw additional current through the resistors R18 and R19 to reduce the enrichment control signal ENR V on the conductor 186, thus reducing the ultimate ratio control signal and causing a greater amount of fuel to be supplied by the metering pump 52. In this case, the enabling of the diode Q4 applies the engine temperature signal ETS to a capacitor C2 which holds the voltage after the start signal is removed. The capacitance is then discharged through a potentiometer A3 over a period of time as, for example, 10 seconds. The signal developed on the poten¬ tiometer A3 is compared with the reference potential on the conductor 194 to control a transistor Q5 in the manner of the transistor Q6 of the cold enrichment circuit 192, adding enrichment. As the charge on the capacitor C2 is dissipated through the potentiometer A3, the added cold start enrichment gradually tapers off. Thus, the cold start enrichment continues for a time after the start switch is disengaged and dies out after a short period during which the engine almost surely starts and reaches a relatively stable condition where it can remain in oper¬ ation after the cold start enrichment has been dissipated. It may be noted that the cold enrichment circuit 192 provides an additional output signal through a resistor R17 to a start circuit 204. This provides a signal corresponding to engine temperature to an amplifi comprising a differential amplifier Nl-8, 9, 10 and its associated components. The gain of the amplifier is de¬ termined by the setting of a potentiometer Al connected as a variable resistor. The purpose of the start circui 204 is to provide a suitable fuel control signal FCV irrespective of air flow through the air flow transducer 44.- This enables fuel to be supplied in order to get the engine started in the first place. There are two enabling signals applied to the start circuit 204: one is the wide open throttle signal WOT applied on the con¬ ductor 90, and the other is the starting switch indicato 12V ST applied on the conductor 102. As stated above, t wide open throttle signal WOT is at ground when the throttle is fully open; otherwise the signal is normally held high by the 12-volt potential applied through a re¬ sistor R43 to the conductor 90. The normally high wide open throttle signal WOT enables a transistor Ql which then acts to turn off a transistor Q2. This permits a 12-vόlt start signal applied to the conductor 1Q2 to enable a transistor Q3 to apply the output of the ampli¬ fier Nl-8, 9, 10 to the conductor 157 as the fuel contro signal FCV. The magnitude of this signal is thus depen¬ dent upon the signal from the cold enrichment circuit 192 and provides a fuel control signal FCV demanding an amount of fuel that depends upon the .engine temperature signal ETS at the time the starting switch is engaged. The function of the WOT signal is to disable the transist Q3 when the throttle is wide open. When the WOT signal is low, indicating a condition of wide open throttle, it disables the transistor Ql, thereby enabling the tran¬ sistor Q2 to ground the 12-volt start signal. This shut the metering pump off during cranking when the throttle is wide open, thus providing an opportunity to clear the engine of flooding merely by flooring the acceleratorBUO pedal. and turning on the start switch to crank the engine. Also responsive, to the engine temperature signal ETS is a cold circuit 206 wherein a comparator Nl-5, 6, 7 senses when the engine temperature signal ETS rises above the reference potential on the conductor 194 and produces an output signal CLD indicating that the engine is cold whenever the engine temperature signal is above the reference. This CLD signal is applied to the con¬ ductor 158 by which it is connected to the accelerator pump circuit 6 as described above.As noted above, the present engine, control is designed to operate an engine with a lean air to fuel ratio, such as a ratio of 20:1, when the engine is in its cruise condition. Such a lean mixture, is unsuitable when the engine is idling, as it will cause misfires.It is therefore desirable to provide a richer ratio upon idle. This is the function of an idle ratio limit cir¬ cuit 210. An idle condition could be sensed by sensing the engine speed as indicated by the engine speed signal RPMV. However, in the circuit illustrated, the mass rate of flow of air signal MFV is utilized as an indication of the idle condition. When the engine is idling and the throttle is depressed to accelerate the engine, the engine speed does not immediately change because of the inertia of the engine and its load. The air flow sensor thus responds more promptly to a change from idle. Fur¬ ther, when the engine is under load there is a greater air flow for the same engine speed.As shown in FIGURE 8, the mass rate of flow of air signal MFV is applied the conductor 146 to the idle ratio limit circuit 210. The signal MFV is compared to a reference potential developed across resistor R3 from the 6-volt power supply. This sets a break point for the control characteristic. The reference potential is set slightly above the signal MFV at idle; thus when the signal MFV is below the reference signal, the idle ratio limit circuit 210 takes the engine to be at idle. When the signal rises above the reference, an output signal is developed across a resistor R7 corresponding t the amount the signal MFV is above the reference. A potentiometer A2 is connected between the resistor R7 an the conductor 186. The tap on the potentiometer A2 thus picks off a signal between that developed across the resistor R7 and the signal ENR V.. The position of the potentiometer determines the magnitude of the effect of the idle ratio limit circuit. As indicated above, it is desirable that the engine operate at idle at the leanest ratio that it will operate smoothly without misfire. The lean limit may be, for example, an air/fue ratio of 16:1. The signal picked off the potentiometer A2 is applied to the + terminal of an amplifier N2-1, 2, 3 which acts to prevent its output on the conductor 188 from rising above the idle limit control signal. This means that even though the run ratio may be set at 20:1 under idle conditions, the idle ratio limit circuit will limit the ratio control signal to correspond to a ratio of 16:1.. Further, as the engine goes above idle toward its normal run condition the mass flow signal MFV causes the idle ratio limit circuit to increase the limitation the ratio control voltage along a slope until the run ratio or some other limit as described below is reached.It has been found that when starting a car, ev with the engine warmed up, the normal run ratio is too lean for proper combustion when the combustion chambers are not hot. That is, after a car has been standing onl a brief time, the combustion chambers will be much below their operating temperature, even though the engine coola temperature is in its operating range. When the engine coolant is cold, as indicated by the engine temperature εignal ETS, the cold enrichment circuit 192 provides additional enrichment to avoid the problem. However, when the engine is not cold a start enrichment circuit 212 is provided to add enrichment. In this circuit 212, the closing of the ignition switch to start the engine applies the 12V ST signal to the conductor 102 which is applied through a transistor Q5 to charge a capacitor C2.. This charge will remain even after the 12-volt start signal 12V ST is removed until such time as the charge leaks off through a resistor R16 and a potentiometer Al as well as through resistors R14 and R15. The time constant for such discharge is made whatever may be convenient for a particular engine, such as 30 seconds. The charge on the capacitor thus develops a signal on the tap of the potentiometer Al that decreases with time after the 12V ST signal is removed. The signal at the tap is applied through an amplifier Nl-12, 13, 14 to enable a transistor Q6 and transfer the signal to the + terminal of the ampli¬ fier N2-1, 2, 3. This reduces the input thereto in accordance with the start enrichment signal as picked off from the potentiometer Al. The gain of the circuit is, of course, controlled by the setting of the potenti¬ ometer Al.Another circumstance that presents drivability problems is operation at low manifold vacuum. When operating at low manifold vacuum, as at a relatively low engine speed, opening the throttle has little effect on power, for the pressure differential is so small that little additional air flows and hence little additional fuel is supplied. It is therefore desirable to increase power under such circumstances by providing an enriched air/fuel ratio. This is achieved by a power I circuit 214 (FIGURE 8). The manifold vacuum signal MW is applied over the conductor 124 to the power I circuit 214. The power I circuit is essentially the same as the idle ratio limit circuit 210 and operates to place an upper limit on .-the xatio control signal RCV. That is, if the air/fue ratio is not limited by some other control signal, it will be limited by the power I output. Thus, when the manifold vacuum signal MW as applied over the conductor 124 falls below the reference signal developed across a-resistor R33, the power I circuit limits the potential on the conductor 188 to prevent the ratio control signal from going above some predetermined limit, such as that corresponding to an air/fuel ratio of 18:1. This limit rises as the manifold vacuum signal rises above the con¬ trol limit. The effect of the power I circuit is to be concerned more with power than with ecology or economy. That is, for drivability and for power- as needed, the power I circuit will override the normal run ratio.Another circumstance requiring power ahead of ecology or economy is in matters of emergency when it is important to accelerate rapidly, as in passing a truck or avoiding difficulty. It is important to be able to get substantial additional power. This .is achieved by a power II circuit 216 (FIGURE 8) . This circuit is acti¬ vated by the wide open throttle signal WOT applied over the conductor 90. As stated before, when the throttle goes wide open,, the WOT signal goes to ground. This causes a transistor Ql to turn off, thereby causing a transistor Q2 to conduct, and thus placing one end of a resistor Rll at ground, the other end being connected through a potentiometer A3 to the conductor 186. Grounding the resistor Rll thus reduces the potential at the tap of the potentiometer A3, depending upon where the poten¬ tiometer A3 is set, and an amplifier N3-8, 9, 14 then operates like the power circuit to provide another uppe limit to the signal on the conductor 188. This signal would, for example, be equivalent to a ratio of perhaps 14:1. As a alternative it would be possible to apply a ramp signal, that is, a signal that varies with throttle position such as a signal based upon the throttle position signal TPV, which ramp signal introduced- the power II limit gradually, as in the case of the power I signal. It is desirable to have even more power for acceleration when the car is already going at relatively high speed. A power III circuit 218 (FIGURE 9) provides such additional power by providing a still lower air/fuel ratio. The power III circuit receives its control input from the transistor Ql in the power II circuit (FIGURE 8). That is, the power III circuit is enabled by the WOT signal at the same time that the power II circuit is activated. The activation signal PWR III is developed on a conductor 220. The conductor 220. is normally held at ground potential by the transistor Ql. This disables a transistor Q7, which in turn disables a transistor Q8, which in turn disables a transistor Q9. However, upon occurrence of a WOT signal indicating a wide open throttle, the transistor Ql is made non-conductive, whereupon the conductor 220 is raised to the higher potential of the 6-volt supply. This turns on the transistor Q7, which in turn turns on the transistor Q8, which in turn turns on the transistor Q9. The engine speed signal RPMV is applied from the conductor 156 through a resistor R42 to the - input terminal of a comparator N4-1, 2, 3. The + terminal is held at a reference potential picked off a potentiometer A6. When the engine speed signal RPMV is below the reference potential set by the potentiometer A6,. the output of the comparator N4-1, 2, 3 is high, and the transistor Q9 does not conduct. This leaves a conduc¬ tor 222 at the 6-volt power supply level. On the other hand, when the engine speed signal RPMV exceeds the refer¬ ence level set by the potentiometer A6, the output terminal N4-1 goes low, whereupon the transistor Q9 conducts, causing a potential drop across a resistor R35 which lowers the potential on the conductor 222. This signal X is then applied by the conductor 222 to an outp circuit N3-10, 11, 13 (FIGURE 8), which acts like the output circuits of the power I and power II'circuits to keep the ratio control signal RCV from rising above some particular level. In this case the ratio limit is made equivalent to the maximum power available which occurs a about a 12:1 air/fuel ratio.Another problem arises in connection with deceleration of an engine. In deceleration, the throttl is normally closed, resulting in high manifold vacuum and low manifold pressure. The pressure may become so low as to be unable to support the combustion at the normal air/ fuel ratio. This results in unburned fuel i the exhaust. A decel ratio limit circuit 224 (FIGURE8) operates to assure a richer mixture under certain de¬ celeration conditions. More particularly, the manifold pressure signal MPV on the conductor 120 is compared to a decel potential DPV applied on a conductor 226. The signal DPV is developed in a manner that will be discuss further below in connection with FIGURE 13. When the manifold pressure is so low that the manifold pressure signal MPV is less than the reference signal DPV, tran¬ sistors Q9 and Q10 are off. This causes a decel ratio limit signal to be applied to a conductor 228 as deter¬ mined by the setting of a potentiometer A6. This signal is applied to an output circuit N3-2, 4, 5 to limit the potential on the conductor 188 to lower the ratio control signal to the decel ratio limit if it is notothe wise more limited by some other control circuit. As the pressure rises so that the manifold pressure signal MPV is greater than the decel pressure reference signal DPV on the conductor 226, the signal on the conductor 228 is raised. This correspondingly raises the decel limit applied by the output circuit N3-2, 4, 5 to the conducto 188. The limit is raised in accordance with how much the manifold pressure signal MPV exceeds the decel refer¬ ence signal DPV. The slope of the characteristic is determined by the resistance of a potentiometer A5 con- nected as a variable resistor.The throttle bypass control circuit 1Q shown in FIGURE 10 is substantially the same as the circuit shown in FIGURE 5 of copending patent application Serial No. 783,614 and functions in the manner of the circuit described in said copending patent application for con¬ trolling the flow of air through the bypass throttle 68. The circuit of the copending application includes a tem¬ perature circuit 178 that is comparable to a cold idle circuit 230 shown in FIGURE 9. As described in the co- pending application in connection with such temperature circuit, the cold idle circuit 230 operates in response to the engine temperature signal ETS on the conductor 93 to.produce a cold idle signal C.I. on a conductor 232 which is applied to the circuit of FIGURE 10. The output of the throttle bypass control 10 applies a control signal B.P. SOL. on the conductor 70 to control the position of the bypass throttle 68 in the manner described in the aforesaid application Serial No. 783,614. An alternative throttle bypass control circuit would provide a more co - plicated characteristic for control by the throttle position signal TPV to provide a progressive throttle bypass control signal in which air flow increases more sharply with throttle position when'the throttle is wider open. This makes for smoother control and drivability. Adverting now to the timing control circuits, the ignition timing control circuit 11 as shown in FIGURE 11, basically responds to the run pickup signal RUN PICKUP on the conductor 106 and a timing control signal TCV as applied to a conductor 236 from the timing advance cir- cuits 12 and 13. The development of the timing control signal TCV will be discussed further below in connection with FIGURES 12.and 13. The run pickup signal RUN PICKU and the timing control signal TCV are applied to a trigg circuit 238 which produces an output pulse on a conducto 240 at a time determined by the timing control signal TC That is, the run pickup signal RUN PICKUP establishes a time reference, and at a time thereafter, as determined by the timing control signal TCV, an output.trigger puls TRIGGER is produced on the conductor 240. As mentioned above, the run pickup sensor 104 may be magnetic means associated with the ignition distributor in the ignition system 24 to provide a time base identification of the position of the engine. For example, the run pickup signals RUN PICKUP may occur 60° before top dead center of each cylinder.The run pickup signals RUN PICKUP are applied to a conditioning circuit 242 which acts to convert the incoming signals to corresponding sharp pulses suitable for triggering a bistable multivibrator 244 comprising transistors Q4 and Q5. When a pulse is applied from the conditioning circuit 242, it turns on the transistor Q4 and thereupon turns off the transistor Q5. It also turn off a transistor Q6 connected across a capacitor CIO. The capacitor CIO is thereupon charged over a conductor 246 at a rate determined by a position-time converter 24 The capacitor CIO charges until the voltage thereon as applied to the - input terminal of a comparator N4-5, 6, 7 rises to the potential on the + input terminal. The latter voltage is determined by the timing control signa TCV applied over the conductor 236. The time it takes for the capacitor CIO to charge to the reference voltage determined by the timing control signal TCV is a time that is determined by the magnitude of the timing contro signal TCV. The time at which the capacitor CIO reaches this potential will therefore occur at a particular timeO following a particular run pickup pulse on the conductor 10.6 which triggered the bistable multivibrator 244. When the signal on the - input terminal of the comparator exceeds the reference potential on the + input terminal, the output goes negative applying a negative trigger signal TRIGGER to an ignition pulse circuit 250.The ignition pulse circuit 250 acts in response to a trigger pulse to produce a suitable ignition pulse on the conductor 112 for application to the ignition system 24. The ignition system thereupon acts to produce a suitable spark discharge in a particular combustion chamber in the usual fashion.The position-time converter 248 is controlled by the engine speed signal RPMV which is developed in an RPM circuit 252. In this case the run pickup signals RUN PICKUP are utilized to mark each cycle of rotation of the engine and hence develop a signal RPMV indicative of engine speed. The run pickup signals RUN PICKUP are con¬ ditioned by a signal conditioner 254 to produce correspond- ing pulses suitable for operating a frequency to voltage converter 256. The frequency to voltage converter 256 operates to produce an output signal RPMV on the conductor 156 which is proportional to the rate of incoming pulses. This signal is therefore indicative of engine speed. The position-time converter 248 operates to control the charging rate of the capacitor CIO and hence the time for the voltage thereon to reach the reference level determined by the timing control signal TCV. To relate engine position to time, it is necessary to' know the speed of rotation of the engine. This relationship is achieved by charging the capacitor CIO at a rate depend¬ ent upon engine speed. In other words, if the engine is traveling twice as fast the capacitor CIO must be charged twice as fast in order that it reach a particular . voltage level at the same relative engine position, and hence at the same relative angle in respect to the run pickup signal RUN PICKUP on the conductor 1Q6. In the position-time converter 248, the engine speed signal RPM is applied to the + terminal of an amplifier N3-1, 2, 3. . With the current mirror circuit shown comprising resistors R33 and R34 and transistors Ql and Q2, the current through the transistor Q2 and hence the current charging the capacitor CIO are proportional.to the engin speed signal RPMV. This makes timing angles independent of engine speed. The ignition pulses on the conductor 1 are thus instituted at a predetermined angular position following each RUN PICKUP pulse on the conductor 1Q6, as determined by the timing control signal TCV applied to the conductor 236., The proportionality factor relatin position to time is determined by the resistance of a resistor R35.During starting it is desirable to operate independently of the timing control voltage, and instead to cause the ignition pulses to occur during starting at a particular angular position in the cycle. A start con dition is sensed by a start timing circuit 258 which sens when the engine speed signal RPMV is less than a referen potential set on a resistor R40. Under such condition a signal is developed on a conductor 260 to keep the transistor Q6 turned on until the engine speed rises abo the reference level. It may be presumed that the engine is in a start condition when the engine speed is belowth reference level, which level is set below idle speed. This assures that the capacitor CIO not be charged and the comparator N4-5, 6, 7 thus not produce an output trigger pulse during starting. Instead, the trigger puls is derived from the start pickup signal START PICKUP applied to the conductor 110. This signal is applied to a pulse conditioning circuit 262 which operates in much the fashion of the pulse conditioning circuit 242.OMP ■ In this case the output pulses operate to reset the bistable multivibrator 244, at which time the multi¬ vibrator applies a trigger pulse directly to the conductor 240. Ignition pulses are therefore produced at the ter- inal 112 at the appropriate time for starting as determined by the start pickup pulses on the conductor 110.The timing control signal TCV as applied to the conductor 236 is developed in the timing advance circuits 12 and 13 of FIGURES 12 and 13 in response to signals from various of the sensors and signals developed in other parts of the controller. In general, the timing control signal TCV may be said to be the sum of a number of timing advance signals with various limits superimposed. The signals are summed in a summing circuit 264. The summing circuit 264 includes a summing point 266 and a summing resistor R8 connected between the summing point and ground. Signals from the various advance and limit cir¬ cuits are applied through switches to the summing point 266. These signals are summed across the resistor R8, and the summed signal is applied through a follower amplifier N3-_L, 2, 3 to develop the timing control signal TCV on the conductor 236.As stated above, conventional timing controls include centrifugal means for advancing the spark as speed increases and vacuum means for advancing the spark as manifold vacuum increases. The spark advance with engine speed is used to compensate for delays in flame propagation in the burning of the fuel during each firing of a cyl- inder. More particularly, because it takes time for the flame front to propagate, a spark that is timed properly at one speed will not be proper at other speeds. If speed is increased and the spark occurs at the same angular position as before the increase, the engine moves faster relative to the flame front and the flame front is there¬ fore relatively delayed. To compensate for this, the εpark is advanced so that the burning starts earlier an peak pressure arrives at the appropriate time in the engine cycle.In respect to the vacuum advanc f t is evident that the flame front will advance more slowly at high vacuum. This is because the air density is lower. Spar timing that is appropriate at one level of vacuum is too late at greater vacuum because the flame front does not propagate as fast. Thus, at high vacuum levels it has been conventional to advance the spark. In the circuit of the present invention spark is advanced pursuant to manifold pressure rather than manifold vacuum, because it is absolute air density that is significant in the rate of propagation of the flame front. On the other hand, a circuit responsive to manifold vacuum could be - used and has the advantage that manifold vacuum sensors are less expensive than manifold pressure sensors.FIGURE 14 illustrates typical controller timin characteristics produced by the timing advance circuits 12 and 13. More particularly, in FIGURE 14A are illustra the RPM advance characteristic RPMA and the manifold pre sure advance characteristic MPA. The RPM advance characteristic is a curve of timing advance as a functio of RPM and the manifold pressure characteristic is a cur of timing advance as a function of manifold absolute pre sure (M.A.P.) in inches of mercury.The RPM advance characteristic RPMA is develop by an RPM advance circuit 270 as shown in FIGURE 12. As there shown, the RPM control signal RPMV is applied over the conductor 156 and through resistors R36 and R35 to the + terminal of an amplifier N2-1, 2, 3. The - te minal is biased by a reference potential developed at the junctions of resistors R34 and R32 connected as a voltage divider across the 6-volt power supply. When the signal applied to the + terminal exceeds the bias level on the - terminal, a transistor Q10 is caused to conduct current in proportion to the magnitude of the signal applied to the + terminal relative to the reference potential. A reference signal RPMI is developed by a potentiometer A7 and applied through a follower circuit to the tap of a potentiometer A5 connected as a variable resistor. The other side of the potentiometer A5 is con¬ nected to the + terminal of an amplifier Nl-1, 2, 3. The transistor Q10 conducts through the potentiometer A5 and hence reduces the potential at the + terminal in proportion to the amount by which the RPM control signal RPMV exceeds the reference level applied to the - terminal of the amplifier N2-1, 2, 3. When the RPM control signal RPMV is below the bias level of the amplifier N2-1, 2 , 3 and the transistor Q10 is therefore off, the reference signal RPMI is applied through the potentiometer A5 to the terminal Nl-3 of an amplifier Nl-1, 2, 3. As the RPM control signal RPMV rises above the bias level, the signal at the terminal Nl-3 falls proportionally. The signal applied at the terminal Nl-3 controls the flow of current through a transistor Q9 to maintain the signal level at the emitter of the transistor Q9 at the level of the signal on the terminal Nl-3. This determines the current through a resistor R31 and thence the current through the transistor Q9. This current is applied through a switch Sl-1 and a conductor 272 to a summing point 274 which is connected by a conductor 276 to the summing point 266. This signal on the conductor 272 corresponds to a number of degrees of spark advance and is the spark advance signal RPMA.In the idle range, engine operation is somewhat unstable. It is therefore desirable that a fixed spark advance be applied during the idling of the engine. Idling may be taken as an engine speed below some reference speed and hence with an RPM control signal RPMV less than some reference potential, in this case the reference level established by the bias across the resistor R32. Up to that point, the transistor Q10 is disabled and the referenc potential RPMI is applied to the amplifier Nl-1, 2, 3 to produce an output RPM advance control signal RPMA cor¬ responding to RPMI as illustrated in FIGURE 14A.Once the transistor Q10 becomes conductive, tha _ ±ε r when the RPM control signal RPMV rises above the idle bias level, current flows through the transistor Q10 and the potentiometer A5 to lower the potential at the input terminal Nl-3. This increases the flow of current throug the transistor Q9 and hence raises the output signal RPMA The relationship between the RPM control signal RPMV and the current flow in the conductor 272 is determined by th resistance of the potentiometer A5, which thus determines ' the slope of the characteristic curve RPMA as shown in FIGURE 14A.At high speeds it is desirable that the rate of advance with speed be less. In fact, at high speeds, turbulence causes the fire front to sweep the cylinder so rapidly that further advance is not necessary or desirable. To limit the advance at high speed, a referenc potential RPMA STOP is established by a potentiometer A8. An amplifier N2-5, 6, 7 and a diode D4 keep the terminal N2-6 from rising above the reference potential RPMA STOP. This means that when the RPM control signal RPMV rises above the reference potential RPMA STOP, the potential at the terminal N2-3 is held to the level- RPMA STOP. This puts, an upper limit to the characteristic curve for- the RPM advance signal as shown in FIGURE 14A.The manifold pressure advance signal MPA is developed in a manifold pressure advance circuit 278. This circuit responds to the manifold pressure signal MPV applied on the conductor 120. The manifold pressure signal MPV is amplified by a follower circuit comprising■ an amplifier N5-1, 2, 3 which develops a corresponding manifold pressure signal MPVB on a conductor 280. This signal is applied through a potentiometer A10 and a re¬ sistor R28 to a pair of amplifiers N6-1, 2, 3 and N7-5, 6, 7. The signal is applied to the amplifier N6-1, 2,3 by way of an integrating circuit consisting of a capaci¬ tor C8 and a variable resistor All. The integrating circuit effectively delays the application of the signal to the amplifier N6-Ϊ, 2, 3. The outputs of the respective amplifiers are applied through respective diodes D4 and D5 to a terminal 282 connected to ground through a resistor R31. The terminal 282 is biased from the 6-volt power supply through a potentiometer A12 and a resistor R30, the potentiometer A12 and the resistances R30 and R31 constituting a voltage divider. The amplifiers N6-1, 2, 3 and N7-5, 6, 7 are connected so that the more positive output of the amplifiers controls the diodes D4 and D5 decoupling the more negative output from the terminal 282. . Because the input to the amplifier N6-1, 2, 3 is applied by way of an integrating circuit, the input thereto is delayed. Thus, when the manifold pressure signal MPV rises, the output of the amplifier N7-5, 6, 7 rises at once, in unison with the manifold pressure voltage MPV, whereas the output of the amplifier N6-1, 2, 3 lags behind. Thus, the output of the amplifier N7- 5, 6, 7 controls as atmospheric pressure increases. On the other hand, the output of the amplifier N6-1, 2, 3 also lags as the pressure drops. As this leaves the output of the amplifier N6-1, 2, 3 higher than the output of the amplifier N7-5, 6, 7, the amplifier N6-1, 2, 3 controls when the manifold pressure drops. This means that the signal appearing on the terminal 282 rises in unison with manifold pressure, but drops more slowly dependent upon the time constant of the integrating circuit comprising the capacitor C8 and the variable resistor All. The resistor All is adjusted to provide a suitable time-BUREAUOMPI constant.The difference between the 6-volt 'supply and the signal on the terminal 282 appears across the poten tiometer A12 in series with the resistor R30. A porti of this difference is picked off at the tap of the pote tiometer A12 and applied to the + terminal of an amplif N7-1, 2, 3. The - terminal is connected to the 6-volt power supply through a resistor R32. A transistor Q6 operates to draw current through the resistor R32 so as to maintain the potential at the - terminal equal to th picked off the tap on the potentiometer A12. The trans tor Q6 is effective until the potential at the tap reac 6 volts at which time the transistor Q6 is turned off, as the potential on the negative terminal N7-2 is as hi as it can get, namely with no current flowing through the resistor R32. In the circuit as illustrated, this occurs at a manifold pressure signal MPV of 6 volts. T sensor 94 is calibrated so that 6 volts represents atmo pheric pressure of 30 inches of mercury. This establis the point at 30 inches of mercury and 0° manifold press advance MPA as shown in FIGURE 14A.As manifold pressure goes down from atmospher a voltage is developed across the tapped portion of the potentiometer A12 and current flows through the resisto R32 and the transistor Q6 in proportion to the signal difference, with a characteristic slope determined by the setting of the potentiometer A12. The potentiomete A12 thus determines the slope SI of the curve shown in FIGURE 14A. The current is applied through a diode D7 and a switch 52-1 to a conductor 284 connected to the summing point 266. In general, it is desirable that th slope of the characteristic at higher pressures be grea than the slope at lower pressures. Indeed at lower pre sures the slope may be as low as zero. To provide a second slope, a manifold pressure break reference signaTΪ is developed on a potentiometer A9« This reference signal is applied through an amplifier N6-5, 6, 7 and a diode D2 to keep a reference terminal 286 from rising above the manifold pressure break reference potential. This means that when the manifold pressure signal at the conductor 280 rises above the reference potential on the terminal 286, the signal picked off the tap of the potentiometer A10 responds to the manifold pressure signal to a lesser degree providing a different slope to the characteristic curve. As shown in FIGURE 14A, the break in the curve occurs at the potential corresponding to the manifold pressure break reference signal developed at the poten¬ tiometer A9, and the slope S2 at lower pressures is determined by the setting of the potentiometer A10.. An idle signal IDLE is developed in an idle timing limit circuit 290 when the engine is idling. The IDLE signal is applied on a conductor 288, and operates at idle to turn on a transistor Q5 to apply the 6-volt power supply potential to the inputs of the amplifiers N6- 1, 2, 3 and N7-5, 6, 7, this simulating a manifold pressure signal indicating 30 inches of mercury. The effect of this is that at idle there is zero manifold pressure advance and the capacitor C8 is entirely discharged. When the engine is speeded up above idle, the manifold pressure advance signal begins from zero and rises slowly in accordance with the time constant of the integrating circuit C8, All and instantly returns to 0° upon idling. The effect of the integrating circuit C8, All is that the manifold pressure advance signal can rise only slowly but can be retarded promptly. The effect of the idle signal in conjunction with the integrating circuit C8, All is that th.e timing is retarded to provide better emissions control during city driving when there are many stops, but slowly rises to an appropriate timing advance for better mileage in highway driving. With 'some engines under some conditions, it ma be necessary or desirable to have a relatively low timin advance to meet emissions standards. On the other hand, when maximum power is needed, it would be desirable to advance the spark. Such advance is provided by a thrott position advance circuit 292. The throttle position ad¬ vance circuit receives its input over the conductor 86 in the form of the throttle position signal TPV. This signal is applied through a follower circuit N3-5, 6, 7 and a resistor R12 to a terminal 294. This signal is the developed across a potentiometer A4 in series with a resistor R16. A portion of the signal is picked off the tap of the potentiometer A4 and applied to an amplifier N 5, 6, 7, the output of which includes a current mirror circuit 296 which produces an output current through a resistor R23 and thence through a switch Sl-4 to a con¬ ductor 298. The amplifier N7-5, 6, 7 is biased by a volt divider comprising a resistor R44 and a resistor R21 and by a voltage divider comprising a resistor R17 and a resistor R16. These potentials determine the throttle position or throttle position signal TPV at which the output of the amplifier N7-5, 6, 7 drives a transistor Q5 of the current mirror 296 into conduction. Above that throttle position, that is, with the throttle wider open, the throttle position advance signal rises with throttle position in accordance with the characteristic illustrated in FIGURE 14B as the curve TPA., the throttle position advance characteristic. The curve begins at zero advance at the throttle position determined by the bias potentials determined by the resistors R17, R16, R44 and R21. The characteristic then rises linearly in accordance with the gain determined by the otentiometer A4.Engines operate at a higher temperature when running at a higher speed. Thus, when the throttle is opened to accelerate the engine, the engine is cooler than it will be when it reaches the desired speed. This indicates the desirability of advancing the timing upon acceleration. A Δ throttle position advance circuit 300 provides such additional spark advance. In this circuit, the signal at the terminal 294 is applied to a differentiating circuit comprising a capacitor C3 and a potentiometer A3. A signal is developed at the tap of the potentiometer A3 that decays with a time constant of perhaps one second to develop a differential signal. This signal is applied through an amplifier N7-1, 2, 3 and a current mirror circuit 302, producing an output signal ΔTPA signal through a switch Sl-3 to a conductor 3O4 connected to the summing point 274. The magnitude of this signal is determined by the change in the throttle position signal TPV and the setting of the potentiometer A3. An amplifier N6-1, 2, 3 and a diode D2 operate to keep the change signal from going negative. That is, the signal ΔTPA can go only positive. This means that addi¬ tional spark advance is provided upon movement of the throttle in the opening direction, but subtracts nothing when the throttle is moved toward its closed position. Because hotter ambient air results in faster burning in the cylinders less advance is needed when the air temperature is high. To this end, a temperature limit circuit 306 is utilized to limit the advance provided by the throttle position advance circuit 292 and the Δ throttle position advance circuit 300. The input signals to the temperature limit circuit 306 are the air density signal ADV applied on the conductor 128 and the barometric pressure signal BPV applied on the conductor 116. The barometric pressure signal is applied to an amplifier N4-5, 6, 7 to produce a corresponding signal at N4-7. This signal is applied across a potentiometer A2 in series with a resistor R5. The tap on the potentiometer A2 thus provides a signal proportional to the barometric pressure signal BPV. Similarly, the air density signal ADV is applied to an amplifier N4-1, 2, 3 which produces at N4- 1 a signal corresponding to air density. As air density is proportional to barometric pressure and inversely pro portional to temperature, the signal developed at the tap of the potentiometer A2 corresponds to air density a some temperature. The setting of this tap determines a temperature TPT at which the signal at the tap is equal to the air density signal at N4-1. In the example illus¬ trated by FIGURE 14B, this temperature is about 170°F. The signal at the tap of the potentiometer A2 is applied through a follower circuit N5-5, 6, 7 and applied throug a resistor R6 to the - terminal of an -amplifier N5-1, 2, 3. A potentiometer Al is connected between N5-6 and N4-1. The tap on the potentiometer Al is connected to the -+..terminal of the amplifier N5-1, 2, 3. The amplifie N5-1, 2, 3 thus amplifies a portion of the difference between the air density signal ADV and the reference signal corresponding to air density at a particular voltag as developed by the potentiometer A2. The output of the amplifier N5-1, 2, 3 is applied through a current mirror 308 to develop a corresponding signal across a resistor R9. That signal is applied through an amplifier N6-5, 6, 7 and a diode Dl to the terminal 294. The setting of the potentiometer Al determines the slope TPT SLOPE of the characteristic temperature limit curve TPTL as shown in FIGURE 14B. The effect of the temperature limit cir¬ cuit 306 is to prevent the signal at the terminal 294 from rising above the signal developed by the temperature limit circuit 306 across the resistor R9. This limits bo the temperature position advance signal TPA and the Δ temperature position advance signal ΔTPA, preventing eith from rising above the limit TPTL set by the temperature limit circuit 306.Burning rate varies with the richness of the air/fuel mixture. It has been determined, for example,--BUROM that .at least in certain engines under certain Conditions the engine begins knocking at an air/fuel ratio of about 16. At leaner ratios more advance can be used due to slower flame propagation. This is achieved by a ratio control advance circuit 31Q to provide a characteristic curve RCA as shown in FIGURE 14C. The ratio control advance circuit receives as an input signal the ratio control signal RCV on the conductor 160. A reference potential is developed by a voltage divider formed by resistors R23 and R24. An amplifier N4-12, 13, 14 develops this same reference potential at N8-14. The ratio control signal RCV is applied to an amplifier N8-1, 2, 3 to produce a signal at N8-2 that is at least as high as the ratio control signal RCV. A diode Dl causes the signal at N8- 2 to be held at the reference level developed at N8-14 should the signal RCV be below the reference potential. A potentiometer A8 is connected between N8-2 and N8-14. The tap of the potentiometer A8 is thus some portion of the amount that the signal at N8-2 is above the reference potential at N8-14. If the ratio control signal RCV is not above the reference potential, then the tap of the potentiometer A8 remains at the reference potential. Amplifiers N8-5, 6, 7 and N8-8, 9, 10 cause current to flow through a resistor R25 in proportion to this differ- ence. This current flows through a transistor Q4 and a switch S2-2 to supply current through a conductor 312 corresponding to the desired ratio control advance RCA according to the characteristic illustrated in FIGURE 14C. The point on the curve at 0° advance is established by the voltage dividers R23 and R24. The slope RCVG of the curve is determined by the setting of the potentiom¬ eter A8. Thus, the reference potential may be equivalent to a 16:1 air/fuel ratio, so that above this ratio, the timing is advanced in accordance with the characteristic illustrated. This current is applied to the summing point 266 through the switch Sl-2. For the sake of emission control, engines are ordinarily operated at less than maximum efficiency. For example, they are usually run slightly retarded duri normal engine operation. There are, however, occasions when it is more important to assure smooth operation.Perhaps the most difficult time an engine has is at star ing. To assure appropriate operation while the engine is being started and until it is warmed up, it is desira to operate at greater efficiency, even though this may for a time increase emissions. To this end, a start adva circuit 314 provides an additional advance signal. The start advance circuit receives its input from the igniti switch as the 12V ST signal over the conductor 102. The 12V ST signal turns on a transistor Q12 to charge a capacitor C6 from the 6-volt power supply when the start switch is closed to operate the starter motor. This cha then leaks off slowly through a potentiometer A6 and a resistor R39 connected in series across the capacitor C6 A portion of the potential across the capacitor C6 is picked off by the tap of the potentiometer A6. As one end of the potentiometer A6 is connected to the 6-volt power supply, the signal at the tap of the potentiometer A6 thus is driven somewhat negative with respect to the 6-volt power supply and gradually rises to 6 volts as the capacitor C6 discharges through the resistor R9 and the potentiometer A6. The time constant may be set, for example, at 90 seconds. The signal on the tap of the potentiometer A6 is applied to an amplifier N3-1, 2, 3 which controls the current flow through a transistor Qll and a resistor R38 to maintain the current through the resistor R38 proportional to the difference between 6 volts and the potential at the tap of the potentiomete A6. This thus introduces current through a switch Sl-2 and thence through a conductor 316 to the summing point 274 as the start advance signal STA. The initial magnitu of the current is determined by the setting of the poten¬ tiometer A6 and the duration of the start advance signal is determined by the time constant of the circuit C6, A6, R39. 90 seconds is a convenient time for expecting the engine to be started and in reasonable running condi¬ tion. A start advance of about 10° has been found accept¬ able in certain engines.When the engine is cold, the burning of the fuel in the cylinders is slower than when the engine is warmed up. To provide appropriate timing when the engine is cold, a cold advance signal is introduced by a cold advance circuit 318. The input to this circuit is the cold signal CLD applied over the conductor 158. This signal, which is high when the engine temperature is below the predetermined level, is used to turn on a tran¬ sistor Q7. This provides an inverted cold signal CLD-2 on a conductor 320. At the same time, the closing of the transistor Q7 causes current to flow through a voltage divider formed of resistors R27 and R28, turning on a transistor Q8 and causing current to fldw through a resistor R30 and a switch Sl-5 and thence through a conductor 322 to the summing point 274. The cold advance signal CLDA is the current thus determined by the relative magnitudes of the resistances R27, R28 and R30. A diode 30 compensates for- the base to emitter drop of the transis¬ tor Q8.The inverted cold signal CLD-2 is also applied by way of the conductor 320 to the manifold pressure advance circuit 278, where the inverted cold signal CLD- 2 is applied to a diode D6. It acts to ground the output of the manifold pressure advance circuit when the engine is cold. This turns off the manifold pressure advance. The purpose of this is to cause the engine to heat up faster under light load and thus to arrive more promptly at its operating temperature where it may be caused to run leaner.Engines often have difficulty running uniforml under idle conditions. Under normal idle conditions, the burning is incomplete in the cylinders and is comple in the hotter exhaust manifold. It is desirable to prov stable idle ignition. This may be achieved by retarding the spark during idle from where it would otherwise be caused to occur with the spark advance circuits describe above. An idle timing limit circuit 324 provides means for assuring a particular spark advance during idle con¬ ditions. The idle timing limit circuit 324 responds to the mass flow signal MFV on the conductor 146. This signal is applied to the + terminal of a comparator N4- 1, 2, 3. A reference potential is developed on a potentiometer A7 and applied to the negative terminal of the amplifier. Until the mass flow signal exceeds the reference potential as set by the potentiometer A7, the potential at the amplifier output terminal N4-1 remains low. A potentiometer A5 and a resistor 11 are connected between the terminal N4-1 and the 6-volt power supply.The tap of the potentiometer A5 can thus be set to provi a potential in between. The potential on the tap A5 is applied through a follower circuit N4-5, 6, 7 and thence through a switch S2-4 through a conductor 326 connected to the summing point 266. The characteristic curve IL for the idle timing limit circuit appears in FIGURE 14D. Below idle speed timing signal break level ITB as deter¬ mined by the potentiometer A7, the idle timing advance is maintained constant at its lower idle timing limit IT as determined by the setting of the potentiometer A5. For example, as shown in FIGURE 14D, the idle timing advance is set at 10° up to a flow rate providing an ai flow signal of 0.18 volts. When the mass flow signal MF rises above that corresponding to idle air flow, the dif ference between the mass flow signal MFV and the idle timing reference signal at the tap of the potentiometer A7 is amplified by the amplifier N4-1, 2, 3 causing the limit signal developed at the tap of the potentiometer A5 to rise in accordance with the characteristic illustrated in FIGURE 14D with a slope determined by the magnitude of the resistance of a variable resistor A6. This slope should be relatively steep to assure prompt release of the low idle timing limit when the engine is above idle. On the other hand, the slope must not be so steep so as to occasion a sharp jump in timing when the engine is operating near idle, as otherwise there would be sharp surges in power.The idle timing limit signal IL operating through the output circuit N4-5, 6, 7 holds the spark advance signal as developed across the resistor R8 to the maximum permitted by the idle timing limit circuit. That is, the output of the output circuit N4-5, 6, 7 can never rise above the idle limit potential IL developed at the tap of the potentiometer A5. At the same time, the signal at the terminalN4-1 is applied to the + terminal of an amplifier N5-5, . 6, 7 which operates to provide a signal IDLE at the output terminal N5-7 indicative of an idle condition. The IDLE signal is applied to control a transistor Q7 to apply the 6-voϊt supply voltage to the conductor 284 through a resistor R35 when the engine is idling. This forces the output of the manifold pressure advance circuit high when the engine is idling, assuring that the signal MPA as applied to the summing point 266 forces the signal developed across the summing resistor R8 to the upper limit permitted, which at idle is the low idle timing limit IT.When the engine overheats, as may be indicated by a signal on a conductor 327 when the overheat warning light goes on, it is desirable to cause the engine to idle so ewhat faster to permit it to cool off. This may be achieved by disabling the idle timing limit when the engine is overheated. To this end, the signal OVERHEAT indicating overheating may be applied to turn on a transis Q3 and thus lower the bias at N4-2.The IDLE signal is also applied over the condu tor 288 to the manifold pressure advance circuit as described above to control the dumping of the charge on the capacitor C8, dumping the charge when the engine spe drops below idle.A particularly bad time for emissions is when an engine is decelerating. Under such conditions, the fuel is much reduced, as is the air intake. Some fuel will then evaporate from the intake manifold, where it may have accumulated along the manifold walls, and pass into the engine. In general, combustion is poor under these conditions, likely resulting in excessive unburned hydrocarbon emissions. Of course, under these condition power is not needed or even desired. Hence, it is pos- sible to reduce hydrocarbon emissions without sacrificin any desired or needed power when the engine is deceleratin This may be achieved by assuring that the spark is not far advanced under deceleration conditions. This is the function of a decel limit circuit 328 which provides a deceleration timing limit signal DECEL L in accordance with the characteristic illustrated in FIGURE 14D. In this case, the controlling input is the modified manifol pressure signal MPVB as applied to the conductor 280 in the manifold pressure advance circuit 278. A decel reference potential signal DPV is developed on the condu tor 226 by a potentiometer Al and an amplifier Nl-5, 6, 7. This reference level DPV is set by the setting of the potentiometer Al connected to the 6-volt power suppl The reference DPV corresponds to a manifold pressure bel which the engine may be considered to be decelerating.A potentiometer A2 is connected between the conductors BUO 226 and 280. The difference between the reference potential, on the conductor 226 and the modified manifold pressure signal MPVB therefore appears across the potentiometer A2 and a portion thereof is picked off at the tap of the potentiometer. The setting of this potentiometer thus determines the gain of the circuit and hence the slope of the characteristic curve illustrated in FIGURE 14D. This difference signal is amplified by an amplifier Nl- •1, 2, 3 and is applied through a current mirror circuit 330 to cause the current to flow through a resistor R6 pro¬ portional to the amount by which the modified manifold pressure signal MPVB exceeds the reference potential DPV. When the manifold pressure signal is below this level, a transistor Q2 is non-conductive and no current there- through flows through the resistor R6.The base of the deceleration limit characteristic as illustrated in FIGURE 14D is provided at a terminal 332 by a voltage divider A3 and an amplifier N3-5, 6, 7.• The setting of the potentiometer A3 determines the base reference potential developed at the terminal 332. In absence of conduction by the transistor Q2, the base reference potential is applied to the + terminal of a comparator N2-5, 6, 7 which acts like the comparator N4- 5, 6, 7 to limit the decel timing advance signal, as devel- oped across the summing resistor R8 to a value no greater than the potential at the + input terminal of the compa¬ rator N2-5, 6, 7. The setting of the potentiometer A3 thus determines the base decel advance limit for the por¬ tion of the characteristic curve below the decel pressure limit DPV set at the conductor 226. This limit is shown as 20° in FIGURE 14D. Above this limit, the characteristic rises with a slope determined by the setting of the po¬ tentiometer A2. The output signal DECEL L of the decel timing limit circuit 328 is applied through a switch S2- 5 and a conductor 334 to the summing point 266.It is necessary that the range of timing advance'BUREAUOMPI A,- WIPO be limited in order that the timing advance not vary so much as to permit firing of the wrong cylinder. That is, the distributor in the ignition system 24 directs ignition current at the appropriate times to the respectiv spark plugs in the respective cylinders. It is necessary that the ignition pulse intended to create a spark in a respective cylinder occur at such time as the distributo is directing current to that cylinder. If the spark is too advanced it will appear as a late spark for a precedin cylinder. An upper limit to the spark advance is provided by an upper advance limit circuit 338. The upper advance limit circuit comprises simply a potentiometer A4 and a comparator N2-1, 2, 3. This circuit acts to prevent the output signal on an output terminal 340 from rising above the reference potential set by the potentiometer A4.This thus limits the decel limit advance DECEL L at the value determined by the potentiometer A4. As shown in the example of FIGURE 14D, this limit is 50°. When the switch S2-5 is closed, this also acts to limit the timing advance signal, however developed, as it limits the voltage rise at the summing point 266.For similar reasons of limiting the range of the timing advance control, a lower limit of timing advanc signal is provided by a lower advance limit circuit 342 (FIGURE 12). The lower advance limit circuit comprises a potentiometer A9 which determines the lower reference limit, an amplifier N8-1, 2, 3 and an output diode D5. The diode D5 causes a lower limit signal LL to be coupled through a switch Sl-6 to a conductor 344 which is connected to the summing point 374 whenever the lower reference limit is greater than the timing advance signal as otherwis developed at the summing point 374. This prevents the timing advance signal from falling below this reference level LL. Under many circumstances, no lower limit is necessary because the various timing advance circuits the selves assure sufficient advance of the spark as to preclude firing in the wrong cylinder.A capacitor C4 is connected across the summing resistor R8 and acts to smooth out rapid changes in the timing advance. Thus, the various timing advance circuits provide current to the summing resistor R8 and develop a cumulative signal which is limited by the various limit circuits and is then applied through the amplifier N3-1, 2, 3 as the timing control signal TCV applied over the conductor 236 to the ignition timing controller 11.Referring to FIGURE 14, a switch position chart shown in FIGURE 14E indicates which of the various switches are operated to put the various limit circuits or timing advance circuits into the timing advance system. Normally, all of the various control circuits are in the system. However, there are many engines for which the throttle position advance circuit and the Δ throttle position advance circuit are not needed. The switch position indicated as PROG represents a programming position and refers to a switch S2-3 which is part of a test circuit 356 connected by a conductor 358 to the summing point 266. The test circuit 356 applies a full test signal to the summing point 266 and forces the timing to its limit as an aid to checking the setting of the circuits. Although a preferred embodiment of the circuitry of the controller 2 has been shown, various modifications may be made therein within the scope of the present invention. For example, as mentioned above, not all of the timing circuits need be switched into the timing control system at the same time. Different engines and the different automobiles in which the engines are to be used may dictate other operating controls within the spirit of the present invention. Further, the various limits, reference potentials, and slopes of various char- acteristics can be adjusted within the skill of the art to meet particular operating requirements and to eet various legal requirements for mileage and emission control.In the exemplary circuits, typical components and component values are specified on the drawings. It is to be understood that various DC power supplies are furnished in a conventional manner and that the various integrated circuits are supplied with power in the usual manner. | CLAIMS:1. An electronic controller for an internal combustion engine having a throttle for controlling the flow of air into an intake manifold wherein rate of air flow into the engine is measured by producing an air flow signal systematically related to the rate of air flow, and rate of fuel flow into the engine is measured by producing a fuel flow signal systematically related to the rate of fuel flow, said electronic controller in¬ cluding means for producing a ratio control signal cor¬ responding to a respective air/fuel ratio, and means re¬ sponsive to said air flow signal, said fuel flow signal and said ratio control signal for controlling fuel flow as to make the ratio of air flow to fuel flow substan¬ tially equal to said respective air/fuel ratio, charac¬ terized in that said means for producing said ratio con¬ trol signal comprises means for providing a base run ratio signal corresponding to a respective run air/fuel ratio suitable for steady state engine operation, means for providing a temperature reference signal correspond¬ ing to a reference engine temperature, means responsive to engine temperature and said temperature reference sig¬ nal for modifying said run ratio signal in systematic relation to engine temperature when said engine tempera¬ ture is below said reference engine temperature to pro¬ duce a run ratio signal corresponding to an air/fuel ratio systematically decreasing with decrease in engine temperature below said reference engine temperature, out¬ put means responsive to applied ratio signals for pro¬ ducing a ratio control signal corresponding to the lowest air/fuel ratio of any applied ratio signal, and means for applying said run ratio signal to said output means. .2.. Apparatus according to Claim 1 character¬ ized by means for providing a base first power ratio signal corresponding to a respective first power air/ fuel ratio, means for providing a manifold vacuum ref¬ erence signal corresponding to a reference manifold vacuum, means responsive to engine manifold vacuum and said manifold vacuum reference signal for modifying said base first power ratio signal in systematic relation to manifold vacuum when said manifold vacuum is above said reference manifold vacuum to produce a first power ratio signal corresponding to an air/fuel ratio systematically increasing with increase in manifold vacuum, and means for applying said first power ratio signal to said out¬ put means.3. Apparatus according to Claim 2 character¬ ized by means responsive to engine temperature and said temperature reference signal for further modifying said first power ratio signal in systematic relation to engine temperature when said engine temperature is below said reference engine temperature to produce a first power ratio signal corresponding to an air/fuel ratio system¬ atically decreasing with decrease in engine temperature below said reference engine temperature.4. Apparatus according to either one of Claims 2 and 3 characterized by means responsive to engine throttle position for producing a second power ratio sig nal corresponding to a respective second power air/fuel ratio less than said first power air/fuel ratio when the throttle is substantially wide open and otherwise corre¬ sponding to a non-limiting air/fuel ratio, and means for applying said second power ratio signal to said output means.5. Apparatus according to Claim 4 character¬ ized by means for providing a high engine speed referenc signal corresponding to a reference high engine speed, means responsive to engine speed and said high engine speed reference signal for providing a base third powerOΛ I ratio signal corresponding to a respective third power air/fuel ratio less than said second power air/fuel ratio when the engine speed is greater than said reference high engine speed and systematically increasing with decrease in engine speed below said reference high engine speed, and means responsive to throttle position for applying said third power ratio signal to said output means when the throttle is substantially wide open.6. Apparatus according to any one of Claims 1 to 5 characterized by means for providing an engine idle reference signal corresponding to engine operation at idle, means for providing a base idle ratio signal corre¬ sponding to a respective idle air/fuel ratio suitable for operation of the engine at idle, means responsive to engine operation and said engine idle reference signal for modifying said base idle ratio signal in systematic relation to engine operation when said engine operates above idle to produce an idle ratio signal corresponding to an air/fuel ratio systematically increasing with in¬ crease in engine operation above idle, and means for applying said idle ratio signal to said output means.7. Apparatus according to Claim 6 character¬ ized in that engine idle is sensed by sensing rate of air flow.8. Apparatus according to Claim 6 character¬ ized in that engine idle is sensed by sensing engine speed.9. Apparatus according to any one of Claims 1 to 5 characterized by means for providng an engine idle reference signal corresponding to a reference engine speed, means for providing a base idle ratio signal corresponding to a respective idle air/fuel ratio suit¬ able for operation of the engine at idle, means respon¬ sive to engine speed and said engine idle reference sig¬ nal for modifying said base idle ratio signal in system-IUJ EATOMPI atic relation to engine speed when said engine speed exceeds said reference engine speed to produce an idle ratio signal corresponding to an air/fuel ratio system¬ atically increasing with increase in engine speed above said reference engine speed, and means for applying said idle ratio signal to said output means.10. Apparatus according to any one of Claims 1 to 5 characterized by means for providing an engine idle reference signal corresponding to a reference air flow, means for providing a base idle ratio signal corre sponding .to a respective idle air/fuel ratio suitable fo operation of the engine at idle, means responsive to rat of air flow into the engine and said engine idle reference signal for modifying said base idle ratio signal in systematic relation to rate of air flow when said rate of air flow exceeds said reference air flow to produce an idle ratio signal corresponding to an air/fuel ratio systematically increasing with increase in air flow above said reference air flow, and means for applying said idle ratio signal to said output means.11. Apparatus according to any one of Claims 6 to 10 characterized by means responsive to engine tem¬ perature and said temperature reference signal for fur¬ ther modifying said idle ratio signal in systematic re¬ lation to engine temperature when said engine temperatur is below said reference engine temperature to produce an idle ratio signal corresponding to .an air/fuel ratio sys tematically decreasing with decrease in engine tempera¬ ture below said reference engine temperature.12. Apparatus according to any one of Claims 6 to 11 characterized by means responsive to starting of the engine for developing a start enrich signal that de¬ cays with time, and means responsive to said start en¬ rich signal for further modifying said idle ratio signal to correspond to a lower air/fuel ratio upon starting, such modification decaying with said start enrich signal.13. Apparatus according to any one of Claims 1 to 12 characterized by means for providing a manifold pressure reference signal corresponding to a reference pressure in said manifold, means for providing a base de¬ cel ratio signal corresponding to a respective decel air/ fuel ratio suitable for engine operation below said ref¬ erence pressure, means responsive to pressure in said manifold and said manifold pressure reference signal for modifying said base decel ratio signal in systematic re¬ lation to manifold pressure when the manifold pressure is above said reference pressure to produce a decel ratio signal corresponding to an air/fuel ratio systematically increasing with increase in manifold pressure above said reference pressure, and means for applying said decel ratio signal to said output means.14. An electronic controller for an internal combustion engine having a throttle for controlling the flow of air into an intake manifold wherein rate of air flow into the engine is measured by producing an air flow signal systematically related to the rate of air flow, and rate of fuel flow into the engine is measured by pro¬ ducing a fuel flow signal systematically related to the rate of fuel flow, said electronic controller including means for producing a ratio control signal corresponding to a respective air/fuel ratio, and means responsive to said air flow signal, said fuel flow signal and said ratio control signal for controlling fuel flow as to make the ratio of air flow to fuel flow substantially equal to said respective air/fuel ratio, characterized in that said means for producing said ratio control sig¬ nal comprises means for providing a run ratio signal corresponding to a respective run air/fuel ratio suit¬ able for engine operation under certain conditions, means for providing at least one other ratio signal correspond- ing to a respective air/fuel ratio suitable for engine operation under certain other conditions, output means responsive to applied ratio signals for producing a ratio control signal corresponding to the lowest air/ fuel ratio of any applied ratio signal, and means for applying said run ratio and said at least one other rati signal to said output means.15. Apparatus according to Claim 14 character ized .in that said means for providing at least one other ratio signal includes means for providing a base first power ratio signal corresponding to a respective first power air/fuel ratio, means for providing a manifold vacuum reference signal corresponding to a reference manifold vacuum, and means responsive to engine manifold vacuum and said manifold vacuum reference signal for modifying said base first power ratio signal in system¬ atic relation to manifold vacuum when said manifold vacuum is above said reference manifold vacuum to pro¬ duce a first power ratio signal corresponding to an air/ fuel ratio systematically increasing with increase in manifold vacuum, and wherein said means for applying said at least one other ratio signal includes means for applying said first power ratio signal to said output means.16. Apparatus according to Claim 15 character ized by means for providing a temperature reference sig¬ nal corresponding to a reference engine temperature, means responsive to engine temperature and said tempera¬ ture reference signal for further modifying said first power ratio signal in systematic relation to engine tem¬ perature when said engine temperature is below said ref¬ erence engine temperature to produce a first power ratio signal corresponding to an air/fuel ratio systematically decreasing with decrease in engine temperature below said reference engine temperature. 17. Apparatus according to either one of Claims 15 and 16 characterized in that said means for providing at least one other ratio signal includes means responsive to engine throttle position for producing a second power ratio signal corresponding to a respective second power air/fuel ratio less than said first power air/fuel ratio when the throttle is substantially wide open and otherwise corresponding to a non-limiting air/ fuel ratio, and wherein said means for applying said at least one other ratio signal includes means for applying said second power ratio signal to said output means.18. Apparatus according .to Claim 17 character¬ ized in that said means for providing at least one other ratio signal includes means for providing a high engine speed reference signal corresponding to a reference high engine speed, and means responsive to engine speed and said high engine speed reference signal for providing a base third power ratio signal corresponding to a respec¬ tive third power air/fuel ratio less than said second power air/fuel ratio when the engine speed is greater than said reference high engine speed and systematically •increasing with decrease in engine speed below said ref¬ erence high engine speed, and wherein said means for applying said at least one other ratio signal includes means responsive to throttle position for applying said third power ratio signal to said output means when the throttle is substantially wide open.19. Apparatus according to any one of Claims 14 to 18 characterized in that said means for providing at least one other ratio signal includes means for pro¬ viding an engine idle reference signal corresponding to engine operation at idle, means for providing a base idle ratio signal corresponding to a respective idle air/fuel ratio suitable for operation of the engine at idle, and means responsive to engine operation and said engine idle reference signal for modifying said base idl ratio signal in systematic relation to engine operation when said engine operates above idle to produce an idle ratio signal corresponding to an air/fuel ratio system¬ atically increasing with increase in engine operation above idle, and wherein said means for applying said at least one other ratio signal includes means for applyin said idle ratio signal to said output means.20. Apparatus according to Claim 19 characte ized in that engine idle is sensed by sensing rate of a flow.21. Apparatus according -to Claim 19 characte ized in that engine idle is sensed by sensing engine • speed.22. Apparatus according to any one of Claims 14 to 18 characterized in that said means for providing at least one other ratio signal includes means for pro¬ viding an engine idle reference signal corresponding to a reference engine speed, means for providing a base id ratio signal corresponding to a respective idle air/fue ratio suitable for operation of the engine at idle, and* means responsive to engine speed and said engine idle reference signal for modifying said base idle ratio sig nal in systematic relation to engine speed when said engine speed exceeds said reference engine speed to pro duce an idle ratio signal corresponding to an air/fuel ratio systematically increasing with increase in engine speed above said reference engine speed, and wherein said means for applying said at least one other ratio signal includes means for applying said idle ratio sig¬ nal to said output means.23. Apparatus according to any one of Claims 14 to 18 characterized in that said means for providing at least one other ratio signal includes means for pro¬ viding an engine idle reference signal corresponding toO a reference air flow, means for providing a base' idle ratio signal corresponding to a respective idle air/fuel ratio suitable for operation of the engine at idle, and means responsive to rate of air flow into the engine and said engine idle reference signal for modifying said base idle ratio signal in systematic relation to rate of air flow when said rate of air flow exceeds said reference air flow to produce an idle ratio signal corresponding to an air/fuel ratio systematically increasing with in¬ crease in air flow above said reference air flow, and wherein said means for applying said at least one other ratio signal includes means for applying said idle ratio signal to said output means.24. Apparatus according to any one of Claims 19 to 23 characterized by means for providing a tempera¬ ture reference signal corresponding to a reference engine temperature, means responsive to engine temperature and said temperature reference signal for further modifying said idle ratio signal in systematic relation to engine temperature when said engine temperature is below said reference engine temperature to produce an idle ratio signal corresponding to an air/fuel ratio systematically decreasing with decrease in engine temperature below said reference engine temperature.25. Apparatus according to any one of Claims 19 to 24 characterized by means responsive to starting of the engine for developing a start enrich signal that decays with time, and means responsive to said start en¬ rich signal for further modifying said idle ratio signal to correspond to a lower air/fuel ratio upon starting, such modification decaying with said start enrich signal.26. Apparatus according to any one of Claims 14 to 25 characterized in that said means for providing at least one other ratio signal includes means for pro¬ viding a manifold pressure reference signal corresponding to a reference pressure in said manifold, means for pro¬ viding a base decel ratio signal corresponding to a re¬ spective decel air/fuel ratio suitable for engine opera¬ tion below said reference pressure, and means responsive to pressure in said manifold and said manifold pressure reference signal for modifying said base decel ratio sig¬ nal in systematic relation to manifold pressure to pro¬ duce a decel ratio signal corresponding to an air/fuel ratio systematically increasing with increase in manifold pressure above said reference pressure, and wherein said means for applying said at least one other ratio signal includes means for applying said decel ratio signal to said output means.27. An electronic controller for an internal combustion engine having a throttle for controlling the flow of air into an intake manifold wherein rate of air flow into the engine is measured by producing an air flow signal systematically related to the rate of air flow, and rate of fuel flow into the engine is measured by pro¬ ducing a fuel flow signal systematically related to the rate of fuel flow, said electronic controller including means for producing a ratio control signal corresponding to a respective air/fuel ratio, and means responsive to said air flow signal, said fuel flow signal and said ra¬ tio control signal for controlling fuel flow as to make the ratio of air flow to fuel flow substantially equal to said respective air/fuel ratio, characterized in that said means for producing said ratio control signal com¬ prises means for providing a manifold pressure reference signal corresponding to a reference pressure in said manifold, means for providing a base decel ratio signal corresponding to a respective decel air/fuel ratio suit¬ able for engine operation below said reference pressure, means responsive to pressure in said manifold and said manifold pressure reference signal for modifying saidO base decel ratio signal in systematic relation to mani¬ fold pressure when the manifold pressure is above said reference pressure to produce a decel ratio signal corre¬ sponding to an air/fuel ratio systematically increasing with increase in manifold pressure above said reference pressure, and means for utilizing said decel ratio sig¬ nal to produce a ratio control signal.28. An electronic controller for an internal combustion engine wherein rate of air flow into the en¬ gine is measured by producing an air flow signal system¬ atically related to the rate of air flow through a tur¬ bine, and rate of fuel flow into the engine is measured by producing a fuel flow signal systematically related to the rate of fuel flow, said electronic controller in¬ cluding means for producing a ratio control signal corre¬ sponding to a respective air/fuel ratio, and means re¬ sponsive to said air flow signal, said fuel flow signal and said ratio control signal for controlling fuel flow as to make the ratio of air flow to fuel flow substan¬ tially equal to said respective air/fuel ratio, charac¬ terized in that means coupled to said turbine for pro¬ ducing a turbine speed signal systematically related to the rate of rotation of said turbine, compensation means responsive to change in said turbine speed signal for producing a compensation signal of magnitude systematic¬ ally related to the magnitude of said change, and means for adding said compensation signal to said turbine speed signal to produce an air flow signal compensated for sluggishness in the response of said turbine to said air flow.29. Apparatus according to Claim 28 character¬ ized in that said compensation means includes means re¬ sponsive to said turbine speed signal for making the magnitude of said compensation signal inversely related to the magnitude of said turbine speed signal, whereby'BUREAUOMPl for a given change in rate of air flow the compensation signal is relatively small when the rate of air flow is relatively large.30. Apparatus according to Claim 29 characte ized in that said turbine speed signal is a DC signal o magnitude proportional to the speed of said turbine, an said compensation means includes a gain control formaki the magnitude of said compensation signal vary in inver proportion to said DC signal.31. An electronic controller for an internal combustion engine wherein rate of air flow into the en¬ gine is measured by producing an air flow signal system atically related to the rate of air flow, and rate of fuei flow into the engine is measured by producing a fue flow signal systematically related to the rate of fuel flow, said electronic controller including means for pr viding a ratio control signal corresponding to a respec tive air/fuel ratio, and control means responsive to sai air flow signal, said fuel flow signal and said ratio control signal for controlling the power supplied to a motor for driving a fuel pump to cause said pump to sup ply fuel at such rate as to make the ratio of air flow to fuel flow substantially equal to said respective air fuel ratio, characterized in that said control means shunts the motor when the fuel flow is in excess of the rate necessary to maintain said respective air/fuel rati32. An electronic controller for an internal combustion engine wherein rate of air flow into the en¬ gine is measured by producing an air flow signal system atically related to the rate of air flow, and rate of fuel flow into the engine is measured by producing a fuel flow signal in the form of first electronic pulses occurring at a rate systematically related to the rate of fuel flow, said electronic controller including mean for providing a ratio control signal corresponding to a respective air/fuel ratio, and control means responsive to said air flow signal, said fuel flow signal and said ratio control signal for driving a fuel pump at such rate as to make the ratio of air flow to fuel flow substantially equal to said respective air/fuel ratio, characterized in that said control means comprises means responsive to said first electronic pulses and said ratio control sig¬ nal for producing second electronic pulses of uniform duration at a rate that is a multiple of the rate of said first electronic pulses and of a magnitude proportional to said ratio control signal, and means for integrating said second electronic pulses to produce a DC signal of magnitude proportional to the product of the rate of occurrence of said first electronic pulses and said ratio control signal.33. Apparatus according to Claim 32 character¬ ized by means responsive to fuel temperature for varying said uniform duration in inverse proportion to fuel tem¬ perature.34. Apparatus according to either one of Claims 32 and 33 characterized by means for reducing -said multiple at relatively high, rates of fuel flow and at the same time compensating for the change in signal gain occasioned thereby.35. An electronic controller for an internal combustion engine having an ignition system responsive to ignition pulses for producing ignition sparks in com¬ bustion chambers and wherein rate of air flow into the intake manifold of the engine is measured by producing an air flow signal systematically related to the rate of air flow, and rate of fuel flow into the engine is mea¬ sured by producing a fuel flow signal systematically re¬ lated to the rate of fuel flow, said electronic control¬ ler including means responsive to engine parameters for producing a ratio control signal corresponding to a re- spective air/fuel ratio, and means responsive to said air flow signal, said fuel flow signal and said ratio control signal for controlling fuel flow as to make the ratio of air flow to fuel flow substantially equal to said respective air/fuel ratio, said controller further including means for generating a reference timing signa indicative of movement of the engine to a reference po¬ sition in the engine cycle, timing advance control mean for producing a timing advance control signal correspond ing to a respective angular displacement of said engine from said reference position, and means responsive to said reference timing signal and'said timing advance co trol signal for producing ignition pulses at positions relative to said reference timing position systematical related to said timing advance control signal, charac¬ terized in that said timing advance control means com¬ prises RPM advance means responsive to engine speed for producing an RPM timing advance signal systematically r lated to engine speed and corresponding to a respective timing advance systematically increasing with increase in engine speed, manifold pressure advance means re¬ sponsive to manifold pressure for producing a manifold pressure timing advance signal systematically related t manifold pressure and corresponding to a respective timing advance systematically decreasing with increase in manifold pressure, ratio control advance means re¬ sponsive to said ratio control signal for producing a ratio control timing advance signal systematically re¬ lated to said ratio control signal and corresponding to a respective timing advance systematically increasing with said increase in respective air/fuel ratio, output means responsive to applied timing advance signals for producing a timing advance control signal corresponding to the sum- of the respective timing advances, and means for applying said RPM timing advance signal, said mani-'BU^OM WI fold pressure timing advance signal and said ratio con¬ trol timing advance signal to said output means.36. Apparatus according to Claim 35 character¬ ized in that said timing advance control means includes limit means for limiting the timing advance control sig¬ nal to a maxiumu total timing advance.37. Apparatus according to Claim 36 character¬ ized in that said limit means comprises means for pro¬ viding an engine idle reference signal corresponding to engine operation at idle, means for providing a low idle timing limit signal corresponding to a respective timing advance suitable for operation of the engine at idle, means responsive to engine operation and said engine idle reference signal for modifying said low idle timing limit signal in systematic relation to engine operation when said engine operates above idle to produce an idle timing limit signal corresponding to a respective timing advance systematically increasing with increase in en¬ gine operation above idle, and means responsive to said idle timing limit signal for limiting the timing advance control signal to a maximum total timing advance corre¬ sponding to said idle timing limit signal.38. Apparatus -according to Claim 37 character¬ ized by means responsive to engine operation and said engine idle reference signal for forcing said timing advance control signal to the limit corresponding to said low idle timing advance when said engine is at idle.39. Apparatus according to Claim 36 character¬ ized in that said limit means comprises means for pro¬ viding an engine idle reference signal corresponding to a reference air flow, means for providing a low idle timing limit signal corresponding to a respective low idle timing advance suitable for operation of the engine at idle, means responsive to rate of air flow into the1-ΛJREAlTOMPI the engine and said engine idle reference signal for modifying said low idle timing limit signal in systemati relation to rate of air flow when said rate of air flow exceeds said reference air flow to produce an idle timi limit signal corresponding to a respective timing advan systematically increasing with increase in air flow abo said reference air flow, and means responsive to said idle timing limit signal for limiting the timing advanc control signal to a maximum total timing advance corre¬ sponding to said idle timing limit signal.40. Apparatus according to Claim 39 characte ized by means responsive to rate of air flow into the engine and said engine idle reference signal for forcin said timing advance control signal to the limit corre¬ sponding to said low idle timing advance when said rate of air flow does not exceed said reference air flow.41. An electronic controller for an internal combustion engine having an ignition system responsive to ignition pulses for producing ignition sparks in com bustion chambers, said controller including means for generating a reference timing signaJ. indicative of move ment of the engine to a reference position in the engin cycle, timing advance control means for producing a tim ing advance control signal corresponding to a respectiv angular displacement of said engine from said reference position, and means responsive to said reference timing signal and said timing advance control signal for pro¬ ducing ignition pulses at positions relative to said reference timing position systematically related to sai timing advance control signal, characterized in that sai timing advance control means comprises RPM advance mean responsive to engine speed for producing an RPM timing advance signal systematically related to engine speed and corresponding to a respective timing advance system atically increasing with increase in engine speed, mani fold pressure advance means responsive to manifold pressure for producing a manifold pressure timing advance signal systematically related to manifold pressure and corresponding to a respective timing advance systematic¬ ally decreasing with increase in manifold pressure, out¬ put means responsive to applied timing advance signals for producing a timing advance control signal correspond¬ ing to the sum of the respective timing advances, means for applying said RPM timing advance signal and said man¬ ifold pressure timing advance signal to said outputmeans, means for providing an engine idle reference signal cor¬ responding to engine operation at idle, means for pro¬ viding a low idle timing limit signal corresponding to a respective timing advance suitable for operation of the engine at idle, means responsive to engine operation and said engine idle reference signal for modifying said low idle timing limit signal in systematic relation to engine operation when said engine operates above idle to pro¬ duce an idle timing limit signal corresponding to a re¬ spective timing advance systematically increasing with increase in engine operation above idle, and means re¬ sponsive to said idle timing limit signal for limiting the timing advance control signal to a maximum total timing advance corresponding to said idle timing limit signal.42. Apparatus according to Claim 41 charac¬ terized by means responsive to engine operation and said engine idle reference signal for forcing said timing ad¬ vance control signal to the limit corresponding to said low idle timing advance when said engine is at idle.43. An electronic controller for an internal combustion engine having an ignition system responsive to ignition pulses for producing ignition sparks in com¬ bustion chambers, said controller including means for generating a reference timing signal indicative of move- ent of the engine to a reference position in the engin cycle, timing advance control means for producing a ti ing advance control signal corresponding to a respectiv angular displacement of said engine from said reference position, and means responsive to said reference timing signal and said timing advance control signal for pro¬ ducing ignition pulses at positions relative to said re erence timing position systematically related to said timing advance control signal, characterized in that sa timing advance control means comprises RPM advance mean responsive to engine speed for producing an RPM timing advance signal systematically related to engine speed and corresponding to a respective timing advance system atically increasing with increase in engine speed, mani fold pressure advance means responsive to manifold pres sure for producing a manifold pressure timing advance signal systematically related to manifold pressure and corresponding to a respective timing advance systematic ally decreasing with increase in manifold pressure, out put means responsive to applied timing advance signals for producing a timing advance control signal correspon ing to the sum of the respective timing advances, means for applying said RPM timing advance signal and said ma ifold pressure timing advance signal to said output mean means for providing an engine idle reference signal cor responding to a reference air flow, means for providing a low idle timing limit signal corresponding to a respe tive low idle timing advance suitable for operation of the engine at idle, means responsive to rate of air flo into the engine and said engine idle reference signal for modifying said low idle timing limit signal in sys¬ tematic relation to rate of flow when said rate of air flow exceeds said reference air flow to produce an idle timing limit signal corresponding to a respective timing advance increasing with increase in air flow above saidOM reference air flow, and means responsive to said idle timing limit signal for limiting the timing advance control signal to a maximum total timing advance corre¬ sponding to said idle timing limit signal.Claim 44. Apparatus according to Claim 43 characterized by means responsive to rate of air flow into the engine and said engine idle reference signal for forcing said timing advance control signal to the limit corresponding to said low idle timing advance when said rate of air flow does not exceed said reference air flow.45. An electronic controller for an internal combustion engine having an ignition system responsive to ignition pulses for producing ignition sparks; in com¬ bustion chambers, said controller including means for generating a reference timing signal indicative of move¬ ment of the engine to a reference position in the engine cycle, timing advance control means for producing a tim¬ ing advance control signal corresponding to a respective angular displacement of said engine from said reference position, and means responsive to said reference timing signal and said timing advance control signal for pro¬ ducing ignition pulses at positions relative to said reference timing .position systematically related to said timing advance control signal, characterized in that said timing advance control means comprises RPM advance means responsive to engine speed for producing an RPM timing advance signal systematically related to engine speed and corresponding to a respective timing advance systematically increasing with increase in engine speed, manifold pressure advance means responsive to manifold pressure for producing a manifold pressure timing ad¬ vance signal systematically related to manifold pressure and corresponding to a respective timing advance system¬ atically decreasing with increase in manifold pressure, said manifold pressure advance means including delay means for causing said manifold pressure timing advance signal to change slowly in the direction of greater timing advance relative to changes in the direction of lesser timing advance, output means responsive to appli timing advance signals for producing a timing advance control signal corresponding to the sum of the respecti timing advances, and means for applying said RPM timing advance signal and said manifold pressure timing advanc signal to said output means.46. Apparatus according to Claim 45 characte ized by means responsive to engine idle for disabling said delay means when said engine idles.47. Apparatus according to any one of Claims 36 to 44 characterized by means for providing a manifol pressure reference signal corresponding to a reference pressure in said manifold, means for providing a base decel timing limit signal corresponding to a respective timing advance suitable for combustion in the engine upon deceleration, means responsive to pressure in said manifold and said manifold pressure reference signal fo modifying said base decel timing limit signal in system¬ atic relation to manifold pressure when the manifold pressure is above said reference pressure to produce a decel timing limit signal corresponding to a respective timing advance systematically increasing with increase in manifold pressure above said reference pressure, and means responsive to said decel timing limit signal for limiting the timing advance control signal to a maximum total timing advance corresponding to said decel timing limit signal.48. Apparatus according to any one of Claims 35 to 47 characterized by means responsive to starting of the engine for producing at start a start advance timing signal decaying with time and corresponding tc aQ respective timing advance decreasing with time, and means for applying said start advance timing signal to said output means.49. Apparatus according to any one of Claims 35 to 48 characterized by means for providing a tempera¬ ture reference signal corresponding to a reference engine temperature, means responsive to engine temperature and said temperature reference signal for producing a cold advance timing signal corresponding to a respective timing advance, and means for applying said cold advance timing signal to said output means. | AUTOTRONIC CONTROLS CORP | MERRICK J |
WO-1979000982-A1 | 1,979,000,982 | WO | A1 | XX | 19,791,129 | 1,979 | 20,090,507 | new | A23J1 | F26B3, A23L1, B02B3, B02B1 | A21D2, A23B9, A23J1, A23L1, B02B3 | A21D 2/36, A23B 9/04, A23J 1/12, A23L 1/025C, A23L 1/10H, A23L 1/185, B02B 3/04C | HIGH-PROTEIN FOOD PRODUCT MADE FROM GRAIN AND METHOD AND APPARATUS OF MANUFACTURE THEREOF | A food product having a high protein content of good nutritional profile and substantially without fiber, fats, or oils is made from grain in storage (16) that has been malted and subjected to a mashing operation in tub (14) to remove fermentable sugars. The grain so treated is dried by microwave heating in (18) and (22) and is subjected from supply (27) to liquid nitrogen to reduce the temperature of the grain greatly while subjecting the grain to mechanical action by rollers (28) to remove the husks. The fats and oils are removed by a solvent in extractor (33) after which the remaining granular material may be ground to a flour in grinder (36). | -1-H1GH-PR0TE1N FOOD MADE FROM GRAIN AND METHOD OF MANUFACTURE THEREOFFIELD AND BACKGROUND OF THE INVENTIONThis invention relates to the field of high-protein food materials and the manufacture of such material from grain. In particular, the invention relates to a food product suit¬ able for human consumption and substantial ly free of fibers, fats, and oi ls, the product being made from grain from which fermentable sugars have been largely extracted but having a higher protein fraction than any untreated grain, the pro¬ tein fraction including effective amounts of all of the es¬ sential amino acids.DESCRIPTION OF THE PRIOR ARTThere is currently a critical and increasing world food shortage. It is not only necessary that nations find ways to increase and to use effectively the total quantity of food available in the world but that the additional food have proper nutritional values. In particular, extra sources of protein a re needed, since protein is the most important foodstuff.The derivation of high-protein foods and food supplements from plants has been the subject of extensive investigation Soybeans have long been known to be a good source of edible protein, and have been the subject of much study, but it is difficult to remove the basic bean taste from foods pro- 2-cessed from soybeans, and therefore, soybean-based food continue to be less desirable than their nutritional pro file indicates that they should be. Cereal grains also contain substantial amounts of protein but generally hav less nutritional value than soybeans. However, foods ma from grain a re not plagued by an undesirable taste.There is a source of grain heretofore overlooked as bein fit for human consump ion. Substantial quantities of gr are used in the brewing industry and at the present time there is In excess of 1.5 mill ion tons of spent grains p duced each year as a by-product of the brewing industry i the United States and four times that amount world-wide. The grains are referred to as spent because a large pe centage of fermentable sugars has been extracted from th leaving material that is of no further value in the prod tion of beer. This material, when dried, consists of needle-sharp particles due to the husks of the grains an especial ly because of these husks, is not suitable for h man consumption but is currently being sold as cattle fo at a price of about one cent a pound on a dry basis. Th removal of spent grains from the brewery poses potential , and sometimes actual, logistical problems, and spent grai are generally looked upon in the brewing industry as an undesirable but unavoidable waste material.The husks of grain processed for direct human consumption as cereals, flour, etc. a re not so troublesome because th are removed while the grain is still in the raw state. I that state, the husks are not bound, tightly to the grain and are relatively easily removed. By the time grain has gone through the mashing process used to extract ferment¬ able sugars in the production of beer and other alcoholic beverages, the husks have been cooked onto the grain, fo ing a tenacious adhesive bond between each seed and its husk. This has heretofore presented an insuperable barri to the use of brewers spent grains as a human food material, although the digestive system of cattle permits dried spent grains to be used as cattle food, for which brewers are pa id very 1 ϊ ttle.The initial process steps appl ied to grain in brewing beer and the l i e result in the production of large amounts of undesirable sewage, the removal of which is enti rely an ex¬ pense. Not only are brewers required to pay high sewer taxes to the communities in which breweries are located, but because of thei r inabi l ity to control the quantity and nature of the material they del iver to the sewage system, the brewers also have to pay high sewage surcharges.SUMMARY OF THE INVENTIONI t is one of the objects of this invention to provide a food formulation that has a high-protein percentage and is subs an ial ly free of fibers, fats, and oi ls.It is another object of the invention to obtain a food hav¬ ing high protein content by removing fermentable sugars from grain and treating the resulting spent grains to re¬ move the husks and fats and oi ls.A particular object of the invention is to uti l ize brewers spent grains in the production of a high-protein food fit for human consumption.Sti l l another object of the invention is to provide a pro¬ cess for removing the husks of grain that has been cooked, and particularly grain that has been subjected to a mashing operation as part of a brewing operation.A sti l l further object of the invention is to produce a food product suitable for human consumption from brewers - k-spent grains without the use of chemical additions or adu terants .Stil l another object of the invention is to evaporate fr brewers spent grains moisture that would otherwise have be drained as a l iquid into the sewer and be treated at high cost by a sewage disposal plant.Further objects will become apparent from the following spec I f i cat i on .In accordance with this invention grain, subjected to a mashing operation, is dried by the appl ication of microw energy, preferably accompanied by mechanical agitation, is then subjected to extremely low temperature to embrit the husks whi le the latter are mechanical ly fractured fr the grain. After that the husks and grain are physical l separated from each other, and the fats and oils in the grain are separated out by. a solvent, leaving a granular material having a high proportion of protein. This mate al can be ground to various degrees of fineness as desi r for processing into different kinds of food products.BRIEF DESCRIPTION OF THE DRAWINGSThe only drawing is, basical ly, a flow chart of the equi ment and process of the present invention.DETAILED DESCRIPTION OF THE INVENTIONAs the source of enzymes for mashing, and because of its decisive influence on the characteris ic taste of beer, barley malt is the one ϊ ndespensabl e brewing material . Malting is simply the control led germination of grain, t germination being stopped at a desired stage by means of heat. The purpose of malting the barley is to develop tO dor aπt enzymes of the barley so that they can break down the carbohydrates and release the fermentable sugars. Malt¬ ed barley has a yield of soluble substances of about 72% to 762, dry basis, which is about five-fold or six-fold increase over the yield of un alted barley.The initial stage in the brewing operation, proper, is the mashing stage in which malted barley, usually referred to simply as malt, that has been crushed between rollers is mixed with water in large tubs until it forms a mash having the consistency of porridge. The malt can be used alone in forming the mash, and in Germany, for example, this is man¬ datory. In other countries, for example the United States of America, adjuncts, such as corn grits or flakes or rice or other materials having high percentages of fer eπtab 1 es , can be added. Malt and adjunct are stored in bins 11 and 12 before being used. fπ the case of corn grits and rice, these adjuncts must be gelatinized by being boi led in a cooker 13 before being added to the mash in a mashtub 1 . Corn flakes, having been subjected to pre-gelat.inizatϊon, require no further boil ing but can be added directly to the mash .The mash is heated in steps going from about 38° C t0 about 7 ° C in a cycle of operation chosen by the brewer. The cycle is normal ly divided into steps to allow various en- zy es to act at the temperatures best suited to such ac¬ tions. Thereafter, the spent grains settle to the bottom of the tub to form a fi lter bed through which the l iquid, cal led wort, is filtered, or lautered.One of the reasons for using barley is that the structure of the barley husks makes the bed of spent barley grains especially suitable as a filter. If the mashing operation just described were appl ied to a different grain, not so much for the purpose of producing wort and eventual ly beerBlJKi-/. *■ but more specifically for the purpose of producing spent grains having the highest possible protein content by usi grain having the highest available natural protein, it might be necessary to provide additional filtering means allow the wort to be removed without washing away the spe grains. The choice of grain to be used may well be eco¬ nomically dictated by the fact that the profit that can b made by a brewer from the high protein material made by t process of this invention may be greater than the profit obtainable from the beer produced from that grain. In short, the by-product may become the main product and vic versa .After lauteriπg, sparge water is flushed through the spen grains and is combined with the wort. Sparging is contin ued until analysis of the sparge water shows only about one percent or one and a half percent of extract. The be of spent grains having a moisture content of about 75* to 80 % must then be removed from the tub as quickly as possi ble to permit a fresh batch of malt to be put in to start - a new mashing operation. While the fastest way of dispos ing of the spent grains might be to wash them down the se er, the enormous load that this would place on the sewage disposal system makes this method of disposal impracticalThe usual practice is to haul the soggy mass of -spent grains away from the brewery in large trucks as soon as a mashing operation has been completed, although some brewe ies store the wet grains in storage tanks and do not use trucks. Any delay In removing the spent grains from the mashtubs quickly brings the brewing operation to a halt, and if trucks are used, it is preferable to have the truc waiting at the brewery prior to the end of each operation even if this is not the most efficient use of the trucks.The spent grains are stored for later use as cattle feed but before being stored must be dried. The conventional drying method used at the present time is to remove the surface effluent from the soggy spent grains by a dewater- ing screen and then to subject the spent grains to the squeezing mechanical action of a Davenport press to effect further moisture reduction. Virtually all of the effluent removed by this conventional technique goes into the sewer and places a substantial load on the sewage disposal system.Even though the drying operation usually takes place away from the brewery (it could be carried out at the brewery before the spent grains are hauled away), a large percent¬ age of the sewer tax the brewery is required to pay is cal¬ culated on the basis of the effluent removed in the drying operation. The sewer surcharge that must be paid by the brewery is a function of four pollutants, the worst of which is the spent grains effluent resulting from the dry¬ ing operation. The others are: beer spillage, yeast spill¬ age, and caustic (PH treatment).In determining the spent grains effluent, no physical mea- sure ent of the volume or weight of spent grains produced at the brewery is made. Instead, the surcharge is deter¬ mined, usually, in one of two ways. One way is to weigh the amount of malt and adjunct that enters the plant and to measure the water input in cubic feet. The figures thus obtained are put into an equation that considers the pro¬ cess at the brewery and determines the amount of effluent that will go into the sewer. The brewer is billed accord¬ ingly.Another way is to use an effluent sample that operates as a in-line sample to take composites of the effluent grain line over a period of time. The B.O.D. (biologic oxygen demand) of the effluent samples, and the amount of malt, adjunct, and water purchased are used to calculate the sew- ■8-er surcharge. If the B-O.D. in the samples exceeds a mi imum value, an additional fine is added to the basic sew tax. Even when the grains are dried at a location away from the brewery, the tax surcharge is made to the brewe because the calculation includes the brewers' raw materi In addition, there is always some grain washed into the sewer when the mash tubs are cleaned and some more due t washings from the conveyors, but these amounts are small compared to the effluent that comes from the drying oper ation.At the present ime, the handling of spent grains is bei subjected to an increasing amount of direct environmenta control, as well as indirect control through taxation, b communities in which breweries are located. A brewery h ing a capacity of a million barrels can deposit, through effluent grains waste, enough polluting material to requ the same amount of sewage water treatment as would be re quired by a town having a population of 25,000 citizens. Most towns today require installation of a total recover system that, in essence, evaporates all of the water fro the spent grains and incorporates a sludge removal syste with chemical treatment. This imposes heavy fuel costs the brewery, virtually eliminates pressing operations us up to the present time, and triples the drying operation in conventional cylindrical rotary drum driers used here tofore.Communities are also becoming increasingly concerned abo air pollution. Special afterburners are being required be installed to burn off all of the fine dust particles that pollute the air and produce an odor in the vicinity of the brewery. The cost of fuel for total recovery sys tems is four times as expensive as the cost for standard systems used for the past fifty years but which are now being outlawed by more and more cities. Furthermore, th pol lution control equipment in existence up unti l now re¬ quires a great deal of space and operates slowly.In accordance with one aspect of this invention, the soggy spent grains are not hauled away from the brewery. Instead, they may be temporari ly stored in a container 16 or else transferred directly to a conveyor 17 which carries them directly through an industrial microwave drier 18 operating at a frequency and output power high enough to impart suf¬ ficient energy to vaporize the moisture contained within the grains. Whi le the grains are passing through the mi¬ crowave drier 18 on the conveyor 17 they are also subjected to mechanical vibration by a vibrator 19 to make it easier for the moisture to escape. The Federal Communica ions Commission has authorized frequencies of 915 MHz and 2^50 MHz for microwave drying equipment, and the higher of these frequencies is preferable for initial drying operation, but other frequencies may be used when and if thei r use is au¬ thor i zed .Drying the spent grains by microwave energy results in great financial savings to the brewer in reducing the spent grains effluent portion of the sewer tax and surcharge. A brewery paying an annual surcharge of $700,000 due to ef¬ fluent grains pol lution could el iminate that charge, al¬ though the brewery would have to pay about one-tenth of that amount as addi tional annual uti l ity cost. The cost of install ing the microwave driers would be about $500,000.A pecul iar aspect of brewers grains is that the concentra¬ tion of moisture is not on the surface, as i t is in almost al l other products, but is trapped inside the kernels of the grain so that it is quite difficult to remove quickly and inexpensively. Microwave energy is absorbed by the electrical ly bipolar water molecules in the kernels to bring the temperature of the water in the wet grains rapid- -10-ly to 100° C. None of the microwave energy is wasted in heating the air or the spent grain material, so that the electric power required to generate the microwaves is ve efficiently util ized. The drying time is reduced by as much as 8 ? in comparison with hot air drying, and the m crowave drier occupies only about 25? of the space requi for a hot air drier. Simply because of the length of ti the spent grains have to remain in a conventional drier, such drier lose more than half of the heat generated and therefore, more than half of the power suppl ied from the power 1 ines .Because microwave energy removes the water quickly and without raising the temperature of the grains excessivel it does not adversely affect the nutritional value, or p file, of the grains. All of the normally effluent water transformed into steam, thereby eliminating a major poll tion problem of the brewing industry.Removal of such high moisture content by application of microwave energy is also unique because there are very f products that have an 80? moisture content prior to dryi A 35? moisture content in a material to be dried is con¬ sidered quite high.I have found it preferable to divide the microwave heati into two separate stages. In the first stage the perceπ age of moisture in the grains is reduced from the Initia approximately 80? value to about 12? to 30? and preferab to about 20?. I have found that the use of microwave en ergy achieves this reduction in moisture content in the same length of time that would be required to reduce the moisture from the 80? level to 75? In a conventional hot air dryI ng system.After passing through the first microwave heating unit 1 the partially dried grains enter a fluffing chamber 21 in which the grains are further agitated by warm air currents for surface rotation. This fluffing operation has been found to be very beneficial in helping to dry the grains quickly without adversely affecting the nutritional profile.After being fluffed, the grains are conveyed, as part of the continuous drying process, through a second microwave drier 22 by a conveyor 23 to reduce the moisture content further to approximately 6? to 10? and preferable, to 8?, which is the desired amount for storage of the grains. Grains having more than 8? moisture become rancid more quickly; those having less than about 8? are more subject to catching fire. The conveyor 23 is also oscillated me¬ chanically by a vibrator 2k while passing through the drier 22 to aid in releasing vaporized water from the vicinity of the grain. Since less energy is required to effect moisture removal in the second microwave dried, the micro¬ wave frequency can be lower, for example, the standard 915 MHz, or other frequencies, if they are authorized. This double microwave system achieves a high degree of uniformi¬ ty of the dried grains and maintains the nutritional pro¬ file. The water is removed as steam, and there are no wastes or pollutants.A further advantage of the use of microwaves in drying is that they sterilize the product. Salmonella and Staphlo- cocci are killed by microwave heat, and any insect eggs are also destroyed. Such eggs may be produced in the spent grains by insects attracted to the soggy mass after it has left the tub ] and before it enters the microwave heating driers. Furthermore the soggy spent grains are an excel¬ lent medium for bacterial growth, and microwave energy elim¬ inates all bacterial problems.Dried grains from the second microwave drier 22 are con- veyed to a chamber 26 cooled to a very low temperature. This chamber may be a tower Into w ich the grains are fe at the top and cooled by a suitable cool ing medium, pre¬ ferably l iquid nitrogen, sprayed from a source 27 onto t fal l ing grains to come into momentary contact with them. Alternatively, the grains may pass through a l iquid nitr gen bath. In either case, the grains are brought to an exceedingly low, sub-freezing temperature and fed betwee mechanical rol lers 28 to be fractured by rubbing abrasiv action. The rol lers may be located at the bottom of the tower and may cons ist of a triple set of rol lers for opti mum operation. The grinds of these rol lers can be set f medium-coarse to fine.Liquid nitrogen has several advantages. For one thing i provides the temperature necessary to separate the husks and fibrous fractions from spent grains, a procedure that could not be carried out satisfactori ly with conventional techniques used by mil lers. Standard mi l l ing operations are appl ied to grains that have not undergone a cooking process. The husks of uncooked grains a re relatively eas to remove, but the husks and fibrous material of spent grains are difficult to separate from the grains themselv because carbohydrate and protein material resulting from incomplete removal during the leaching and sparging pro- cesses in the brewery forms films that are sol idified dur ing the drying operation and act as an adhesive that bind the husks and fibrous materials more tenaciously to each seed. A relatively smal l amount of husks and fibrous ma¬ terial is already separated at the time the grains reach the rol lers 28 at the output of the cool ing tower 26, but the greater portion of the husks and fibrous material is bound to the grains by means of the fi lms just described.Although it is the drying operation that sets the adhesiv film, it is the cooking operation in the mashtub 1 k that BUO preceeded the drying operation that causes the fi lm to be generated. Yet the cooking operation is necessary, not only because f Is required to obtain the wort in producing beer but also because it is the part of the process that removes a substantial fraction of the total grain material and leaves the remainder with a higher protein percentage by virtue of the removal of the non-protein material .The embr i tt lement of the grains by the l iquid nitrogen causes individual pieces of crushed grain to fracture quite easily in the rol lers 28, which makes it easier to dislodge the fibrous fractions from the grain pieces. The grain is kept at a very low temperature during the abrasive action to faci l itate the fracture between the grain and the fi¬ brous port i ons .An additional important reason for choosing l iquid nitrogen as a coolant is that it is non-toxic. As i t evaporates, it simply becomes part of the atmosphere and has no i l l ef¬ fects on anyone who may-breathe it. It also has no i ll ef¬ fects on the grains being processed. Liquid ni trogen is commonly used in processing of frozen foods and thus repre¬ sents a material that has already been approved by appro¬ priate governmental agencies. tt cannot leave any residue or have any chemical reaction with the spent grains. It is readily avai lable and is economical to use and is general ly preferred for producing extremely low temperatures in food manufacturing operations. Its use in helping to fracture the pieces of crushed grain in the present invention is not to freeze the grains but to bring them to an extremely low temperature, thereby making the adhesive fi lm brittle.The fractured material passes into an air-classification chamber 29, usual ly a vertical tower in which air is blown up through the fractured material , causing both the husks and the fractured grains to rise. The husks are less dense and are therefore carried to higher points by the risin air so that they may be drawn off and stored in suitabl receptacles 31 for later use. The more dense granular terial is drawn off at lower levels from the a I r-class i cation chamber and. stored In a bin 32 for a period of a least kS minutes to three hours, but preferably at leas one hour, to allow settling of both the granular materi and dust.The husks taken from the air-classification chamber rec tacles may be ground further according to specification furnished by a purchaser. Fibrous materials have recen become popular as food additives because of the benefici effects attributed to the Inclusion of fibers in humanAfter the grains have been allowed to settle, the fats oils are extracted by a suitable solvent in an extracti chamber 33- The solvent must be non-toxic and volatile as to leave no residue on the grains nor impart any und sirable flavor to them. Petroleum ether may be used as solvent, but hexane, which is well known as a solvent i the food industry, is preferred. The solvent Is passed through grains to dissolve the fats and oils so that th latter may be drawn off into a storage tank _\k, leaving fat-free grains that are also free of husks. These grai now devoid of husks, oils, and fats, a re In condition t ut through a milling and grinding operation in a grind 36, for example an alpine impact mill, with a special li quid nitrogen cooling chamber. The mill may be set to grind the fat-free grains into whatever particle size is desired by the purchaser and stored in sections of a co tainer 37 according to particle size. For example, bak ies will normally require grain ground into a flour, whi those manufacturers of meat extenders require a semi-co grind. The material may be fortified at this stage to raise the protein content by yeast injection or to adjust the nutri¬ tional profile by the addition of suitable amino acids or to insert flavoring material of any desired type. These fortifications are not mutually exclusive, but instead, two or more can be carried out on the same granular mater¬ ial .In the case of the addition of food flavors, the fact that the granular materials produced according to this invention have no strong taste of their own to be overcome, in con¬ trast to soybean material, is an advantage. Thus, any type of flavoring can be added, a fact that has been found to be unexpectedly important in the case of high-protein material to be furnished to people in certain countries. It has been found in the past that there are ethnic groups indi¬ genous to certain countries who insist upon certain flavors and reject other flavors, even though their total diet may be marginal in quantity, A lack of a pronounced adverse taste ϊ-n the material provided by the present invention makes it easy to satisfy the requirements of such people. Of course, the lack of an irremovable distinct taste that is unpleasant in certain combinations of tastes is advan¬ tageous in all kinds of food products.After the grain has been fortified, if such fortification is considered necessary, it may be packaged or sent to a bulk storage location. It is preferable to limit storage to approximately 40,000 pounds per bin for safety and ig¬ nition considerations.The quality of the protein material produced by the pro- cess just described is illustrated in the analysis in Table I. In this sample, the starting material had a relatively high amount of protein. However, even with lower initial protein, this invention enhances the concentration, and no grain-based food haying a protein percentage in excess about 36? and free of fats and ofls and fibers has been known heretofore. The profile of the material represen in Table I In w-hich the protein is concentrated to 41? i typical of what may be expected from brewers spent grai obtained In north-eastern section of the United States. Proteins taken from grains In other parts of the country and in other parts of the world will vary to some exten but in all cases, the percentages of protein will be hig than has been obtainable in the past.Not only is the total quantity of protein high, but the percentage represented by those a ino acids deemed bene¬ ficial to the diet Is also high. As may be seen, these amino acids, which are specifically named in Table I, ac count for about 35? of the total grain, and the addition approximately 6? of protein is protein that is not of pa ticular nutritional value. TABLE \NEW ENRICHED PROTEIN GRAINPROTEIN 41.0?MOISTURE 8.0?ASH (minerals) 4.0?FATS S OILFIBERCARBOHYDRATES 47.0?AMINO ACIDS (Nutritional Profile)Arginine 1.57? of the grain 3,8? of proteinHistidine .74 1.8Isoleucine 1.50 3.7Lysiπe .95 2.3LeucIne 4.08 9 :Meth ion ine .62 1.6Phenylalanine 1.95 4.7Threonine 1.19 2.9Tryptophan .31 .76Tyrosine 1.12 2.7Valine 1.83 4.6Aspartic acid 2.37 5.8SerIne 1.55 3 8Gluta ic acid 7.93 19 3Proline 3.80 9 2Glycine 1.15 2 8Ala'nine 2.33 5 7 Table I I shows a protein profi le that has been deemed to represent a high-qual it protein. This table includes i formation taken from Recommended Dietary Allowances, ed . Washington, D. C. 1974, Food and Nutrition Board, Nationa Research Counci l , p. 44, as publ ished by Orten, J. M. and Newhaus, 0. W. , in Human Biochemistry, publ ished by the C. V. Mosby Company (1975) , p, 523- Comparison of the c umn titled New Formulation, which represents the amino acid profi le of the high-protein food according to the pr sent invention, show-s that the profi le of the new formula tion compares- favorably with the desired pattern and has serious amino acid deficiencies.This invention has been described in terms of specific materials and processes, but it wi l l be obvious to those ski l led in the art that modifications may be made therein within the scope of the invention as defined by the fol lo ing c1 a i s .■fuKOM TABLΕ I -Amino acid pattern for NewAmino acid high-quality proteins Formu la i on g/gm of protein)H i sti d Ine 17 181 so 1euci ne 42 37Leuci ne 70 99Lys i ne 51 23Total S-contalning amino acids (Met, Cys) 26 16Total aromatic amino acids (Phe, Tyr) 73 74Threon i ne 35 29Tryptophan 11 7.6Va 1 i ne 48 46 | WHAT IS CLAIMED IS;1. A food product made o grain and containing at least substantially 36? protein and being substantially free o fibers and fats and oils.2. The product of claim 1 in which the grain is barley.3. The product of claim 2 in which the barley is pre¬ cooked.4. The process of making high-protein food comprising th steps of: directing microwave energy into a mass of soggy spent grains following a mashing operation in which a substanti proportion of fermentables have been removed from the gra said soggy spent grains having at least approximately 70? moisture by weight, said microwave energy being su ficien intense to vaporize moisture associated with said spent gra i ns ; continuing the application of microwave energy to dry the spent grains until the moisture content thereof is re duced to approximately 5 to 10? by weight; and removing the substantially dry spent grains from the path of microwave transmission.5. The process of claim 4 in which the soggy spent grain have an initial moisture content by weight of approxi ate 80?.6. The process of claim 4 in which the grains are dried microwave energy to approximately 8? moisture by weight.7. The process of claim 4 comprising the additional step of mechanically vibrating the grains while they are being subjected to microwave energy. 8. The process of claim 7 in which the grains are contin¬ uously being conveyed through the transmission path of the microwave energy and are being vibrated at the same time.9. The process of claim 4 in w-h i ch the microwave energy is produced at a frequency greater than about 2000 MHz.10. The process of claim 4 comprising: first exposing the soggy grains to relative high fre¬ quency microw-ave radiation to reduce the moisture content of the grains to about one-fifth to one-third of its ini- t i al va 1 ue; fluffing the grains by passing warm air through them; and subsequently exposing the partial ly dried, fluffed grains to lower frequency microwave radiation to extract additional moisture to the remainder level .11. The process of separating husks from dried spent grains comprising the steps of: subjecting the dried spent grains to a temperature sufficiently low to embrittle the same; and exerting mechanical force on the embri ttled grains whi l maintaining those grains at a sufficiently low tem¬ perature to keep them embrittled.12. The process of claim 11 in which the step of subject¬ ing the dry spent grains to low temperature comprises ap¬ plying l iquid nitrogen to the grains.13. The process of claim 12 in which the l iquid nitrogen is sprayed on the grains as the grains move past a source of sprayed l iquid nitrogen.14. The process of claim 12 in which the grains are passed through a bath of l iquid nitrogen. 15. The process of removing fats and oi ls from spent gra from which the husks ha-ve heen removed, the process com¬ prising: passing a yolatl le solvent of the fats and oi ls thro a quantity of husk-free grains; and drawing off the dissolved fats and oi ls,16. The process of cla.ϊm 15 in which the solvent is petr leum ether.17- The process of claim 15 in which the solvent is hexa18. The process of manufactu ing a high-protein food com prising the steps of: mixing a quantity of malted, partial ly crushed grain wi h wa er; heating the water with the grain it it; drawing off the resul ting l iquid; removing the remaining granular material in soggy form; applying microwave radiation to the soggy material t drive off moisture therefrom; subjecting the substantial ly dried granular material to temperature sufficiently cold to embrittle the granula mater I al ; applying mechanical pressure to the grains of the granular material to fracture husks therefrom; separating the husks and the remaining granular ma¬ ter i a 1 ; and dissolving the fats and oi ls from the remaining gran ular material by means of a volati le solvent leaving no substantial residue and having no substantial after taste remaining in the fat-free, oi l-free granular material .19. Apparatus for producing a high-protein food product fit for human consumption, said apparatus comprising: means to dry cooked grains having husks thereon; a cooling tower; means to feed the dried grains Into the upper part of the cooling tow-er; means to apply liquid nitrogen to the grains in the cooling tower to embrittle the grains; and grinding means to grind the e br i 1 1ed graIns .20. The apparatus of claim 19 in which the means to dry the grains comprises microwave drying means.21. The apparatus of claim 20 in which the microwave dry¬ ing means comprises: a first microw-ave drier operating at a relatively high microwave frequency; and a second microwave drier operating at a microwave fre- quency substan ially low-er than said first microwave drier.22. The apparatus of claim -21 comprising, in addition: a fluffing chamber including air supply means to blow air up through said grains in said fluffing chamber; and conveying means to convey said grains through said first microwave drier and from there into said fluffing chamber and from said fluffing chamber into said second microwave drier.23. The apparatus of claim 22 comprising means to vibrate said grains in both of said microwave driers.f OMPI . WIPO - | GANNON J | GANNON J |
WO-1979000984-A1 | 1,979,000,984 | WO | A1 | EN | 19,791,129 | 1,979 | 20,090,507 | new | B60R1 | null | B60R1 | B60R 1/064 | CONTROL GEAR FOR REARVIEW MIRRORS AND THE LIKE | A control gear for adjustment of an external rear view mirror, comprising a body fixed in a suitable detail of a coachwork (A), a support (3) attached to said body and movable in two planes or about two axes, to which support the minor is fixed, a tubular part extending through said coachwork detail, a control handle (5) arranged at the inner end of said tubular part and transmission means (6, 16) arranged between said handle and said movable support. The novel feature is that the transmission means consist of a rotatable as well as axially displaceable rod (6) extending through the tubular part (1, 4) and an arm (16) which is articulated to an eccentrically onset outer end (17) of said rod and rigidly secured to the support (3) and that the e control handle is non-rotatably, relative to the axis (Z) of the rod but pivotally connected to said rod (6) and that the handle (5) is so mounted, that independently of the relative rotational position of the handle (5) and the rod (6) the turning of the handle and the axial displacement of the rod is permitted. | CONTROL GEAR FOR REARVIEW MIRRORS AND THE LIKEThe present invention relates to a control gear for adjustment of an external rearview mirror, comprising a body fixed in a suitable detail of the coachwork, a support attached to said body and movable in two planes or about two axes, to which support the mirror is fixed, a tubular part extending through said coachwork detail, a control handle arranged at the inne_c end of said tubular part, and trans¬ mission means arranged between said handle and said movable support. It is already known to provide control gears for rearview mirrors and the like with a tubular passage means and to dispose in said tube wires or the like which at one end are actuated by a handle and at the opposite end act upon the rearview mirror. It is also known- to use two rocs one of which is hollow and rotatable in the passage means and surrounds an axially displaceable rod, and the rotation of the mirror in one plane is brought about by turning of the first rod and the rotation of the mirror in the second plane is brought about by turning of the second rod. The object of this invention is to provide a device which is simplified by reduction of the number of rods and permits mounting in one hole and also permits simple adjustment and which is of such a nature that the risk of the. irror being subjected to the influence of the speed wind is reduced.The essential characteristic of the new device is that the transmission means consist of a rotatable as well as axially displaceable rod extending through the tubular part and an arm which is articulated with the eccentrically offset outer end of said rod and rigidly secured to the support, in which axial displacement of the rod causes the support to move about one axis and rotation of the rod causes the support to move about the second axis, that the control handle is non-rotary relative to the rod axis by means of a pin or the like fitted at the inner end of the rod but is pivotally / „. -,,, wι;]o connected to the rod transversely of said axis, and that the handle by means of a further pin or the like is mounte in a U-shaped and outwardly open notch disposed concentric ly and in the form of an arc at the inner end of the tubul part, said notch permitting turning of the handle and axia displacement of the rod independently* of the rotational po tion of the handle and the rod.A preferred embodiment of the new device will be described in greater detail below with reference to the accompanying drawing-, in which Fig 1 is a perspective view diagonally showing the device in assembled condition from the outside, Fig 2 is a partial section of the mounted bed prior to the mounting of the control rod, Fig 3 shows the outer portion of- Fig 2 from the other side and Fig 4 is a top plan view of the mobile parts of the device and the nut sleeve.The device comprises a body consisting of a tube 1 at the outer end of which there is attached a housing 2 fc a support 3 which is movable in two planes and to which a rearview mirror is intended to be attached in a per se known manner. The tube 1, which is intended to extend through a car door or other detail A of the coachwork, is at its inner end connected with a nut sleeve 4 which carries a control handle 5 and retains the device to the car door.The mobile components of the device are three in number and consist of the aforementioned control handle 5, a control rod 6 and said support 3.The control handle includes a grip portion 7 and at the end thereof two parallel pins 8 and 9.The control rod 6 comprises a straight part 10 extending through the tube 1 of the body and the nut sleev 4. At. the end of the part 10 there is a bore 11 through which the pin 8 of the handle is intended to extend. At the opposite end of the rod is an angled portion 15 which supports an eccentrically situated ball socket 13.The control rod is so mounted in the tube of the body and the nut sleeve 4 attached thereto that can turn about its longitudinal axis and also be displaced axially. .The support consists of a cylindrical part 14 frcr which two diametrically opposite pins 15 extend. Attache:: to- the part 14 is an arm 16 which at its free end supports a ball 17 to be received in the ball -socket 13.The pins 15 of the support 3 are mounted between twc washers 18 and 19, respectively, fitted in the housing 2 and provided with opposite arc-shaped recesses. These washers are -provided with elongate openings oriented transversely cf the recesses for the pins 15, whereby the support can be- swung on an axis X extending through the pins 15.The washers are rotatable relative to the hcυsir.c and the support 3 can therefore be turned on an axis ϊ e.tend r. through the center of the washers or housing. The washers bear resiliently against the pins 15.The movement of the support about the first-ment. cr.ed axis X is obtained in that the control rod 6 is turned abc t its longitudinal axis, whereby the ball socket, like a era.-..-: , will describe an arc-shaped movement and carry the ball¬ bearing arm 16 of the support 3 upwardly or downwardly ar.c thus turn the support 3 about the axis X.The difference in radius of rotation between, cr. one hand, the geometrical centre of the ball socket and the axis Σ • of the control rod and, on the other hand, the geometrical centre of the ball and the axis X extending throug'h the pins 15 of the support 3 is compensated for in that a relative movement is permitted between ball socket and ball.The rotary motion of the rod is obtained by means of the handle 5. Since the -pin 8 extends through the roc 6 it is possible to turn the rod by turning the handle.The movement of the support about the axis Y is carried out by displacing the rod 6 in axial direction. Since the ball socket 13 engages the ball 17 attached on the arm 16 axial displacement of the rod 6 will cause the support 3 and the washers 18, 19 to turn in the housing 2 about the axis Y .The, axial movement of the rod is also carried out by means of the handle. One 8 of the' pins in the handle is, as mentioned, attached to the end of the rod. The other pin 9 in the handle passes through a notch 20 of U-shaped cross-section in the end of the nut sleeve 4, extending in the form of the arc of a circle'and adapted to the pin diameter and serving as a bearing for- the pin 9 which is attached to the handle 5. When the handle turns, the pin 9 will thus form a lever shaft and the rod 6 will thereby be axially displaced in the tube 1 via the pin 8. The pin 9 is retained in.position because the handle is radially fixed by the other pin 8 which passes through the rod 1, which is guided in the tube 1. Because the notch 20 follcv.'s the arc of a circle around the central axis of the rod 6 be possible for the handle to turn about the pin 9, ihdepencer. of the position of rotation of the handle and the rod.As the distance between the pins 8 and 9 is subs ar.tιal smaller than the distance between the axis Y of the suppcrt 3 and the geometrical turning point between the rod 6 and the arm 16 there is obtained a gearing of the turning movement of the handle.A similar gearing is obtained in connection with mcver.e about the axis X because the geometrical turning point between the ball 17 and the ball socket 13 is more distant from the axis X than from the rod axis Z. As a result of the indicated gear ratios the rearview mirror attached on the support 3 will be firmly retained in set position and will not be unintentionally reversed under the influence of the speed wind.The simple construction of, especially, the part passing through the coachwork ,makes it possible to adapt the control device to various door designs with a minimum of trouble. If the door or the part to which the device is to be secured is, for example, narrower than that shown in the drawings, use' is made of a shorter rod and a corre- spondingly shorter tube.Owing to the described construction the mounting of the device is most simple and is reduced to making circular holes in the external and internal sheets. The tube (1) isEAS ORIGINAL introduced through these holes, whereupon the nut sleeve 4 i> screwed on and the handle 5, which may be provided with the. pin 9, is pulled on and secured to the rod by means of the pin 8.As concerns the embodiment of details it is obvious that the device can be varied within -wide limits. Thus, the invention must not be considered limited to that described and shown in the drawing but may be modified in various ways within the scope of the following claims. | CLAIMS1. A control gear for adjustment of an external rearview mirror, comprising a body fixed in a suitable detail of the coa work (A) , a support attached to said body and movable in two planes or about two axes, to which support the mirror is fixed, tubular part extending through said coachwork detail, a control handle arranged at the inner end of said tubular part, and tran mission means arranged between said handle and said movable support, the transmission means consisting of a rotatable as we as axially displaceable rod (6) extending through the tubular p (1, 4) and an arm (16) which is articulated to the eccentricall offset outer end (17) of said rod and rigidly secured to the support (3) , wherein axial displacement of the rod (6) causes t support to move about a first axis (Y) and rotation of the rod causes the support to move about a second axis (X) , characteriz in that the control handle is non-rotatably, relative to the ax of the rod, but pivotally connected to said rod by means cf a transverse pin or the like (8) fitted at the inner end of the ro provided along an axis transverse to the rod axis, and that the handle (5) by means of a further pin or the like (9) mounted sub stantially in parallel with the first pin and adapted to engage U-shaped and outwardly open notch (20) at the inner end of the tubular part disposed concentrically with the rod and serving as fulcrum and independently of the relative rotational position of the handle (5) and thepart (4) permitting turning of the handle about the transverse further pin and thereby axial displacement the rod relatively to the tubular part.2. A contro 1 gear according to claim 1, characterized in th the outer end of the rod (6) is provided with an eccentrically offset ball socket (13) which embraces a ball (17) disposed on t arm (16) which is rigidly secured to the support (3) , the centre of the ball socket (13) being beyond the axis of the rod and the axis of the support being on the opposite side of said axis (Z) .3. A control gear according to claim 1 or 2, characterized in that the axis (X) about which the support (3) is rotatable by turning of the rod (6) is situated at an angle with the axis of rotation (Z) of the rod.4. A control gear according to claim 1, 2 or 3, characteriz in that the tubular part comprises a part (1) which extends thro the coachwork detail (A) and to the outer end of which a housing for the movable support (3) is attached, and a part (4) in the f of a nut sleeve retaining the device to the coachwork detail, th U-shaped notch (29) , formed as the arc of a circle, being situat at the inner end of said retaining part.'B KtA^ | ALLANDER C; BRAAS SPEGELINDUSTRI AB; HOLMQVIST G; BRAAS SPEGELIND AB | ALLANDER C; HOLMQVIST G |
WO-1979000988-A1 | 1,979,000,988 | WO | A1 | EN | 19,791,129 | 1,979 | 20,090,507 | new | C10L5 | C08L1, C08L97 | C10L5, C10L11 | C10L 11/04, C10L 5/44 | FUEL PELLETS | A fuel pellet comprises from about 90 to about 99% by weight natural cellulosic material and from about 1 to about 10% by weight synthetic polymeric thermoplastic material. The free moisture content of the cellulosic material is from about 5% to about 25% by weight. The thermoplastic material is generally finer than 5 mesh. The synthetic thermoplastic material is distributed throughout the fuel pellet. The thermoplastic material is solid at room temperature and has an injection molding temperature of at least 95`C. Such a fuel pellet can be prepared in a pelletizer (70) where the temperature of the pellet as it emerges from the die is from about 66 to about 122`C. | FUEL PELLETSBackground of the InventionDue to diminishing quantities of coal, petroleum, and natural gas products, attention is being directed to other energy sources, including oil shale, solar energy, and nuclear energy. One source which is receiving considerable attention is biomass materials such as wood and its byproducts. Recently, much attention has been directed to preparing briquets from wood waste.Use of available pelletized wood waste as a fuel source has achieved only limited acceptance to date.One reason for this is the relatively low heating value of pelletized wood as compared to coal. Other problems with use of available pelletized wood as a fuel source is that it has a slow burning rate and it exhibits incomplete burnout, resulting in formation of carbonaceous residues and low combustion efficiency. In addition, pelletized wood can be harder to ignite than coal and pelletized wood can be more fragile than coal, requiring special handling to avoid crumbling and to prevent weathering. To overcome the crumbling and weathering problems, inorganic binders such as cement and silicate of soda, and organic binders such as tar, pitch, rosin, glues, and fibers have been included in the pellets. However, no binder has been found which solves the above problems, and which also is inexpensive and does not reduce the heating value of the wood.It has been attempted to use the self-binding characteristics of various species of wood due to lignin present to avoid the crumbling problem. This can be effected with some species of wood, but not all species, by heating the wood above its minimum plastic tempera¬ ture of 163°C. However, such high temperatures can severely limit the operating life of the pelletizing equipment and drive high BTU volatile components from the wood.Therefore, there is a need for a fuel pellet which resists crumbling, is easily ignitable, burns fast and completely, and has a good heating value. There is also a need for a method for preparing the fuel pellet which does not require high pelletizing temperature. Summary of the Invention This invention provides a fuel pellet with the above features and a method for preparing the fuel pellet. The fuel pellet comprises from about 90 to about 99% by weight natural cellulosic material, and from about 1 to about 10% by weight synthetic polymeric thermoplastic material. The free moisture content of the cellulosic material is from about 5% to about 15%. The plastic is generally finer than 5 mesh. The thermoplastic material is chosen so it is solid at room temperature and has an injection molding temperature of at least 95°C. Preferably, the thermoplastic material is distributed throughout the pellet. The thermoplastic material serves to bind the pellet together, increase the heating value of the pellet, lubricate the pelletizing die, and improve the ignition and burning characteristics of the pellet. Fuel pellets of the present invention exhibit complete burnout, burn faster than pellets not containing thermoplastic material, and can have a heating value in excess of 5,005 K.Cal/Kg. The fuel pellet can be made by preparing a feed of particulate natural cellulosic material and particulate synthetic thermoplastic material. Substantially all of the thermoplastic material is -5 mesh, and preferably -10 mesh. The plastic and cellulosic materials are intimately combined by compressing the feed in a die. Brief Description of the DrawingsFIGURE 1 llustrates in a perspective view a pellet representative of pellets prepared according to the present invention; andFIGURES 2A and 2B illustrate a process embodying features of the process of the present invention. These two Figures are to be considered serially. 1 Detailed DescriptionWith reference to Figure 1, there is shown a fuel pellet 10 prepared from cellulosic and thermoplastic materials. Fuel pellet 10, which is cylindrical in shape,5. preferably has a minimum dimension of at least 4.75 m.m. and comprises from about 90 to about 99% by weight natural cellulosic material and from about 1 to about 10% by weight thermoplastic material.The natural cellulosic material used to form the10 pellets 10 can be particulate woody material such as sawdust, wood shavings, sander's dust, hog fuel, peat, and bark. Agricultural waste such as banana and papaya stalks, straw, bamboo, jute, bagasse, corn husks, corn cobs, cotton gin trash , sisal, seed hulls, and peanut15 hulls can also be used. Also, paper and cardboard can be included in the pellets. Combinations of the above natural cellulosic materials can also be used. Preferred natural cellulosic materials are those with low moisture content to minimize drying costs, and low contamination20 levels to minimize pelletizer die wear. As used herein, the term cellulosic material includes lignin.Particulate wood material preferably is used in the pellets because it has a higher heating value and lower moisture content than agricultural waste. Inclusion25 of banana and/or papaya stalks in the pellets is desirable because banana and papaya latex are good binding agents and contribute to the cohesiveness of the pellets.The synthetic thermoplastic material can be30 practically any available synthetic thermoplastic such as, but not limited to, polystyrene, polyethylene, polypropylene, acrylonitrile-butadiene-styrene, acetal copolymer, acetal homopolymer, acrylic, polybutylene, and combinations thereof. Although thermoplastics35 combinations thereof. Although thermoplastics containing a halogen such as polyvinylchloride can be used, for most applications these are to be avoided becaus of corrosion and emission problems associated with the combustion products of halogen-containing thermoplastics. It has been noted that for fast burning and ease of ignition of the fuel pellets, polypropylene and polyethylene are the preferred synthetic thermoplastic materials.The term synthetic thermoplastic materials excludes naturally occurring thermoplastic materials and naturally occurring cellulosic materials. For ease of handling, the synthetic thermoplastic material must be solid at room temperature. Preferably the synthetic thermoplastic material has an injection molding temperature of at least 95°C. The minimum injection molding temperature of common thermoplastics as reported in Modern Plastics Encyclopedia, Vol. 49, McGraw-Hill, 1972-3 Edition, is presented in Table 1.TABLE 1 Minimum InjectionSynthetic Thermoplastic Molding Temperature (°F.) Polystyrene 163°C. (325°F.)Polyethylene 122°C. (250°F. )Polypropylene 191°C. (375°F.) ABS 183°C. (360°F. )Cellulosics 168°C. (335°F.)Nylon 191°C. (360°F. )Polyesters 132°C. (270°F.)It has been found difficult to pelletize a feed containing more than about 1.25% by weight high impact polystyrene. It was noted that pelletizer production rate decreased with such a feed and it was difficult to thoroughly disperse the high impact polystyrene in the pellets. Therefore, when the pellets include high impact polystyrene, it is preferred that feed to aOM pelletizer contains only up to about 1.25% by weight high impact polystyrene. It is desirable to include polystyrene in the pelletizer feed because it has been found that polystyrene contributes greatly to the cohesiveness of the fuel pellets, such cohesiveness is important because it is undesirable for the pellets to break or disintegrate during handling and storage. Such breakage and disintegration can produce fines and dust, which can be a serious fire and explosion hazard. It is critical to the present invention that at least 1% by weight thermoplastic material be included in the fuel pellets. This is because fuel pellets containing thermoplastic material have many significant advantages compared to fuel pellets containing only cellulosic material. For example, inclusion of thermoplastic material in fuel pellets allows the fuel pellets to be formed easily in a pelletizer at temperatures lower than temperatures required for forming a fuel pellet with only cellulosic material. Thus, the thermoplastic material serves as a processing aid for forming pellets from the cellulosic material. In addition, the thermoplastic material has a higher heating value than the cellulosic material, and the resulting pellets have a correspondingly high heating value.Another advantage of the presence of synthetic thermoplastic material in fuel pellets is that the thermoplastic material provides a substantially water-impervious coating, or sheath on the outside of the pellets, thereby both preventing uptake of moisture by the pellets and resisting weathering in storage. Because of the uniform distribution of the plastic within the pellets, there is plastic even at the ends of a cylindrical pellet. This also prevents uptake of water by the pellets. Furthermore, the hydrophobic nature of the plastic prevents water uptake.A portion of the thermoplastic material can be in the fuel pellets in the form of discrete subparticles. The presence of discrete thermoplastic subparticles in fuel pellets results in easy ignition because the discrete subparticles provide an ignition situs.Surprisingly, it has been found that the fuel pellets exhibit burning and ignition characteristics which are superior to the burning and ignition characteristics of either the cellulosic material and thermoplastic material which make up the fuel pellets. .For example, burning tests were conducted with (1) conventional fuel pellets made only with sawdust, (2) polypropylene, and (3) fuel pellets according to the present invention prepared with 91% by weight sawdust (different from the sawdust used for the all sawdust pellets) and 9% by weight polypropylene. The all sawdust fuel pellets burned at a rate equal to about 1/2 the rate of the fuel pellets of the present invention. The two types of fuel pellets were about the same size, but it should be noted that the all sawdust fuel pellets were denser than the sawdust/polypropylene fuel pellets, but this accounts for only part of the difference in burning rate. It has been noted that fuel pellets containing plastic burn faster than less dense conventional all wood pellets.Therefore, in a boiler of a fixed size, the fuel pellets of the present invention can be used to generate heat and steam at a faster rate than conventional fuel pellets. In addition, the sawdust/polypropylene fuel pellets left practically no residue, while the conventional fuel pellets left a carbonaceous residue. Furthermore, the fuel pellets consisting only of thermoplastic material did not burn completely, but kept self-extinguishing. This was not a problem with the fuel pellets of the present invention. Therefore, fuel pellets prepared from cellulosic material and plastic material burn better than either the cellulosic material alone or the plastic material alone.It is believed that thermoplastic material in fuel pellets acts as a binder for the cellulosic materials. Pellets containing at least 5% by weight thermoplastic material have been demonstrated to have sufficient toughness to withstand exposure to the shocks of transportation, storage, and stoking. When a pellet includes thermoplastic material, crumbling and excessive softening from weathering are avoided. Furthermore, thermoplastic materials typically have a higher heating value than cellulosic material. The pellets should contain at least 1% by weight of the thermoplastic material, and more preferably at least about 2.5% by weight, to obtain these advantages.Preferably, the fuel pellets contain from about 1 to about 10% by weight thermoplastic material, and more preferably from about 2.5 to about 10% by weight thermoplastic material.Materials other than natural cellulosic material and synthetic thermoplastic materials can be included in the pellets. For example, materials such as comminuted tires, thermosetting' resins and/or petroleum distillation residue can be added to improve the heating value of the pellets.Oxidizing agents such as sodium perchlorate and ammonium nitrate to facilitate combustion can also be included in the pellets. Also, binding agents in addition to thermoplastic materials can be used. Exemplary of such binding agents are paraffin slack wax, carnuba wax, and lignosulfonates, such as ammonium lignosulfonate, sodium lignosulfonate, calcium lignosulfonate, and magnesium lignosulfonate. Certain cellulosic materials can be added to the pellets as a pelletizing or processing aid. Preferred materials in this category are oil seeds and their products, which by their fatty acid content reduce wear on the dies of the pelletizing equipment. Exemplary of such materials which can be included are coconut husks, 'soy beans, peanuts, sunflower seeds, corn cake, pressing residuals, and the like.As used herein, the term pellet refers to a discrete particle of any size or shape which contains both natural cellulosic material and synthetic thermoplastic material. The pellet need not be symmetrical, but it is preferred that pellet 10 be substantially symmetrical in shape, such as cylindrical, parallelepiped, or the like, having a diameter within the range of from about 4.75 m.m. to about 25.4 m.m. While it is most practical to form the pellets in a cylindrical shape, the pellets can be in any suitable symmetrical configuration such as the shape of a cube. The larger the diameter of the particles, the slower their burning rate. This is because of the fact that as the diameter increases, the surface area to volume ratio of the particles decreases. Depending upon the flame temperature and burning rate required in any given boiler, the optimum feed diameter for that boiler can vary within the range of about 4.75 m.m. to about 25.4 m.m.It is necessary that the particulate cellulosic feed and particulate synthetic thermoplastic feed have a maximum particle size less than about 60% of the minimum dimension of the pellet to avoid crumbling of the pellet in storage. For example, if the pellet is cylindrical and has a diameter of 1/4 inch, then the cellulosic feed and thermoplastic feed should have a maximum particle size of about 3.82 m.m. (0.6 x 6.35), i.e. about 5 mesh.OΛiP The bulk density of the particles can vary in the range of from about 482 to about 643 kilograms per cubic meter. It has been found that pellets 25.4 m.m. long and 6.3 m.m. in diameter made from about 90% sawdust and about 10% polyethylene thermoplastic can have a bulk density of about 611 kilograms per cubic meter.A process for preparing fuel pellets is shown schematically in Figures 2A and 2B. Cellulosic feed material, plastic feed particles, and plastic feed sheet are delivered by trucks (not shown) and stored in storage bins 20a, 20b, and 20c, respectively. Additional feed storage bins can be provided for segregating different types of feed. The feed, either before or after introduction into the feed bins, can be treated to separate foreign materials such as metallic impurities and soil. This can be done by means of such equipment as pneumatic conveyers, screen, magnets, and combinations thereof. Magnets conventionally are built into the equipment, described below, used for comminuting the feed materials. The feed from the cellulosic feed storage bin 20a is transferred via a belt conveyer 24a to a classifying device such as a vibrating screen 26 to separate oversize particles 28 from particles 30 which are suitable for direct feed to a pelletizing operation. The size of the holes in the screen depend upon the size of the pellets to be made, but in any case, the size of the holes is necessarily smaller than the minimum dimension of the pellets.In the comminution device, the feed cellulosic material is comminuted to a desired particle size. As used herein, the term comminution refers to any physical act of size reduction, including, but not limited to chopping, crushing, and grinding by suitable machinery. There are at least three types of machines useful for reducing the size of wood. Veneer and comparable fine scrap can be reduced to chips in a hammer ill, in which rotating bars of various designs break up the material by impact. A disk chipper can be used for solid scrap and round wood of various sizes. This chipper has knives set in radial slots. A knife hog is similar in action to the chipper, but the knives are set in the sloping surfaces of a V-shaped drum. The knife is suitable for solid wood and for scraps that may be somewhat smaller than the disk chipper can handle. Exemplary of the operation of the hammermill 32 is comminuting cellulosic feed for making cylindrical pellets having a diameter of 9.5 m.m. and cylindrical pellets having a diameter of 6.35 m.m. For pellets having a diameter of 9.5 m.m., preferably, all of the particles are -5 mesh, and at least 50% of the particles are -10 mesh. If the pellets have a diameter of 6.35 m.m., then preferably all of the cellulosic material is comminuted to -10 mesh. Preferably, the comminuting equipment is operated so that substantially all of the particulate cellulosic material has a particle size greater than about 30 mesh. This is to avoid the presence of fines and dust in the feed to the pelletizer, and the explosion hazard associated with such small particles of cellulosic material. The particles 30 not requiring comminution and the comminuted particles 34 from the hammermill 32 are collected on a belt conveyer 36 and passed via ducts 37 to two rotary driers 38 in parallel to reduce the moisture content of the cellulosic material. To develop the necessary strength and hardness in the pellets, it is essential that the free moisture content of the cellulosic material be reduced to less than about 15% by weight. By free moisture there is meant moisture which can be removed by evaporation at normal temperatures and does not include any bound water such as chemicallyBUO bound water that might be present in the feed material. Various types of dryers such as steam-heater plates, and dry steam pipes over which the feed is cascaded can be used to bring the feed to the desired moisture content. Flash dryers using a short exposure to hot gases can be used. The heat from drying can be provided by burning the fuel pellets and/or fines produced by this process in a heater 40 which supplies hot gas via ducts 41 to the dryers. When the free moisture content of the cellulosic material is reduced to less than about 5% by weight, the pellets upon discharge from the pelletizer burst and demonstrate a Christmas tree effect. These pellets are unsatisfactory because they tend to form fines in storage and handling. This problem can be overcome by introducing steam, as necessary, at the pelletizer. In summary then, preferably the dryers reduce the moisture content of the feed to about 5% to about 15% by weight, the same as required for feed to the pelletizer. For high production rates from a pelletizer, and for production of pellets which exhibit excellent cohesiveness and high strength, preferably the free moisture content of the feed to the pelletizer is from about 8% to about 12% by weight, and most preferably about 10% by weight.To aid in drying the cellulosic feed material, dry slaked lime, i.e. calcium carbonate, can be combined with the dryer feed. The calcium carbonate combines with water of the feed material and then releases moisture more easily in the dryer, thereby aiding more rapid drying of the feed material. Use of calcium carbonate in an amount of from about 2 to about 10% by weight of the feed, and preferably in an amount of about 5% by weight, significantly aids in the drying process. The preferred grade of calcium carbonate is a fine grade having a particle size of less than 100 mesh. When this drying technique is used, the product fuel pellets contain at least 1% by weight calcium.It is believed that to make good pellets with bark, it is necessary to first comminute the bark, then dry the comminuted bark and then comminute the dried bark one more time before feeding to the pelletizer. This is because raw bark is usually available only as large particles which are difficult to dry efficiently. Water can be removed from the feed material upstream of the dryers when the feed material contains gross quantities of water. For example, water can be removed from peat, bark, or sawdust with presses that operate on the roller or clothes-wringer principle. Screw presses, using tapered screws, are also useful for dewatering of bark. The drying operation can be run as a batch operation to avoid the expense of duplicating drying, cooling and conveying equipment for different cellulosic feed materials. The gases and water evolved in the dryers 38 are withdrawn from the dryers via lines 42 into two cyclones 44 in parallel, one for each dryer, by an exhaust fan 46. The discharge from the fan 46 can be passed to a dust collector (not shown) or passed directly to the atmosphere. Particulate matter withdrawn via line 42 is separated in the cyclones 44 and dropped into a fines bin 47. The particulate matter in bin 47 is fed by a rotary valve 48 to a fines bin 77 (Figure 2A). The dried feed material is transferred by a storage bin tank feed conveyer 49 to one or more storage bins 52a or 52b (Figure 2B). The different storage bins are used for storing different types of feed material. More storage bins than the two storage bins shown in Figure 2A can be used. The storage bins 52a and 52b preferably are tumbled bins to avoid compaction of the feed material and to maintain dehydration of the feed. A rotary cooler (not shown) using ambient air to cool the material dis¬ charged by the dryer can be used if required to avoid caking of the feed material in storage. The plastic feed is passed from the plastic feed bins 20b and 20c via belt conveyers 24b and 24c, respectively, to comminution devices such as granulators 56a and 56b, respectively. The smaller the particle size of the thermoplastic feed, the stronger the fuel pellets and the more even and uniform their burning characteristics, and the less plastic required in the fuel pellets. In addition, when the pellets are to be pulverized before burning, it is important that the plastic be comminuted to a small size so that each- particle resulting f om the pulverization contains both plastic and cellulosic material. Therefore, the granulators are operated so that substantially all of the particulate thermoplastic material is minus 5 mesh. Preferably, the bulk, i.e. at least 50% by weight of the particulate thermoplastic material is minus 10 mesh, and more preferably substantially all is minus 10 mesh. It is believed that optimumly substantially all of the plastic is -20 mesh. The comminuted plastic feed discharged by the granulators 56a and 56b passes to belts 57a and 57b, respectively, for transport to plastic feed storage bins 52c and 52d, respectively. More than two plastic storage bins can be used if required.Each of the storage bins has associated with it a weigh belt conveyer 62a, 62b, 62c, or 62d. The four conveyers 62a, 62b, 62c, and 62d are used to provide the proper weight ratios of the feed materials to a pellet mill 70. The four conveyers drop their feed onto a belt conveyer 64 which carries it to a chamber 65 for preheating of the feed with dry steam, if desired. From the chamber 65 the feed passes into a mixer 66OMPI W1P0 such as a combination mill to obtain uniform mixing of the different types of feed material. The mixer discharges mixed feed onto a belt conveyer 67 which lifts the feed to a pellet mill feed bin 68. The feed is gravity fed from the bin 68 to a conveyer 69 which drops the feed into the pellet mill 70 in which the pellets of the present invention, such as a pellet shown in Figure 1, are formed. Any suitable pelletizing machin can be used. In this apparatus, the material is fed into a hopper and pressed into dies having the desired configuration and shape.The pellet mill must be capable of producing a pressure in the die during compression which causes the temperature of the feed material to increase so that the pellets have a temperature of from about 66°C. to about 122°C. where they are discharged from the pellet mill, i.e. where the pressure is released. When the discharged pellets are at a temperature in excess of abou 122°C. , degradation and carbonization of the thermoplastic material can occur, and when the discharged pellets are at a temperature of less than about 66°C. , the pellets can have insufficient cohesiveness. Preferably, the discharge temperature of the pellets is from about 88 to about 123°C. to produce pellets with excellent burning properties and good cohesion. As the discharge temperature of the pellets increases, their density increases.Supplemental heat and moisture for the pellet mill 70 can be provided by steam 71 which can be generated in a boiler 72 fueled by pellets produced by this process or reject fines. The steam can be used for drying the feed in the dryers 38.Pellet mills can produce a high pressure at the impact point of the rollers to produce the desired temperature during pelletizing. A portion of the thermoplastic material forms a surface skin on the pellet at these temperatures. This skin protects the pellets from shattering and from significant changes in moisture content. Before introducing the feed to the pelletizer, it can be combined with a binding agent such as an aqueous solution of sodium silicate. For example, the material can be sprayed with about 5% by weight based on the total feed of 40 Bau e alkali stabilized sodium silicate solution added to the mixer 66. During the drying step, the moisture content needs to be adjusted to compensate for the water added by spraying with the silicate solution. It is believed that destabilized alkali sodium silicate solubilizes lignin of the cellulosic feed and the lignin then polymerizes, resulting in a stronger pellet.From the pellet mill, the formed pellets are cooled in a cooler 72 by ambient air supplied by a blower 73, and transferred to a screen 74 for separation of any fines 75 which are carried by a conveyer 76 to a fines storage bin 77. The fines are transferred from the storage bin 77 by a rotary valve 78 and a blower 79 for feed to the boiler 72 used to generate steam for the pellet mill. The product pellets 80 can be sent to storage, bagged, or transferred to trucks or railroad cars for shipment. | WHAT IS CLAIMED IS:1. A fuel pellet comprising from about 90 to about 99 percent by weight natural cellulosic material and from about 1 to about 10 percent by weight synthetic polymeric thermoplastic material, the synthetic thermoplastic material being distributed throughout the fuel pellet, the thermoplastic material being solid at room temperature and having an injection molding temperature of at least 95°C. , the free moisture content of the cellulosic material being from about 5 to about 15% by weight.2. The fuel pellet of Claim 1 wherein the thermoplastic material comprises polypropylene.3. The fuel pellet of Claim 1 wherein the thermoplastic material is selected from the group consisting of polystyrene, polyethylene, polypropylene, acrylonitrile-butadiene-styrene, acetal copolymer, acetal homopolymer, acrylic, polybutylene, and combinations thereof. 4. The fuel pellet of Claim 3 comprising up to about 1.25 percent by weight polystyrene.5. The fuel pellet of any of the preceding claims including at least about one percent by weight calcium.6. The fuel pellet of any of the preceding claims wherein the cellulosic material includes one or more of banana stalks or papaya stalks.7. The fuel pellet of any of the preceding claims wherein the cellulosic material includes oil seeds, products of oil seeds, or both. 8. The fuel pellet of any of the preceding claims having a minimum dimension of about 4.75 m.m..9. The fuel pellet of any of the preceding claims wherein the cellulosic material includes at least one member selected from the class consisting of peat and bagasse.^B 10. The fuel pellet of any of the preceding claims wherein the thermoplastic material is present in an amount of from about 2.5 percent to about 10 percent by weight. 11. A fuel pellet of any of the preceding claims wherein the synthetic thermoplastic material covers the pellet to present a substantially hydrophobic surface.12. A method for preparing a fuel pellet from particulate natural cellulosic material and particulate synthetic polymeric thermoplastic material comprising the steps of: a) providing particulate natural cellulosic material having a free moisture content of from about 5 to about 15 percent by weight, and substantially all of the particulate cellulosic material being minus 5 mesh; b) providing particulate synthetic polymeric thermoplastic material which is solid at room temperature and has an injection molding temperature of at least 90°C. , substantially all of the particulate thermoplastic material being minus 5 mesh; c) preparing a feed comprising from about 90 percent to about 99 percent by weight of the particulate cellulosic material and from about 1 percent to about 10 percent by weight of the particulate thermoplastic material; and d) compressing the feed in a die at a pressure whereby the temperature of the resulting pellet as it emerges from the die is from about 66°C. to about 122°C.13. The method of Claim 12 in which the temperature of the pellet as it emerges from the die is from about88°C. to about 123°C. 14. The method of any preceding Claim 12 and 33 in which particulate thermoplastic material is selected from the group consisting of polystyrene, polyethylene, polypropylene, acrylonitrile-butadiene-styrene, acetal copolymer, acetal homopolymer, acrylic, polybutylene, and combinations thereof.15. The method of any preceding Claim 12 through14 in which the particulate thermoplastic material includes polystyrene and the die eed comprises up to about 1.25 percent by weight of polystyrene.16. The method of any preceding Claim 12 through15 in which the particulate cellulosic material comprises banana stalks, papaya stalks, or both.17. The method of any preceding Claim 12 through 16 in which the step of providing particulate cellulosic material comprises combining particulate cellulosic material having a free moisture content greater than 55 percent by weight with calcium carbonate, and then drying the particulate cellulosic material to the prescribed free moisture content.18. The method of Claim 1 in which the particulate cellulosic material is combined with an amount of calcium carbonate equal to about 2 to about 10 percent by weight of the particulate cellulosic material. 19. The method of Claim 17 in which the particulate cellulosic material is combined with an amount of calcium carbonate equal to about 5 percent by weight of the cellulosic material.20. The method of any preceding Claim 12 through 19 in which the particulate cellulosic material includes oil seeds, products of oil seeds, or both, for lubricatio of the die. 21. The method of any preceding Claim 12 through 20 in which the step of preparing a die feed comprises preparing a die feed including from about 2.5 to about 10 percent by weight of the particulate thermoplastic material.22. The method of any preceding Claim 12 through15 in which the particulate cellulosic material comprises peat.23. The method of any preceding Claim 12 through 15 in which the particulate cellulosic material comprises bagasse.24. The method of any preceding Claim 12 through23 including the step of combining the cellulosic material with alkali stabilized sodium silicate. 25. The method of any preceding Claim 12 through24 in which the particulate cellulosic material has a free moisture content of from about 8 to about 12 percent by weight.26. The method of any preceding Claim 12 through ' 25 in which the bulk of the particulate thermoplastic material is minus 10 mesh.27. The method of any preceding Claim 12 through25 in which substantially all of the particulate thermoplastic material is minus 10 mesh. AMENDED CLAIMS(received by the International Bureau on 2 October 1979 (02.10.79)) 10. The fuel pellet of any of the preceding claims wherein the thermoplastic material is present in an amount of from about 2.5 percent to about 10 percent by weight. 11. A fuel pellet of any of the preceding claims wherein the synthetic thermoplastic material sheaths the pellet to present a substantially hydrophobic surface.12. A method for preparing a fuel pellet from particulate natural cellulosic material and particulate synthetic polymeric thermoplastic material comprising the steps of: a) providing particulate natural cellulosic material having a free moisture content of from about 5 about 15 percent by weight, and substantially all of the particulate cellulosic material being minus 5 mesh; b) providing particulate synthetic polymeric thermoplastic material which is solid at room temperatur and has an injection molding temperature of at least 90°C. , substantially all of the particulate thermoplasti material being minus 5 mesh; c) preparing a feed comprising from about 90 percent to about 99 percent by weight of the particulate cellulosic material and from about 1 percent to about 10 percent by weight of the particulate thermoplastic material; and d) compressing the feed in a die at a pressur whereby the temperature of the resulting pellet as it emerges from the die is from about 66°C. to about 122°C.13. The method of Claim 12 in which the temperatur of the pellet as it emerges from the die is from about88°C. to about 123°C. 14. The method of any preceding Claim 12 and 13 in which particulate thermoplastic material is selected from the group consisting of polystyrene, polyethylene, polypropylene, acrylonitrile-butadiene-styrene, acetal copolymer, acetal homopolymer, acrylic, polybutylene, and combinations thereof.15. The method of any preceding Claim 12 through14 in which the particulate thermoplastic material includes polystyrene and the die feed, comprises up to about 1.25 percent by weight of polystyrene.16. The method of any preceding Claim 12 through15 in which the particulate cellulosic material comprises banana stalks, papaya stalks, or both.17. The method of any preceding Claim 12 through 16 in which the step of providing particulate cellulosic material comprises combining particulate cellulosic material having a free moisture content greater than 55 percent by weight with calcium carbonate, and then drying the particulate cellulosic material to the prescribed free moisture content.. 18. The method of Claim12 in which the particulate cellulosic material is combined with an amount of calcium carbonate equal to about 2 to about 10 percent by weight of the particulate cellulosic material. 19. The method of Claim 17 in which the particulate_ cellulosic material is combined with an amount of calcium carbonate equal to about 5 percent by weight of the cellulosic material. x20. The method of any preceding Claim 12 through 19 in which the particulate cellulosic material includes oil seeds, products of oil seeds, or both, for lubrication of the die. | JOHNSTON I | JOHNSTON I |
WO-1979001003-A1 | 1,979,001,003 | WO | A1 | EN | 19,791,129 | 1,979 | 20,090,507 | new | F03G7 | F24J3 | F03G6, F24J2, F28D20 | F03G 6/06R2, F24J 2/12, F28D 20/02, R03G 6/00T150 | SOLAR ENERGY SYSTEM | A solar energy system (10) including a collector (12) for collecting and concentrating solar radiation, a receiver (14) associated with the collector for converting the radiation concentrated by the collector into thermal energy, a thermal energy accumulator (16), and a thermal energy transfer system (18) for transferring thermal energy from the receiver to the thermal energy accumulator is disclosed. The collector includes a primary reflector (30) having a shell and a removable reflective liner for concentrating radiant energy directed at it and a secondary reflector (34) for directing to the receiver the radiant energy concentrated by the primary reflector. The receiver, situated at the vertex of the primary reflector, has an internally finned compound paraboloidal cavity for receiving radiation. The thermal energy transfer system includes at least one heat pipe (82) thermally coupled to the receiver in such a way that the receiver and collector can rotate freely about the heat pipe. The thermal energy accumulator comprises a mixture of fusible salts (20) which begin nucleation at different temperatures. In one embodiment a control system includes a radiation seeker (130) which tracks the movement of the sun. | DescriptionSolar Energy System Technical FieldThe present invention relates generally to solar energy systems, and in one of its aspects, to a high temperature collector system using a salt mixture storage. Another aspect of the invention relates to a method and apparatus for tracking the movement of a radiation .source such as the movement of the sun across the sky.Background ArtThe recovery of useful energy directly from solar radiation has been the subject of much work in recent years. Collector systems including collector systems using parabolic-shaped collectors are known. Various kinds of thermal energy accumulators are known including those using mineral* storage, oil and mineral storage and liquid storage. Salt eutectics, also known as salt eutectic mixtures, have also been used for thermal energy storage as shown in ϋ. S. Patent No. 3,709,209 issued to Schroder.Mineral storage is limited to sensible heat only since there is no realistic operating range wherein the heat of fusion might be utilized. Further, since there is air in the mineral media itself, expanding gases must be dealt with. Further, the transfer of thermal energy within the mineral media itself is slow. Oil and mineral storage of thermal energy is not suitable for high temperatures due to the flammability of most oils. Additionally, oil and mineral storage systems pose drastic environmental problems in the event of either a fire or a spill. O PI « WIPO Liquid thermal energy storage systems normally have low boiling points and excessive vapor pressure and often present fla mability problems.Salt eutectics overcome many of the problems presented by the other thermal storage systems, but usually have narrow thermal bandwidths and cannot be utilized at extremely high temperatures.Compound parabolic structures are known for light collectors as described by Winston, Light Collection within the Framework of Geometric Optics , J. Optical Soc. Am., Vol. 60, pp. 245-247 (1970). The structures described by Winston were, however, developed for compound parabolic troughs of such a nature that they can be used for solar radiation collection in a fixed position relative to the earth and not have to track the sun. The present invention, on the other hand, makes use of a compound paraboloidal geometry for a radiation absorbing receiver which has no exit aperture, substantially does not reflect and is not fixed relative to the earth.A sun tracking system is shown in ϋ. S. Patent No. 3,996,917 issued to Trihey which includes two pairs of light sensitive elements disposed on opposite sides of an optical axis so that the two elements of each pair will be exposed to a different degree of solar radiation when the optical axis is misaligned with the direction of the sun, and a shading element to increase the sensitivity of the tracker to small movements of the sun. The shading element is fixed in size and position relative to the light-sensitive elements and does not take into account the differences between sunny days where the solar image is small but intense and cloudy days when the solar image is large but less intense. Disclosure of InventionThe present invention concerns a system for utilizing solar energy by collecting and concentrating solar radiation and converting the radiation concentrated into thermal energy and then storing that thermal energy at a high temperature. The solar energy system utilizes at least one collector for collecting and concentrating the solar radiation and a receiver associated with the at least one collector for converting the radiation concentrated by the collector into thermal energy at a high temperature. The thermal energy is then transferred from the receiver to a thermal energy accumulator which includes a mixture of fusible salts. The salts are fused by the high temperature of the solar energy system so that during periods of reduced sunshine, the system can continue to supply thermal energy not only from the sensible heat of the salts but also from the salts giving up the heat of fusion as various salts in the mixture nucleate. The salts of the mixture are chosen in such a way that they nucleate at different temperatures, thus spreading the time over which significant energy can be extracted from the thermal energy accumulator and maintaining the mixture in a fluid state over a wide range of temperature.One important feature of the invention is a collector for concentrating radiation from sub¬ stantially a single direction which is used as the collector for collecting and concentrating solar radiation. The collector includes a primary reflector including a concave substantially paraboloid-shaped reflecting surface for concentrating radiation and . a secondary reflector for directing to the receiver the radiation concentrated by the primary reflector. The primary reflector forms an aperture substantially at the vertex of the substantially paraboloid-shaped reflecting surface, and the receiver is disposed outside of the primary reflector opposite the aperture whereby the radiation reflected from the secondary reflector is directed through the aperture to the receiver. The primary reflector also includes a removable reflective liner for lining the concentrating side of the reflector so that the reflecting surface can actually be removed and replaced rather than polished, thus simplifying maintenance of the collector. One embodiment of the solar energy system utilizes at least one heat pipe for transferring thermal energy from the receiver to the thermal energy accumulator. The at least one heat pipe includes a means for substantially stopping the transfer of thermal energy. According to another important feature of the invention, a radiation seeker is used as a sun-seeker, and as part of a control system, the sun-seeker can be used for guiding the collector. The sun-seeker includes three photosensitive elements disposed around a central axis and an adjustable aperture along the axis so that the elements are exposed to a different amount of solar radiation when the tracker is misaligned with the direction of maximum usable solar radiation and to the same amount of solar radiation when the radiation axis is aligned with the direction of maximum usable solar- radiation. This arrangement also prevents the tracker from mistakenly tracking a bright cloud rather than the sun.The solar energy system also utilizes a control system which adjusts the position of the primary reflector with respect to its support and can stop the transfer of thermal energy from the receiver to the thermal energy accumulator as well as perform other system functions. The control system is responsive to the expected position of the sun and the position of the sun as tracked by the sun-seeker, as well as certain predetermined potentially dangerous conditions.The novel features which characterize the invention are defined by the appended claims. The foregoing and other objects, advantages and features of the invention will hereinafter appear, and for purposes of illustration of the invention, but not of limitation, an exemplary embodiment of the invention is shown in the appended drawings. Brief Description of DrawingsFigure 1. is a schematic diagram of the overall system;•Figure 2 is an elevational view of a collector according to this invention;Figure 3 is a plan view of a collector according to this invention with the collector oriented to receive radiation from straight overhead;Figure 4 is a sectional view of a collector, a receiver and part of a thermal energy transfer system utilized in the present invention;Figure 5 is a detail view taken from FIGURE 4; Figure 6 is a perspective view of a receiver and part of a thermal transfer system according to this invention;Figure 7 is a pictorial representation of a meridian view of a compound paraboloid of revolution;Figure 8 is a detail section view taken from Figure 1; Figure 9 is an isometric view in partial section of a sun-seeker according to this invention;Figure 10 diagramatically shows a sun-seeker according to the present invention;Figure 11 is a schematic diagram of the overall system showing much of the major feedback and control flow of the control system; andFigure 12 is a schematic diagram of a commercial size power station utilizing the present invention. Best Mode for Carrying Out the Invention Referring now to the drawings, a solar energy system constructed according to the present invention is indicated generally by reference numeral 10. The solar energy system 10 includes at least one collector 12 for collecting and concentrating solar radiation, a receiver 14 associated with said at least one collector 12 for converting the radiation concentrated by the collector into thermal energy, a thermal energy accumulator 16, and a thermal energy transfer system 18 for transferring thermal energy from the receiver to the thermal energy accumulator. The thermal energy accumulator 16 comprises a mixture of fusible salts 20 wherein the nucleation temperature of at least one salt of the mixture differs from the nucleation temperature of at least one other salt of the mixture.One embodiment of solar energy system 10 further comprises a means 22 thermally coupled to the fusible salt mixture for producing electric potential from the thermal energy stored in fusible salt mixture 20. Means 22 for producing electric potential includes a working fluid 24, a heat exchanger 26 thermally coupled to the fusible salt mixture for transferring heat from fusible salt mixture 20 to working fluid 24, and a means 28 driven by working fluid 24 for producing electric potential.Collector 12 of this invention is generally a collector for concentrating radiation from substantially a single direction and directing the concentrated radiation to a receiver such as receiver 14. In this embodiment, collector 12 is used for concentrating solar radiation which is substantially from a single direction at any given moment and generally comprises a pivotal means for receiving solar radiation and directing the solar radiation to receiver 14. In this embodiment, collector 12 includes a pivotal joint 15 to allow the collector to pivot. Pivotal joint 15 also houses receiver 14.Collector 12 comprises a primary reflector 30 including a concave substantially paraboloid-shaped reflecting surface 32 for concentrating radiation, a secondary reflector 34 for directing to receiver 14 the radiation concentrated by a primary reflector 30, and a means for fixing the position of secondary reflector 34 with respect to primary reflector 30 wherein the secondary reflector reflects substantially all of the radiation reflected from the primary reflector. Preferably, secondary reflector 34 is a convex i \j i -- O P reflector positioned to reflect the radiation reflected from primary reflector 30 before the radiation passes through focus. In one preferred embodiment, secondary reflector 34 is a convex parabolic reflector with a diameter roughly 10 percent as large as that of primary reflector 30. Means for fixing the position of secondary reflector 34 with respect to primary reflector 30 includes three support elements 36 disposed peripherally to primary reflector 30 and secondary reflector 34. Support elements 36 include a means for adjusting the position of secondary reflector 34 with respect to primary reflector 30, the means in. this case consisting of extensors 38.Primary reflector 30 forms an aperture 40 substantially at the vertex of paraboloid-shaped reflecting surface 32. Receiver 14 is disposed outside of primary reflector 30 opposite aperture 40 whereby the radiation reflected from secondary reflector 34 is directed through aperture 40 to receiver 14. The radiation reflected from secondary reflector 34 is preferably focused at a point interior to receiver 14.Referring now to Figures 2 through 5, collector 12 is used in conjunction with a support element 42. Collector 12 further comprises a base support 44 for pivotally mounting primary reflector 30, and a plurality of linear actuators which in this case consist of three hydraulic jacks 46 for adjusting the position of primary reflector 30 with respect to base support 44, the linear actuators being disposed from one another between primary reflector 30 and support element 42.Primary reflector 30 comprises a removable liner 48, better shown in Figure 5, for lining the concentrating side of reflector 30, the liner having a reflective side for concentrating the radiation. When in place, the reflective side of liner 48 becomes reflecting surface 32 for concentrating radiation. Primary reflector 30 further comprises a means 50 for evacuating air from between liner 48 and the adjacent portion of the rest of primary reflector 30 whereby liner 48 is held in place by air pressure. A ring 52, preferably made of silicone or thermo resistant plastic, is also included in primary reflector 30 in this embodiment to aid in holding liner 48 in place and to assist in installing a new removable liner.Primary reflector 30 comprises a reinforced plastic shell 54 which forms a concave substantially paraboloid-shaped surface 56 for receiving removable liner 48. Rubber ring 52 grips outer edge 58 of reinforced plastic shell 54 and grips removable liner 48 in slit 59. Thus, when replacing removable liner 48, a workman slides a new liner 48 into slit 59 and then establishes a vacuum underneath the liner by means 50. Means 50, in one embodiment, includes a plurality of porous areas through which air can be evacuated while still providing support to liner 48. By means of this invention, maintaining a high quality reflecting surface for a collector becomes a simple matter which can be routinely performed by relatively unskilled labor. Maintaining the reflecting surface no longer requires elaborate cleaning or buffing operations. Removable liner 48 is made of metal coated plastic such as aluminized plastic, and secondary reflector 34 comprises a highly polished surface such as the mirrors used in high powered lasers, although suitable substitute materials such as an electroplated metal stamping might be found. Referring now to Figures 6 and 7, a preferred embodiment of- receiver 14 forms a cavity 60 with an aperture 62 for receiving the collected and concentrated solar radiation into cavity 60. Aperture 62 is oppositely disposed to vertex aperture 40. formed by primary reflector 30. Receiver 14 further comprises a plurality of radiation absorptive and thermally conductive fins 64 projecting from the wall of cavity 60. The wall of cavity 60 formed by theO PI receiver is generally a compound paraboloid of revolution. The generating compound parabola of this embodiment is composed of four parabolic sections 66, 68, 70 and 72 which intersect at intersection points 74, 76, and 78. The generating compound parabola is revolved around an axis of revolution 81 to generate the compound paraboloid surface which describes the wall of cavity 60. The extensions of the parabolic sections beyond the intersection points are shown for illustration only. The curve formed by the inner edge of one of fins 64 is geometrically similar to the generating compound parabola. The solar radiation directed into receiver 14 by secondary reflector 34 is preferably focused at a point 80 which is interior to cavity 60.Receiver 14 further comprises a means for increasing the radiation absorptive surface area of the cavity wall and plurality of fins 64. In this case the means includes surface roughness of the radiation absorptive surfaces. It can thus be seen, that due to its compound paraboloid of revolution shape along with the use of fins and surface roughness all aiding in its radiation absorptive and thermally conductive characteristics, that receiver 14 is well suited for converting the radiation concentrated by collector 12 into thermal energy. Due to the nature and characteristics of the receiver, very little of the energy reradiated from the surface of the wall of cavity 60 and fins 64 will be lost from the receiver. The wall of cavity 60 and the plurality of fins 64 are preferably colored black to aid in radiation absorption. Receiver 14 is substantially enclosed in thermal insulation 65 for preventing loss of thermal energy. A preferred embodiment of thermal energy transfer system 18 comprises at least one heat pipe 82, heat pipe 82 including an evaporator section 84 thermally coupled to receiver 14 and a condensor section 86 thermally coupled to thermal energy accumulator 16 by means of terminator 87. Terminator 87, in a preferred embodiment, comprises a ceramic material such as berrylium oxide. At least one heat pipe 82 comprises a liquid metal working fluid for high temperature applications.Thermal energy transport system 18 further comprises a thermally conducting coupling 88 thermally coupled to receiver 14 and the at least one heat pipe 82, wherein coupling 88 rotates freely about the at least one heat pipe 82 and coupling 88 rotates freely within base 90 of receiver 14. The axis of rotation 92 of coupling 88 is in a direction substantially perpendicular to the axis of rotation 94 of receiver 14. It can thus be seen that heat is transferred from receiver 14 to the at least one heat pipe 82, and receiver 14 pivots freely with respect to the at least one heat pipe 82 so that the collector heat pipe combination is free to track the sun. In one embodiment of thermal energy accumulator 16, mixture of fusible salts 20 comprises a mixture of sodium salts. The mixture of sodium salts consists mainly of sodium sulphate and at least one salt from the group of sodium sulfide, sodium chloride and sodium metasilicate. Preferably, the mixture of sodium salts consists mainly of sodium sulphate, sodium sulfide, sodium chloride and sodium metasilicate. Sodium sulphate has a relatively low -fusion temperature of'31°C. Once the sodium sulphate has fused, the entire mixture can be kept in a flowable condition since, if the salts of the mixture are carefully chosen, the nonfused salts will remain in gelling pockets throughout the mixture. Once the entire mixture is brought to its normal operating temperature, all of the salts of the mixture will be in a liquid state. During periods when the energy received by the solar energy system from the sun is inadequate to keep up with the demands on the system by the system's energy thermal energy accumulator 16 can continue to supply usable energy over a long period of time and considerable temperature range since mixture of fusible salts 20 can yield not only sensible heat, but can also yield the heat of fusion for each of the salts as each of the salts nucleates. Since at least one of the salts of the mixture remains in a liquid state throughout all of the useful operating temperatures of the mixture, transfer of thermal energy within the mixture of fusible salts 20 itself and transfer of thermal energy from mixture of fusible salts 20 to heat exchanger 26 is facilitated. The mixture of fusible salts 20 of this embodiment can be kept at an average temperature between 1000°C and the boiling temperature of the entire mixture. In another embodiment of the present invention, mixture of fusible salts 20 is a mixture of sodium salts which consist mainly of sodium chloride, sodium nitrate, sodium hydroxide, sodium sulfide, sodium sulphate and sodium metasilicate. Referring now to Figure 1 and Figure 8, thermal energy accumulator 16 further comprises a refractory material lining 96 for substantially enclosing mixture of fusible salts 20, a plurality of metal plates 98 for supporting refractory material lining 96, and a plurality of structural members such as H-beam 100 external to metal plates 98 and engaging metal plates 98 for providing structural strength to thermal energy accumulator 16. A preferred embodiment of refractory material lining 96 comprises fused cast aluminum oxide although other suitable refractories are known in the art.Thermal energy accumulator 16 also comprises a reinforced concrete wall 102 substantially enclosing the structure made up of refractory material lining 96, plurality of metal plates 98 and the plurality of structural members such as H-beam 100. The structural members such as H-beam 100 act as • spacers between plurality of metal plates 98 and reinforced concrete wall 102. This allows the use of an insulation such as alumina-silica insulation between plurality of metal plates 98 and reinforced concrete wall 102. As used here the term metal plates includes but is not limited to steel plates. Reinforced concrete wall 102 is preferably a steel-reinforced concrete wall. The term wall includes the floor and ceiling structure also. Reinforced concrete wall 102 is not necessary for systems that are sufficiently small. Referring again to Figure 1, one means for producing electric potential 22 includes a Rankine cycle power system which includes means 28 driven by working fluid 24 for producing electric potential. Means 28 includes a turbine 108 and a generator 106 driven by turbine 108 through gearing means 110. In this configuration, heat exchanger 26 acts as the boiler or heater for the Rankine cycle power system. For further efficiency, means 22 for producing electric potential can also include a second cycle, the second cycle including heat exchanger 112 and working fluid 114 in a heat exchange relationship with working fluid 24.- Heat- exchanger 112 thus acts as the condenser for the first cycle as in a normal binary cycle system. Pump 25 is included in the first cycle to recompress working fluid 24 and pump 115 is added in the second cycle to recompress working fluid 114 after working fluid 114 has been passed through a condenser 113.A preferred embodiment of means 22 for producing electric potential includes a relief valve 116 for releasing working fluid 24 in the event of excessive pressure in working fluid 24 caused by some malfunction in the overall system such as an overheating of mixture of fusible salts 20. Relief valve 116 should only be opened in extreme emergency since the release of working fluid 24 into the environment would normally be undesirable. Means 22 further includes normally open bypass valve 117 for bypassing turbine 108 during nor al operating conditions with some percentage of working fluid 24 in its high pressure gas stage. Turbine 108 can immediately respond to increased load by closing normally open bypass valve 117. A preferred embodiment of solar energy system 10 also includes a control system. Referring now to Figure 11, the control system includes a means 118 for driving the plurality of linear actuators such as hydraulic jacks 46 whereby the control system adjusts the position of primary reflector 30 with respect to base support 44.The control system further comprises a means for tracking the expected direction of maximum usable solar radiation relative to the axis of substantially paraboloid-shaped reflecting surface 32 of the primary reflector which will also be referred to as the axis of the primary reflector. The tracking means comprises basically a calculator or table lookup for computing or storing information regarding the solar ephemeris. The calculations or lookup can be performed by cams or a computer. The tracking means is cooperatively coupled to means 118 for driving the plurality of linear actuators and is responsive to misalignments between the primary reflector and the expected direction of maximum usable solar radiation.The control system further comprises a means for sensing the true orientation of primary reflector 30 relative to base support 44, and a means for detecting a predetermined potentially damaging condition affecting the solar energy system. One embodiment of the means for sensing the true orientation of primary reflector 30 relative to base support 44 includes a plurality of linear displacement transducers 120 disposed between support element 42 and primary reflector 30. Each linear displacement transducer 120 measures the length of a cord 122 between a given point on support element 42 and a given point on primary reflector 30. One type of such linear displa transducer includes a rotary encoder such as a shaft positioned encoder which is turned as cord 122 is pulled out by primary reflector 30 or drawn back by a spring element. The location of the given points and the lengths of cord 122 give the true orientation of primary reflector 30. The orientation sensing means and the detecting means are cooperatively coupled to means 118 for driving the plurality of linear actuators such as hydraulic jacks 46 whereby the means 118 for driving the plurality of linear actuators is responsive to the predetermined potentially damaging condition whereby the control system adjusts the position of primary reflector 30 with respect to base support to lessen the effects of the predetermined potentially damaging condition and adjusts the position of the primary reflector for normal operation when the predetermined potentially dangerous condition has passed.One embodiment of the means for detecting a predetermined potentially damaging condition affecting solar energy system 10 comprises a means for detecting potentially damaging wind strain on .the collector. The means for detecting potentially damaging wind strain on the collector includes strain gauges 124 and data link 126 to transmit data from strain gauges 124 to the decision making portion of the control system, whereby the control system adjusts the position of primary reflector 30 with respect to base support 44 to lessen the effects of the wind strain. One embodiment of the means for detecting a predetermined potentially dangerous condition affecting solar energy system 10 includes a means 128 for detecting potentially damaging high temperature in mixture of fusible salts 20 whereby the control system adjusts the position of primary reflector 30 with respect to base support 44 to misalign primary reflector 30 and the sun in order to decrease the energy flow from the collector to mixture of fusible JUREOMP i A, WI? salts 20. This misaligning of primary reflector 30 and the sun prevents the further overheating of mixture of fusible salts 20 and allows means for producing electric potential 22 or other means for using the stored thermal energy to reduce the temperature within mixture of fusible salts 20. Means 128 for detecting potentially damaging high temperature in mixture of fusible salts 20 can also include means for detecting potentially damaging pressure, thermal loss or salt leakage.The control system further comprises a radiation seeker 130 used as a sun seeker. Sun seeker 130 is cooperatively coupled to means 118 for driving the . plurality of linear actuators, in this case hydraulic jacks 46. Seeker 130 includes at least three photosensitive elements 132 and a means for shading photosensitive elements 132, the means for shading comprising a substantially encircling wall 134 and a variable shading means 136 which forms aperture 138. In this embodiment of radiation seeker 130, the at least three photosensitive elements 132 consist of three roughly coplanar photosensitive elements. The locus of points equidistant from three photosensitive elements 132 defines a radiation axis so that three photosensitive elements 132 are substantially equally spaced from one another around the radiation axis, and aperture 138 is substantially concentric about the radiation axis, wherein the elements 132 are exposed to a different amount of radiation when the radiation axis is misaligned with the direction of maximum usable radiation and to the same amount of radiation when the radiation axis is aligned with the direction of maximum usable radiation. At least three photosensitive elements 132 are preferably somewhat angled in toward the radiation axis.Radiation seeker 130 is cooperatively coupled to means 118 for driving the plurality of linear actuators through the decision making portion of the control system and data link 140. The decision making portion of the control system includes differential amplifier 142 and comparators 143a, 143b and 143c. The voltage output 144 of differential amplifier 142 is the average of the output voltages of elements 130a, 130b and 130c. Each of the comparators will have a non-zero output whenever the voltage output of its associated element 130 exceeds the average voltage as indicated by output 144. The outputs 145 of comparators 143 are used to drive hydraulic jacks 46, and in this case, are part of the means for driving the plurality of linear actuators. Thus, means 118 for driving the plurality of linear actuators is responsive to misalignments between primary reflector 30 and the direction of maximum usable solar radiation. As used here, the term photosensitive is used in a broad sense of meaning not just light sensitive, but rather sensitive to all radiation in the range of interest. Similarly, how well radiation seeker 130 aligns with the direction of maximum usable radiation is dependent upon how sensitive photosensitive elements 132 are. to radiation in the usable range of frequencies.-Variable shading means 136 is responsive to the amount of available usable radiation whereby the size of aperture 138 is responsive to actual radiation conditions. When radiation seeker 130 is used to track the sun, the size of aperture 138 is responsive to the size of the solar image as affected by distance from the sun, clouds, etc. as well as other conditions, thus aiding in more accurately tracking the maximum usable solar radiation. Additionally, by varying the size of aperture 138 according to the amount of available usable radiation, radiation seeker 130 will track the actual solar image and not mistake a bright cloud for the image to be followed. The radiation of interest for solar energy system 10 is solar radiation, but the principals used in radiation seeker 130 work equally well for other forms of radiation.'BU RO . At least one heat pipe 82 includes a means 146 for substantially stopping the transfer of thermal energy from receiver 14 to thermal energy accumulator 16. The control system includes a means 148 for detecting a predetermined level of solar radiation cooperatively coupled to means 146 for substantially stopping the transfer of thermal energy whereby means 146 for substantially stopping the transfer of thermal energy is responsive to the predetermined level of solar radiation. Normally, the predetermined level of solar radiation is a level of solar radiation so low that it takes more energy to operate solar energy system 10 than is received by the system, so that there would be a net energy drain on the system to try to continue to operate. This situation would exist between a certain time in the evening and a certain time in the morning as well as on extremely overcast days. Means 146 for substantially stopping the transfer of thermal energy is also used to prevent reverse heat flow in heat pipe 82 which would drain heat from accumulator 16.Means 128 for detecting a predetermined temperature within thermal energy accumulator 16 is also cooperatively coupled to means 146 for substantially stopping, the transfer of thermal energy whereby means 146 for substantially stopping the transfer of thermal energy is responsive to the predetermined temperature within thermal energy accumulator 16. Thus, if the predetermined temperature is a dangerously high temperature, means 146 can be actuated to substantially stop the transfer of thermal energy from receiver 14 to thermal energy accumulator 16 so that the temperature in thermal energy accumulator 16 is not raised further.One suitable means 146 for substantially stopping the transfer of thermal energy is a magnetically operated butterfly valve within at least one heat pipe 82, although other suitable means for thermally switching heat pipes are known. One embodiment of the control system also includes a data link 150 for transmitting information regarding the pressure, temperature and leakage of working fluid 24 within heat exchanger 26, data link 152 for reporting the speed and torque of turbine 108, and data link 154 for reporting the current and frequency of generator 106. The term data link is used throughout to refer to both digital and analog data. Data link 150 is also another means for detecting a predetermined potentially damaging condition.The control system of this embodiment also includes a means 156 for controlling relief valve 116 responsive to data link 150 for reporting pressure,. temperature and leakage of working fluid 24 within heat exchanger 26. Thus, dangerously high working fluid pressure can be relieved by opening relief valve 116. The control system further comprises means 158 for throttling the flow of working fluid 24.Solar energy system 10 further comprises retaining wall 168 which in cooperation with thermal energy accumulator 16 forms moat 170 for retaining salt spills or at least impeding the flow of released salts and, thus, preventing ecological havoc. In general, small installations such as residential installations would not have as much need for retaining wall 168 as would large installations.Although a preferred embodiment of the invention has been described in detail, it should be understood that various changes, substitutions, and alterations can be made therein without departing from the spirit and scope of the invention as defined by the appended claims. In general, collector 12 is a means for directing concentrated solar radiation to receiver 14. Thermal energy accumulator 16 in combination with either means 22 for producing electric potential or any other means for utilizing the thermal energy from thermal energy accumulator 16 make up one means for utilizing thermal energy.-BUREOMPI r W1PO In embodiments in which at least one collector 12 must substantially face a certain direction with respect to the sun, the embodiment of at least one collector 12 illustrated is only one pivotal means for receiving solar radiation and directing the solar radiation to receiver 14.In an alternative embodiment of at least one collector 12, primary reflector 30 comprises a substantially paraboloid-shaped reflecting surface and secondary reflector 34 comprises a hyperbolic reflecting surface, changing the diameter of secondary reflector 34 relative to the diameter of primary reflector 30 to. approximately 50 percent.Many features and subcombinations of this invention are of utility and other applications are contemplated within the scope of the claims. For instance, radiation seeker 130 can also be used for surveying as in laser alignment of large pipelines now being done by conventional optical methods or for the precise guidance of telescopes. At least one collector 12 can be used to provide commercial or residential heat directly.Referring now to Figure 12, solar energy system 160 includes an array 162 of collectors 12, suitable for commercial power generation, to collect and concentrate solar radiation. A receiver 14 is associated with each of said collectors for converting the radiation concentrated by the collectors into thermal energy. Thermal energy transfer system 18 transfers thermal energy from receivers 14 to thermal energy accumulator 16. Solar energy system 160 further comprises a means 22 thermally coupled to mixture of fusible salts 20 within thermal energy accumulator 16 for producing electric potential from the thermal energy stored in the fusible salt mixture. Solar energy system 160 further comprises a cooling tower 164 for cooling working fluid 24 used by solar energy system 160, and a maintenance building 166.- wipo Thus, it will be appreciated that the present solar energy system solves the problems of many collector type systems of the past. First, there is no need to suspend a boiler or any liquid carrying element at the focal point of the primary reflector. Secondly, the receiver which converts radiation into thermal energy is situated at the base of the primary reflector, near the thermal energy transfer system, rather than at the focal point of the primary reflector. Further, the receiver itself does not need to transfer any liquid medium to the thermal energy transfer system, although the receiver could be filled with such medium to be heated in certain applications. Additionally, a preferred embodiment of the system is one in which the only liquid transfer is the liquid metal of the liquid metal heat pipe which is highly efficient and of high reliability. Still further, the thermal energy accumulator not only yields sensible heat, but also yields the heat of fusion of the salts in the mixture over a wide range of temperatures while still remaining in a liquid state. Besides these advantages, the primary collector of the system can be maintained in good condition by simply replacing the reflective liner. Other advantages of the solar energy system of this invention are obvious from the description and the appended claims.Although a preferred embodiment of the invention has been described in detail, it should be understood that various changes, substitutions and alterations can be made therein without departing from the spirit and scope of the invention as defined by the appended claims. | Claims1. A solar energy system comprising, in combination: at least one collector for collecting and concentrating solar radiation; a receiver associated with said at least one collector for converting the radiation concentrated by the collector into thermal energy; a thermal energy accumulator; and a thermal energy transfer system for transferring thermal energy from the receiver to the thermal energy accumulator; wherein the thermal energy accumulator comprises a mixture of fusible salts, and wherein the nucleation temperature of at least one salt of the mixture differs from the nucleation temperature of at least one other salt of the mixture.2. A solar energy system according to Claim 1, wherein the at least one collector comprises, in combination: a primary reflector including a concave substantially paraboloid-shaped reflecting surface for concentrating radiant energy from the sun; a secondary reflector for directing to the receiver the radiant energy concentrated by the primary reflector; and a means for fixing the position of the secondary reflector with respect to the primary reflector wherein the secondary reflector reflects substantially all of the radiant energy reflected from the primary reflector. 3. A solar energy system according to Claim 2, wherein the primary reflector forms an aperture substantially at the vertex of the substantially paraboloid-shaped reflecting surface and the receiver is secured to the outside of the aperture whereby the radiant energy reflected from the secondary reflector is directed through the aperture to the receiver.4. A solar energy system according to Claim 3 to be used in conjunction with a support element, wherein the collector further comprises: a base support for pivotally mounting the primary reflector; and a plurality of linear actuators for adjusting the position of the primary reflector with respect to the base support, wherein the linear actuators are disposed from one another between the primary reflector and the support element.5. A solar energy system according to Claim 4 further comprising a control system comprising a means for driving the plurality of linear actuators whereby the control system adjusts the position of the primary reflector with respect to the base support.6. A solar energy system according to Claim 5 wherein the control system further comprises a means for tracking the expected direction of maximum usable solar radiation relative to the axis of the primary reflector, the tracking means cooperatively coupled to the means for driving the plurality of linear actuators whereby the means for driving the plurality of linear actuators is responsive to misalignments between the primary reflector and the expected direction of maximum usable solar radiation. 7. A solar energy system according to Claim 6 wherein the control system further comprises: a means for sensing the true orientation of the primary reflector relative to the base 5 support; and a means for detecting a predetermined potentially damaging condition affecting the solar energy system; wherein the orientation sensing means and the10 detecting means are cooperatively coupled to the means for driving the plurality of linear actuators whereby the means for driving the plurality of linear actuators is responsive to the predetermined potentially damaging condition15. whereby the control system adjusts the position of the primary reflector with respect to the base support to lessen the effects of the predetermined potentially damaging condition and adjusts the position of the primary reflector for normal20 operation when the predetermined potentially dangerous condition has passed.8. A solar energy system according to Claim 7 wherein the means for detecting a predetermined potentially damaging condition affecting the solar25 energy system comprises a means for detecting potentially damaging wind strain on the collector whereby the control system adjusts the position of the primary reflector with respect to the base support to lessen the effects of the wind strain. 9. A solar energy system according to Claim 7 wherein the means for detecting a predetermined potentially dangerous condition affecting the solar energy system comprises a means for detecting potentially damaging high temperature in the mixture of fusible salts whereby the control system adjusts the position of the primary reflector with respect to the base support to misalign the primary reflector and the sun to decrease the energy flow from the collector to the mixture of fusible salts.10. A solar energy system according to Claim 5 wherein the control system further comprises a sun seeker cooperatively coupled to the means for driving the plurality of linear actuators, the sun seeker having a radiation axis arranged to be substantially parallel to the axis of the primary reflector and including at least three photo¬ sensitive elements substantially equally spaced from one another around the radiation axis and also including means for shading the photo¬ sensitive elements, wherein the shading means forms an aperture substantially concentric about the radiation axis, the elements being exposed to a different amount of solar radiation when the radiation axis is misaligned with the direction of maximum usable solar radiation, and to the same amount of solar radiation when the radiation axis is aligned with the direction of maximum usable solar radiation, whereby the means for driving the plurality of linear actuators is responsive to misalignments between the primary reflector and the direction of maximum usable solar radiation.BUO 11. A solar energy system according to Claim 4 wherein the thermal energy transfer system comprises at least one heat pipe, the heat pipe including an evaporator section thermally coupled to the receiver and a condensor section thermally coupled to the thermal energy accumulator.12. A solar energy system according to Claim 11 wherein the at least one heat pipe comprises a liquid metal working fluid.13. A solar energy system according to Claim 11 wherein the thermal energy transport system further comprises a thermally conducting coupling thermally coupled to the receiver and the at least one heat pipe for receiving the at least one heat pipe, wherein the coupling rotates freely about the at least one heat pipe and the coupling rotates freely within the base of the receiver, the axis of rotation of the coupling being in a direction substantially perpendicular to the axis of rotation of the receiver whereby heat is transferred from the receiver to the at least one heat pipe and .the receiver pivots freely with respect to the at least one heat pipe.14. A solar energy system according to Claim 13, wherein the at least one heat pipe comprises a means for substantially stopping the transfer of thermal energy from the receiver to the thermal energy accumulator, the solar energy system further comprising a control system, the control system comprising a means for detecting a pre¬ determined level of solar radiation cooperatively coupled to the means for substantially stopping the transfer of thermal energy whereby the means for substantially stopping the transfer of thermal energy is responsive to the predetermined level of solar radiation. 15. A solar energy system according to Claim 14 wherein the receiver forms a cavity with an aperture oppositely disposed to the vertex aperture formed by the primary reflector wherein the wall of the cavity is generally a compound paraboloid of revolution, the receiver further comprising a plurality of radiation absorptive and thermally conductive fins projecting from the wall of the cavity.16. A solar energy system according to Claim 12 wherein the mixture of fusible salts comprises a mixture of sodium salts.17. A solar energy system according to Claim 16 wherein the thermal energy accumulator comprises: a refractory material lining for sub¬ stantially enclosing the mixture of fusible salts; a plurality of metal plates for supporting the refractory material lining; and a plurality of structural members external of the metal plates and engaging the metal plates for providing structural strength to the thermal energy accumulator.18. A solar energy system according to Claim 17 wherein the refractory material lining comprises fused cast aluminum oxide. 19. A solar energy system according to Claim 17, wherein the at least one heat pipe comprises a means for substantially stopping the transfer of thermal energy from the receiver to the thermal energy accumulator, the solar energy system further comprising a means for detecting a predetermined temperature within the thermal energy accumulator cooperatively coupled to the means for substantially stopping the transfer of thermal energy whereby the means for substantially stopping the transfer of thermal energy is responsive to the predetermined temperature within the thermal energy accumulator.20. A solar energy system according to Claim 19 further comprising a means thermally coupled to the fusible salt mixture for producing electric potential from the thermal energy stored in the fusible salt mixture.21. A solar energy system according to Claim 20 wherein the means for producing electric potential from the thermal energy stored in the fusible salt mixture comprises, in combination; a working fluid; a heat exchanger thermally coupled to the fusible salt mixture for transferring heat from the fusible salt mixture to the working fluid; and a means driven by the working fluid for producing electric potential.22. A solar energy system according to Claim 1 wherein the at least one collector comprises a primary reflector for concentrating radiant energy from the sun, the primary reflector comprising a reinforced plastic shell. 23. A solar energy system according to Claim 22 wherein primary reflector further comprises in combination: a removable liner for lining the concen- trating side of the shell, the liner having a reflective side facing away from the shell for concentrating radiant energy from the sun; and a means for evacuating air from between the shell and the liner whereby the liner is held in place by air pressure.24. A solar energy system according to Claim 23 to be used in conjunction with a support element, wherein the primary reflector includes a concave substantially paraboloid-shaped reflecting surface, the at least one collector further comprising: a base support for pivotally mounting the primary reflector; and a plurality of linear actuators for adjusting the position of the primary reflector with respect to the base support, wherein the linear actuators are disposed from one another between the primary reflector and the support element.25. A solar energy system according to Claim 24 further comprising a control system, the control system comprising a means for driving the plurality of linear actuators whereby the control system adjusts the position of the primary reflector with respect to the base support.O > r W 26. A solar energy system according to Claim 25 wherein the control system further comprises a means for tracking the expected direction of maximum usable solar radiation relative to the axis of the primary reflector, the tracking means cooperatively coupled to the means for driving the plurality of linear actuators whereby the means for driving the plurality of linear actuators is responsive to misalignments between the primary reflector and the expected direction of maximum usable solar radiation.27. A solar energy system according to Claim 26 wherein the control system further comprises: a means for sensing the true orientation of the primary reflector relative to the base support; and a means for detecting a predetermined potentially damaging condition affecting the solar energy system; wherein the orientation sensing means and the detecting means are cooperatively coupled to the means for driving the plurality of linear actuators whereby the means for driving the at least three linear actuators is responsive to the predetermined potentially damaging condition whereby the control system adjusts the position of the primary reflector with respect to the base support to lessen the effects of the predetermined potentially damaging condition and adjusts the position of the . primary reflector for normal operation when the predetermined potentially dangerous condition has passed. 28. A solar energy system according to Claim 25 wherein the control system further comprises a sun seeker cooperatively coupled to the means for driving the plurality of linear actuators, the sun seeker having a radiation axis arranged to be substantially parallel to the axis of the primary reflector and including at least three photo¬ sensitive elements substantially equally spaced from one another around the radiation axis and also including means for shading the photo¬ sensitive elements, wherein the shading means forms an aperture substantially concentric about the radiation axis, the elements being exposed to a different amount of solar radiation when the radiation axis is misaligned with the direction of maximum usable solar radiation and to the same amount of solar radiation when the radiation axis is aligned with the direction of maximum usable solar radiation, whereby the means for driving the plurality of linear actuators is responsive to misalignments between the primary reflector and the direction of maximum usable solar radiation.29. A solar energy system according to Claim 25 wherein the at least one collector further comprises, in combination: a secondary reflector for directing to the receiver the radiant energy concentrated by the primary reflector; and a means for fixing the position of the secondary reflector with respect to the primary reflector wherein the secondary reflector reflects substantially all of the radiant energy reflected from the primary reflector. 30. A solar energy system according to Claim 29 wherein the primary reflector forms an aperture substantially at the vertex and the receiver is secured to the outside of the aperture whereby the radiant energy reflected from the secondary reflector is directed through the aperture to the receiver.31. A solar energy system according to Claim 1 wherein the receiver forms a cavity with an aperture for receiving the collected and concentrated solar radiation into the cavity, the receiver further comprising a plurality of radiation absorptive and thermally conductive fins projecting from the wall of the cavity.32. A solar energy system according to Claim 31 wherein the wall of the cavity formed by the receiver is generally a compound paraboloid of revolution.33. A solar energy system according to Claim 32 wherein the receiver further comprises a means for increasing the radiation absorptive surface area of the cavity wall and the plurality of fins, the means including surface roughness of the radiation absorptive surfaces.34. A solar energy system according to Claim 1 wherein the mixture of fusible salts comprises a mixture of sodium salts. 35. A solar energy system according to Claim 34 wherein the thermal energy accumulator comprises: a refractory material lining for substantially enclosing the mixture of fusible salts; a plurality of metal plates for supporting the refractory material lining; and a plurality of structural members external to the metal plates and engaging the metal plates for providing structural strength to the thermal energy accumulator.36. A solar energy system according to Claim 35 wherein the refractory material lining comprises fused cast aluminum oxide.37. A solar energy system according to Claim 36 further comprising a means thermally coupled to the fusible salt mixture for producing electric potential from the thermal energy stored in the fusible salt mixture.38. A solar energy system according to Claim 37 wherein the means for producing electric potential from the thermal energy stored in the fusible salt mixture comprises, in combination; a working fluid; a heat exchanger thermally coupled to the fusible salt mixture for transferring heat from the fusible salt mixture to the working fluid; and a means driven by the working fluid for producing electric potential.39. A solar energy system according to Claim 34 wherein the mixture of sodium salts consists mainly of sodium sulfate and at least one salt from the group of sodium sulfide, sodium chloride and sodium metasilicate. 40. A solar energy system according to Claim 1 further comprising a means thermally coupled to the fusible salt mixture for producing electric potential from the thermal energy stored in the fusible salt mixture.41. A solar energy system according to Claim 40 wherein the means for producing electric potential from the thermal energy stored in the fusible salt mixture comprises, in combination; a working fluid; a heat exchanger thermally coupled to the fusible salt mixture for transferring heat from the fusible salt mixture to the working fluid; and a means driven by the working fluid for producing electric potential.42. A solar energy system according to Claim 1 wherein the at least one collector comprises a pivotal means for receiving solar radiation and directing the solar radiation to the receiver, the solar energy system further comprising a control system including a means for driving the pivotal means for receiving solar radiation and directing the solar radiation to the receiver.43. A solar energy system according to Claim 42 wherein the control system further comprises a sun seeker cooperatively coupled to the means for driving the pivotal means for receiving solar radiation and directing the solar radiation to the receiver, the sun seeker comprising a means for sensing misorientations between the actual direction of the pivotal means and direction of the pivotal means for directing the maximum usable solar radiation to the receiver, the sensing means having a radiation axis and including at least three photosensitive elements substantially equally spaced from one another around the radiation axis and also including means for shading the photosensitive elements, wherein the shading means forms an aperture substantially concentric about the radiation axis, the elements being exposed to a different amount of solar radiation when the radiation axis is misaligned with the direction of maximum usable solar radiation and to the same amount of solar radiation when the radiation axis is aligned with the direction of maximum usable solar radiation.44. A solar energy system comprising, in combination: a receiver for converting radiation into thermal energy; a means for directing concentrated solar radiation to the receiver; a means for utilizing thermal energy; and a thermal energy transfer system for transferring thermal energy from the receiver to the thermal energy utilizing means whereby the thermal energy utilizing means can utilize the thermal energy transferred from the receiver; wherein the thermal energy transfer system comprises at least one heat pipe, the heat pipe including an evaporator section thermally coupled to the receiver and a condensor section thermally coupled to the means for utilizing thermal energy. B_ - ^- 45. A solar energy system according to Claim 44 wherein the thermal energy transport system further comprises a thermally conducting coupling thermally coupled to the receiver and the at least one heat pipe for receiving the at least one heat pipe, wherein the coupling rotates freely about the at least one heat pipe and the coupling rotates freely within the base of the receiver, the axis of rotation of the coupling being in a direction substantially perpendicular to the axis of rotation of the receiver whereby heat is transferred from the receiver to the at least one heat pipe and the receiver pivots freely with respect to the at least one heat pipe.46. A solar energy system according to Claim 45 wherein the at least one heat pipe comprises a means for substantially stopping the transfer of thermal energy, the solar energy system further comprising a control system, the control system comprising a means for detecting a predetermined level of solar radiation cooperatively coupled to the means for substantially stopping the transfer of thermal energy whereby the means for substantially stopping the transfer of thermal energy is responsive to the predetermined level of solar radiation.47. A solar energy system according to Claim 46 wherein the receiver forms a cavity with an aperture oriented to receive the concentrated solar energy from the directing means wherein the wall of the cavity is generally a compound paraboloid of revolution, the receiver further comprising a plurality of radiation absorptive and thermally conductive fins projecting from the wall of the cavity. 48. A solar energy system comprising, in combination: a receiver for converting radiation into thermal energy; a means for directing concentrated solar radiation to the receiver; a means for utilizing thermal energy; and a thermal energy transfer system for transferring thermal energy from the receiver to the thermal energy utilizing means whereby the thermal energy utilizing means can utilize the thermal energy transferred from the receiver; wherein the receiver forms a cavity with an aperture oriented to receive the concentrated solar radiation from the directing means, the receiver comprising a plurality of radiation absorptive and thermally conductive fins projecting from the wall of the cavity.49. A solar energy system according to Claim 48 wherein the wall of the cavity formed by the receiver is generally a compound paraboloid of revolution.50. A solar energy system according to Claim 49 wherein the receiver further comprises a means for increasing the radiation absorptive surface area of the cavity wall and the plurality of fins, the means including surface roughness of the radiation absorptive surfaces. | SOLAR DYNAMICS LTD | MARKE R |
WO-1979001004-A1 | 1,979,001,004 | WO | A1 | EN | 19,791,129 | 1,979 | 20,090,507 | new | F24H7 | F28D13, F27B14, C09K3 | C09K5, F03G6, F24J2, F28D20 | C09K 5/06B, F03G 6/06R2, F24J 2/07, F24J 2/18, F24J 2/32, F28D 20/02D, R03G 6/00T150 | THERMAL ENERGY ACCUMULATOR | A solar energy system (10) including a collector (12) for collecting and concentrating solar radiation, a receiver (14) associated with the collector for converting the radiation concentrated by the collector into thermal energy, a thermal energy accumulator (16), and a thermal energy transfer system (18) for transferring thermal energy from the receiver to the thermal energy accumulator is disclosed. The thermal energy accumulator comprises a mixture of fusible salts (20) which begin nucleation at different temperatures whereby the latent heat of fusion of the contained salts can be used to spread the time over which usable heat can be extracted from the thermal energy accumulator, while maintaining the total mixture in a flowable state. | DescriptionThermal Energy AccumulatorTechnical FieldThe present invention relates generally to solar energy systems, and in one of its aspects, to a high temperature collector system using a salt mixture storage. Another aspect of the invention relates to a method and apparatus for tracking the movement of a radiation source such as the movement of the sun across the sky.Background ArtThe recovery of useful energy directly from solar radiation has been the subject of much work in recent years. Collector systems including collector systems using parabolic-shaped collectors are known. Various kinds of thermal energy accumulators are known including those using mineral storage, oil and mineral storage and liquid storage. Salt eutectics, also known as salt eutectic mixtures, have also been used for thermal energy storage as shown in ϋ. S. Patent No. 3,709,209 issued to Schroder.Mineral storage is limited to sensible heat only since there is no realistic operating range wherein the heat of fusion might be utilized. Further, since there is air in the mineral media itself, expanding gases must be dealt with. Further, the transfer of thermal energy within the mineral media itself is slow.Oil and mineral storage of thermal energy is not suitable for high temperatures due to the flammability of most oils. Additionally, oil and mineral storage systems pose drastic environmental problems in the event of either a fire or a spill. Liquid thermal energy storage systems normally have low boiling points and excessive vapor pressure and often present flammability problems.Salt eutectics overcome many of the problems presented by the other thermal storage systems, but usually have narrow thermal bandwidths and cannot be utilized at extremely high temperatures.Compound parabolic structures are known for light collectors as described by Winston, Light Collection within the Framework of Geometric Optics , J. Optical Soc. Am., Vol. 60, pp. 245-247 (1970). The structures described by Winston were, however, developed for compound parabolic troughs of such a nature that they can be used for solar radiation collection in a fixed position relative to the earth and not have to track the sun. The present invention, on the other hand, makes use of a compound paraboloidal geometry for a radiation absorbing receiver which has no exit aperture, substantially does not reflect and is not fixed relative to the earth.A sun tracking system is shown in U. S. Patent No. 3,996,917 issued to Trihey which includes two pairs . of light sensitive elements disposed on opposite sides of an optical axis so that the two elements of each pair will be exposed to a different degree of solar radiation when the optical axis is misaligned with the direction of the sun, and a shading element to increase the sensitivity of the tracker to small movements of the sun. The shading element is fixed in size and position relative to the light-sensitive elements and does not take into account the differences between sunny days where the solar image is small but intense and cloudy days when the solar image is large but less intense. Disclosure of InventionThe present invention concerns a system for utilizing solar energy by collecting and concentrating solar radiation and converting the ' radiation concentrated into thermal energy and then storing that thermal energy at a high temperature. The solar energy system utilizes at least one collector for collecting and concentrating the solar radiation and a receiver associated with the at least one collector for converting the radiation concentrated by the collector into thermal energy at a high temperature. The thermal energy is then transferred from the receiver to a thermal energy accumulator which includes a mixture of fusible salts. The salts are ' fused by the high temperature of the solar energy system so that during periods of reduced sunshine, the system can continue to supply thermal energy not only from the sensible heat of the salts but also from the salts giving up the heat of fusion as various salts in the mixture nucleate. The salts of- the mixture are chosen in such a way that they nucleate at different temperatures, thus spreading the time over which significant energy can be extracted from the thermal energy accumulator and maintaining the mixture in a fluid state over a wide range of temperature.One important feature of t'he invention is a collector for concentrating radiation from sub¬ stantially a single direction which is used as the collector for collecting and concentrating solar radiation. The collector includes a primary reflector including a concave substantially paraboloid-shaped reflecting surface for concentrating radiation and a secondary reflector for directing to the receiver the radiation concentrated by the primary reflector. The primary reflector forms an aperture substantially at the vertex of the substantially paraboloid-shaped reflecting surface, and the receiver is disposed outside of the primary reflector opposite the aperture whereby the radiation reflected from the secondary reflector is directed through the aperture to the receiver. The primary reflector also includes a removable reflective liner for lining the concentrating side of the reflector so that the reflecting surface can actually be removed and replaced rather than polished, thus simplifying maintenance of the collector. One embodiment of the solar energy system utilizes at least one heat pipe for transferring thermal energy from the receiver to the thermal energy accumulator. The at least one heat pipe includes a means for substantially stopping the transfer of thermal energy. According to another important feature of the invention, a radiation seeker is used as a sun-seeker, and as part of a control system, the sun-seeker can be used for guiding the collector. The sun-seeker includes three photosensitive elements disposed around a central axis and an adjustable aperture along the axis so that the elements are exposed to a different amount of solar radiation when the tracker is misaligned with the direction of maximum usable solar radiation and to the same amount of solar radiation when the radiation axis is aligned with the direction of maximum usable solar radiation. This arrangement also prevents the tracker from mistakenly tracking a bright cloud rather than the sun.The solar energy system also utilizes a control system which adjusts the position of the primary reflector with respect to its support and can stop the transfer of thermal energy from the receiver to the thermal energy accumulator as well as perform other system functions. The control system is responsive to the expected position of the sun and the position of the sun as tracked by the sun-seeker, as well as certain predetermined potentially dangerous conditions.The novel features which characterize the invention are defined by the appended claims. The foregoing and other objects, advantages and features of the invention will hereinafter appear, and for purposes of illustration of the invention, but not of limitation, an exemplary embodiment of the invention is shown in the appended drawings. _ / BUR. OM WΪ Brief Description of DrawingsFigure 1 is a schematic diagram of the overall system;Figure 2 is an elevational view of a collector according to this invention;Figure 3 is a plan view of a collector according to this invention with the collector oriented to receive radiation from straight overhead;Figure 4 is a sectional view of a collector, a receiver and part of a thermal energy transfer system utilized in the present invention;Figure 5 is a detail view taken from FIGURE 4; Figure 6 is a perspective view of a receiver and part of a thermal transfer system according to this invention;Figure 7 is a pictorial representation of a meridian view of a compound paraboloid of revolution;Figure 8 is a detail section view taken from Figure 1; Figure 9 is an isometric view in partial section of a sun-seeker according to this invention; *-Figure 10 diagramatically shows a sun-seeker according to the present invention;Figure 11 is a schematic diagram, of the overall system showing much of the major feedback and control flow of the control system; andFigure 12 is a schematic diagram of a commercial size power station utilizing the present invention.* Best Mode for Carrying Out the Invention Referring now to the drawings, a solar energy system constructed according to the present invention is indicated generally by reference numeral 10. The solar energy system 10 includes at least one collector12 for collecting and concentrating solar radiation, a receiver 14 associated with said at least one collector12 for converting the radiation concentrated by the collector into thermal energy, a thermal energy accumulator 16, and a thermal energy transfer system 18 for transferring thermal energy from the receiver to the thermal energy accumulator. The thermal energy accumulator 16 comprises a mixture of fusible salts 20 wherein the nucleation temperature of at least one salt of the mixture differs from the nucleation temperature of at least one other salt of the mixture.One embodiment of solar energy system 10 further comprises a means 22 thermally coupled to the fusible* salt mixture for producing electric potential from the thermal energy stored in fusible salt mixture 20. Means 22 for producing electric potential includes a working fluid 24, a heat exchanger 26 thermally coupled to the fusible salt mixture for transferring heat from fusible salt mixture 20 to working fluid 24, and a means 28 driven by working fluid 24 for producing electric potential.Collector 12 of this invention is generally a collector for concentrating radiation from substantially a single direction and directing the concentrated radiation to a receiver such as receiver 14. In this embodiment, collector 12 is used for concerrtrating solar radiation which is substantially from a single direction at any given moment and generally comprises a pivotal means for receiving solar • radiation and directing the solar radiation to receiver 14. In this embodiment, collector 12 includes a pivotal joint 15 to allow the collector to pivot. Pivotal joint 15 also houses receiver 14.Collector 12 comprises a primary reflector 30 including a concave substantially paraboloid-shaped reflecting surface 32 for concentrating radiation, a secondary reflector 34 for directing to receiver 14 the radiation concentrated by a primary reflector 30, and a means for fixing the position of secondary reflector 34 with respect to primary reflector 30 wherein the secondary reflector reflects substantially all of the radiation reflected from the primary reflector. Preferably, secondary reflector 34 is a convex reflector positioned to refle.ct the radiation reflected from primary reflector 30 before the radiation passes through focus. In one preferred embodiment, secondary reflector 34 is a convex parabolic reflector with a diameter roughly 10 percent as large as that of primary reflector 30. Means for fixing the position of secondary reflector 34 with respect to primary reflector 30 includes three support elements 36 disposed peripherally to primary reflector 30 and secondary reflector 34. Support elements 36 include a means for adjusting the position of secondary reflector 34 with respect to primary reflector 30, the means in this case consisting of extensors 38.Primary reflector 30 forms an aperture 40 substantially at the vertex of paraboloid-shaped reflecting surface 32. Receiver 14 is disposed outside of primary reflector 30 opposite aperture 40 whereby the radiation reflected from secondary reflector 34 is directed through aperture 40 to receiver 14. The radiation reflected from secondary reflector 34 is preferably focused at a point interior to' receiver 14.Referring now to Figures 2 through 5, collector 12 is used in conjunction with a support element 42. Collector 12 further comprises a base support 44 for pivotally mounting primary reflector 30, and a plurality of linear actuators which in this case consist of three hydraulic jacks 46 for adjusting the position of primary reflector 30 with respect to base support 44 , the linear actuators being disposed from one another between primary reflector 30 and support element 42.Primary reflector 30 comprises a removable liner 48, better shown in Figure 5, for lining the concentrating side of reflector 30, the liner having a reflective side for concentrating the radiation. When in place, the reflective side of liner 48 becomes reflecting surface 32 for concentrating radiation. Primary reflector 30 further comprises a means 50 for evacuating air from between liner 48 and the adjacent portion of the rest of primary reflector 30 whereby liner 48 is held in place by air pressure. A ring 52, preferably made of silicone or thermo resistant plastic, is also included in primary reflector 30 in this embodiment to aid in holding liner 48 in place and to assist in installing a new removable liner.Primary reflector 30 comprises a reinforced plastic shell 54 which forms a concave substantially paraboloid-shaped surface 56 for receiving removable liner 48. Rubber ring 52 grips outer edge 58 of reinforced plastic shell 54 and grips removable liner 48 in slit 59. Thus, when replacing removable liner 48, a workman slides a new liner 48 into slit 59 and then establishes a vacuum underneath the liner by means 50. Means 50, in one embodiment, includes a plurality of porous areas through which air can be evacuated while still providing support to liner 48. By means of this invention, maintaining a high quality reflecting surface for a collector becomes a simple matter which can be routinely performed by relatively unskilled labor. Maintaining the reflecting surface -no longer requires elaborate cleaning or buffing operations. Removable liner 48 is made of metal coated plastic such as aluminized plastic,., and secondary reflector 34 comprises a highly polished surface such as the mirrors used in high powered lasers, although suitable substitute materials such as an electroplated metal stamping might be found. Referring now to Figures 6 and 7, a preferred embodiment of receiver 14 forms a cavity 60 with an aperture 62 for receiving the collected and concentrated solar radiation into cavity 60. Aperture 62 is oppositely disposed to vertex aperture 40 formed by primary reflector 30. Receiver 14 further comprises a plurality of radiation absorptive and thermally conductive fins 64 projecting from the wall of cavity 60. The wall of cavity 60 formed by the receiver is generally a compound paraboloid of revolution. The generating compound parabola of this embodiment is composed of four parabolic sections 66, 68, 70 and 72 which intersect at intersection points 74, 76, and 78. The generating compound parabola is revolved around an axis of revolution 81 to generate the compound paraboloid surface which describes the wall of cavity 60. The extensions of the parabolic sections beyond the intersection points are shown for illustration only. The curve formed by the inner edge of one of fins 64 is geometrically similar to the generating compound parabola. The solar radiation directed into receiver 14 by secondary reflector 34 is preferably focused at a point 80 which is interior to cavity 60.Receiver 14 further comprises a means for increasing the radiation absorptive surface area of the cavity wall and plurality of fins 64. In this case the means includes surface roughness of the radiation absorptive surfaces. It can thus be seen, that due to its compound paraboloid of revolution shape along with the use of fins and surface roughness all aiding in its . radiation absorptive and thermally conductive characteristics, that receiver 14 is well suited for converting the radiation concentrated by collector 12 into thermal energy. Due to the nature and characteristics of the receiver, very little of the energy reradiated from the surface of the wall of cavity 60 and fins 64 will be lost from the receiver. The wall of cavity 60 and the plurality of fins 64 are preferably colored black to aid in radiation absorption. Receiver 14 is substantially enclosed in thermal insulation 65 for preventing loss of thermal energy. A preferred embodiment of thermal energy transfer system 18 comprises at least one heat pipe 82, heat pipe 82 including an evaporator section 84 thermally coupled to receiver 14 and a condensor section 86 thermally coupled to thermal energy accumulator 16 by means of terminator 87. Terminator 87, in a preferred embodiment, comprises a ceramic material such as berrylium oxide. At least one heat pipe 82 comprises a liquid metal working fluid for high temperature applications.Thermal energy transport system 18 further comprises a thermally conducting coupling 88 thermally coupled to receiver 14 and the at least one heat pipe 82, wherein coupling 88 rotates freely about the at least one heat pipe 82 and coupling 88 rotates freely within base 90 of receiver 14. The axis of rotation 92 of coupling 88 is in a direction substantially perpendicular to the axis of rotation 94 of receiver 14. It can thus be seen that heat is transferred from receiver 14 to the at least one heat pipe 82, and receiver 14 pivots freely with respect to the at least one heat pipe 82 so that the collector heat pipe combination is free to track the sun. In one embodiment of thermal energy accumulator 16, mixture of fusible salts 20 comprises a mixture of sodium salts. The mixture of sodium salts consists mainly of sodium sulphate and at least one salt from the group of sodium sulfide, sodium chloride and sodium metasilicate. Preferably, the mixture of sodium -salts consists mainly of sodium sulphate, sodium sulfide, sodium chloride and sodium metasilicate. Sodium sulphate has a relatively low fusion temperature of 31°C. Once the sodium sulphate has fused, the entire mixture can be kept in a flowable condition since, if the salts of the mixture are carefully chosen, the nonfused salts will remain in gelling pockets throughout the mixture. Once the entire mixture is brought to its normal operating temperature, all of the salts of the mixture will be in a liquid state. During periods when the energy received by the solar energy system from the sun is inadequate to keep up with the demands on the system by the system's energy thermal energy accumulator 16 can continue to supply usable energy over a long period of time and considerable temperature range since mixture of fusible salts 20 can yield not only sensible heat, but can also yield the heat of fusion for each of the salts as each of the salts nucleates. Since at least one of the salts of the mixture remains in a liquid state throughout all of the useful operating temperatures of the mixture, transfer of thermal energy within the mixture of fusible salts 20 itself and transfer of thermal energy from mixture of fusible salts 20 to heat exchanger 26 is facilitated. The mixture of fusible salts 20 of this embodiment can be kept at an average temperature between 1000°C and the boiling temperature of the entire mixture. In another embodiment of the present invention, mixture of fusible salts 20 is a mixture of sodium salts which consist mainly of sodium chloride, sodium nitrate, sodium hydroxide, sodium sulfide, sodium sulphate and sodium metasilicate. Referring now to Figure 1 and Figure 8, thermal energy accumulator 16 further comprises a refractory material lining 96 for substantially enclosing mixture of fusible salts 20, a plurality of metal plates 98 for supporting refractory material . lining 96, and a plurality of structural members such as H-beam 100 external to metal plates 98 and engaging metal plates 98 for providing structural strength to thermal energy accumulator 16. A preferred embodiment of refractory material lining 96 comprises fused cast aluminum oxide although other suitable refractories are known in the art.Thermal energy accumulator 16 also comprises a reinforced concrete wall 102 substantially enclosing the structure made up of refractory material lining 96, plurality of metal plates 98 and the plurality of structural members such as H-beam 100. The structural members such as H-beam 100 act as spacers between plurality of metal plates 98 and reinforced concrete wall 102. This allows the use of an insulation such as alumina-silica insulation between plurality of metal plates 98 and reinforced concrete wall 102. As used here the term metal plates includes but is not limited to steel plates. Reinforced concrete wall 102 is preferably a steel-reinforced concrete wall. The term wall includes the floor and ceiling structure also. Reinforced concrete wall 102 is not necessary for systems that are sufficiently small. Referring again to Figure 1, one means for producing electric potential 22 includes a Rankine cycle power system which includes means 28 driven by working fluid 24 for producing electric potential. Means 28 includes a turbine 108 and a generator 106 driven by turbine 108 through gearing means 110. In this configuration, heat exchanger 26 acts as the boiler or heater for the Rankine cycle power system. For further efficiency, means 22 for producing electric potential can also include a second cycle, the second cycle including heat exchanger 112 and working fluid 1.14 in a heat exchange relationship with working fluid 24. Heat exchanger 112 thus acts as the condenser for the first cycle as in a normal binary cycle system. Pump 25 is included in the first cycle to recompress wprking fluid 24 and pump 115 is added in the second cycle to recompress working fluid 114 after working fluid 114 has been passed through a condenser 113.A preferred embodiment of means 22 for producing electric potential includes a relief valve 116 for releasing working fluid 24 in the event of excessive pressure in working fluid 24 caused by some malfunction in the overall system such as an overheating of mixture of fusible salts 20. Relief valve 116 should only be opened in extreme emergency since the release of working fluid 24 into the environment would normally be undesirable. Means 22 further includes normally open bypass valve 117 for bypassing turbine 108 during fURE_QMPI normal operating conditions with some percentage of working fluid 24 in its high pressure gas stage. Turbine 108 can immediately respond to increased load by closing normally open bypass valve 117. A preferred embodiment of solar energy system 10 also includes a control system. Referring now to Figure 11, the control system includes a means 118 for driving the plurality of linear actuators such as hydraulic jacks 46 whereby the control system adjusts the position of primary reflector 30 with respect to base support 44.The control system further comprises a means for tracking the expected direction of maximum usable solar radiation relative to the axis of substantially paraboloid-shaped reflecting surface 32 of the primary reflector which will also be referred to as the axis of the primary reflector. The tracking means comprises basically a calculator or table lookup for computing or storing information regarding the solar ephemeris. The calculations or lookup can be performed by cams or a computer. The tracking means is cooperatively coupled to means 118 for driving the_ plurality of linear actuators and is responsive to misalignments between the primary reflector and the expected direction of maximum usable solar radiation.The control system further comprises a means for sensing the true orientation of primary reflector 30 relative to base support 44, and a means for detecting a predetermined potentially damaging condition affecting the solar energy system. One embodiment of the means for sensing the true orientation of primary reflector 30 relative to base support 44 includes a plurality of linear displacement transducers 120 disposed between support element 42 and primary reflector 30. Each linear displacement transducer 120 measures the length of a cord .122 between a given point on support element 42 and a given point on primary reflector 30. One type of such linear displacement transducer includes a rotary encoder such as a shaft positioned encoder which is turned as cord 122 is pulled out by primary reflector 30. or drawn back by a spring element. The location of the given points and the lengths of cord 122 give the true orientation of primary reflector 30. The orientation sensing means and the detecting means are cooperatively coupled to means 118 for driving the plurality of linear actuators such as hydraulic jacks 46 whereby the means 118 for driving the plurality of linear actuators is responsive to the predetermined potentially damaging condition whereby the control system adjusts the position of primary reflector 30 with respect to base support to lessen the effects of the predetermined potentially damaging condition and adjusts the position of the primary reflector for normal operation when the predetermined potentially dangerous condition has passed.One embodiment of the means for detecting a predetermined potentially damaging condition affecting solar energy system 10 comprises a means for detecting potentially damaging wind strain on the collector. The means for detecting potentially damaging wind strain on the collector includes strain gauges 124 and data link 126 to transmit data from strain gauges 124 to the decision making portion of the control system, whereby the control system adjusts the position of primary reflector 30 with respect to base support 44 to lessen the effects of the wind strain. One embodiment of the means for detecting a predetermined potentially dangerous condition affecting solar energy system 10 includes a means 128 for detecting potentially damaging high temperature in mixture of fusible salts 20 whereby the control system adjusts the position of primary reflector 30 with respect to base support 44 to misalign primary reflector 30 and the sun in order to decrease the energy flow from the collector to mixture of fusibleB_ salts 20. This misaligning of primary reflector 30 and the sun prevents the further overheating of mixture of fusible salts 20 and allows means for producing electric potential 22 or other means for using the stored thermal energy to reduce the temperature within mixture of fusible salts 20. Means 128 for detecting potentially damaging high temperature in mixture of fusible salts 20 can also include means for detecting potentially damaging pressure, thermal loss or salt leakage.The control system further comprises a radiation seeker 130 used as a sun seeker. Sun seeker 130 is cooperatively coupled to means 118 for driving the plurality of linear actuators, in this case hydraulic jacks 46. Seeker 130 includes at least three photosensitive elements 132 and a means for shading photosensitive elements 132, the means for shading comprising a substantially encircling wall 134 and a variable shading means 136 which forms aperture 138. In this embodiment of radiation seeker 130, the at least three photosensitive elements 132 consist of three roughly poplanar. photosensitive elements. The locus of points equidistant from three photosensitive elements 132 defines a radiation axis so that three photosensitive elements 132 are substantially equally spaced from one another around the radiation axis, and aperture 138 is substantially concentric about the radiation axis, wherein the elements 132 are exposed to a different amount of radiation when the radiation axis is misaligned with the direction of maximum usable radiation and to the same amount of radiation when the radiation axis is aligned with the direction of maximum usable radiation. At least three photosensitive elements 132 are preferably somewhat angled in toward the radiation axis.Radiation seeker 130 is cooperatively coupled to means 118 for driving the plurality of linear actuators through the decision making portion of the control system and data link 140. The decision making portion of the control system includes differential amplifier 142 and comparators 143a, 143b and 143c. ' The voltage output 144 of differential amplifier 142 is the average of the output voltages of elements 130a, 130b and 130c. Each of the comparators will have a non-zero output whenever the voltage output of its associated element 130 exceeds the average voltage as indicated by output 144. The outputs 145 of comparators 143 are used to drive hydraulic jacks 46, and in this case, are part of the means for driving the plurality of linear actuators. Thus, means 118 for driving the plurality of linear actuators is responsive to misalignments between primary reflector 30 and the direction of maximum usable solar radiation. As used here, the term photosensitive is used in a broad sense of meaning not just light sensitive, but rather sensitive to all radiation in the range of interest. Similarly, how well radiation seeker 130 aligns with the direction of maximum usable radiation is dependent upon how sensitive photosensitive elements 132 are to radiation in the usable range of frequencies.Variable shading means 136 is responsive to the amount of available usable radiation whereby the size of aperture 138 is responsive to actual radiation conditions. When radiation seeker 130 is used to track the sun, the size of aperture 138 is responsive to the size of the solar image as affected by distance from the sun, clouds, etc. as well as other conditions, thus aiding in more accurately tracking the maximum usable solar radiation. Additionally, by varying the size of aperture 138 according to the amount of available usable radiation, radiation seeker 130 will track the actual solar image and not mistake a bright cloud for the image to be followed. The radiation of interest for solar energy system 10 is solar radiation, but the principals used in radiation seeker 130 work equally well for other forms of radiation. At least one heat pipe 82 includes a means 146 for substantially stopping the transfer of thermal energy from receiver 14 to thermal energy accumulator 16. The control system includes a means 148 for detecting a predetermined level of solar radiation cooperatively coupled to means 146 for substantially stopping the transfer of thermal energy whereby means 146 for substantially stopping the transfer of thermal energy is responsive to the predetermined level of solar radiation. Normally, the predetermined level of solar radiation is a level of solar radiation so low that it takes more energy to operate solar energy system 10 than is received by the system, so that there would be a net energy drain on the system to try to continue to operate. This situation would exist between a certain time in the evening and a certain time in the morning as well as on extremely overcast days. Means 146 for substantially stopping the transfer of thermal energy is also used to prevent reverse heat flow in heat pipe 82 which would drain heat from accumulator 16.Means 128 fo.r detecting a predetermined temperature within thermal energy accumulator 16 is also cooperatively coupled ' to means 146 for substantially stopping the transfer of thermal energy whereby means 146 for substantially stopping the transfer of thermal energy is responsive to the predetermined temperature within thermal energy accumulator 16. Thus, if the predetermined temperature is a dangerously high -temperature, means 146 can be actuated to substantially stop the transfer of thermal energy from receiver 14 to thermal energy accumulator 16 so that the temperature in thermal energy accumulator 16 is not raised further.One suitable means 146 for substantially stopping the transfer of thermal energy is a magnetically operated butterfly valve within at least one heat pipe 82, although other suitable means for thermally switching heat pipes are known. One embodiment of the control system also includes a data link 150 for transmitting information regarding the pressure, temperature and leakage of working fluid 24 within heat exchanger 26, data link 152 for reporting the speed and torque of turbine 108, and data link 154 for reporting the current and frequency of generator 106. The term data link is used throughout to refer to both digital and analog data. Data link 150 is also another means for detecting a predetermined potentially damaging condition.The control system of this embodiment also includes a means 156 for controlling relief valve 116 responsive to data link 150 for reporting pressure, temperature and leakage of working fluid 24 within heat exchanger 26. Thus, dangerously high working fluid pressure can be relieved by opening relief valve 116. The control system further comprises means 158 for throttling the flow of working fluid 24.Solar energy system 10 further comprises retaining wall 168 which in cooperation with thermal energy accumulator 16 forms moat 170 for retaining salt spills or at least impeding the flow of released salts and, thus, preventing ecological havoc. In general, small installations such as residential installations would not have as much need for retaining wall 168 as would large installations.Although a preferred embodiment of the invention has been described in detail, it should be understood that various changes, substitutions, and alterations can be made therein without departing from the spirit and scope of the invention as defined by the appended claims. In general, collector 12 is a means for directing concentrated solar radiation to receiver 14. Thermal energy accumulator 16 in combination with ■ either means 22 for producing electric potential or any other means for utilizing the thermal energy from thermal energy accumulator 16 make up one means for utilizing thermal energy. In embodiments in which at least one collector 12 must substantially face a certain direction with respect to the sun, the embodiment of at least one collector 12 illustrated is only one pivotal means for receiving solar radiation and directing the solar radiation to receiver 14.In an alternative embodiment of at least one collector 12, primary reflector 30 comprises a substantially paraboloid-shaped reflecting surface and secondary reflector 34 comprises a hyperbolic reflecting surface, changing the diameter of secondary reflector 34 relative to the diameter of primary reflector 30 to approximately 50 percent.Many features and subcombinations of this invention are of utility and other applications are contemplated within the scope of the claims. For instance, radiation seeker 130 can also be used, for surveying as in laser alignment of large pipelines now being done by conventional optical methods or for the precise guidance of telescopes. At least one collector 12 can be used to provide commercial or residential heat directly.Referring now to Figure 12, solar energy system 160 includes an array 162 of collectors 12, suitable for commercial power generation, to collect and concentrate solar radiation. A receiver 14 is associated with each of said collectors for converting the radiation concentrated by the collectors into thermal energy. Thermal energy transfer system 18 transfers thermal energy from receivers 14 to thermal energy accumulator 16. Solar energy system 160 further comprises a means 22 thermally coupled to mixture of fusible salts 20 within thermal energy accumulator 16 for producing electric potential from the thermal energy stored in the fusible salt mixture. Solar energy system 160 further comprises a cooling tower 164 for cooling working fluid 24 used by solar energy system 160, and a maintenance building 166. Thus, it will be appreciated that the present solar energy system solves the problems of many collector type systems of the past. First, there is no need to suspend a boiler or any liquid carrying element at the focal point of the primary reflector. Secondly, the receiver which converts radiation into thermal energy is situated at the base of the primary reflector, near the thermal energy transfer system, rather than at the focal point of the primary reflector. Further, the receiver itself does not need to transfer any liquid medium to the thermal energy transfer system, although the receiver could be filled with such medium to be heated in certain applications. Additionally, a preferred embodiment of the system is one in which the only liquid transfer is the liquid metal of the liquid metal heat pipe which is highly efficient and of high reliability. Still further, the thermal energy accumulator not only yields sensible heat, but also yields the heat of fusion of the salts in the mixture over a wide range of temperatures while still remaining in a liquid state. Besides these advantages, the primary collector of the system can be maintained in good condition by simply replacing the reflective liner. Other advantages of the solar energy system of this invention are obvious from the description and the appended claims.Although a preferred embodiment of the invention has been described in detail, it should be understood that various changes, substitutions and alterations can be made therein without departing from the spirit and scope of the invention as defined *by the appended claims.'BURO /1 | Claims1. A thermal energy accumulator comprising a mixture of fusible salts, wherein the nucleation temperature of at least one salt of the mixture differs from the nucleation temperature of at least one other salt of the mixture.2. A thermal energy accumulator according to Claim 1 wherein the mixture of fusible salts comprises a mixture of sodium salts.3. A thermal energy accumulator according to Claim 2 further comprising, in combination: a refractory material lining for substantially enclosing the mixture of fusible salts; a plurality of metal plates for supporting the refractory material lining; and a plurality of structural members external to the metal plates and engaging the metal plates for providing structural strength to the thermal energy .accumulator.4. A thermal energy accumulator according to Claim 3 wherein the refractory material lining comprises fused cast aluminum oxide.5. A thermal energy accumulator according to Claim 3 further comprising, in combination: a reinforced concrete wall substantially enclosing the structure made up of the refractory material lining, the plurality of metal plates and the plurality of structural members whereby the structural members act as spacers between the plurality of metal plates and the reinforced concrete wall; and alumina-silica insulation between the plurality αf metal plates and the reinforced concrete wall.6. A thermal energy accumulator according to Claim 2 wherein the mixture of sodium salts consists mainly of sodium sulfate and at least one salt from the group of sodium sulfide, sodium chloride and sodium metasilicate.7. A thermal energy accumulator according to Claim 6 wherein the mixture of sodium salts consists mainly of sodium sulfate, sodium sulfide, sodium chloride and sodium metasilicate.8. A thermal energy accumulator according to Claim 2 wherein the mixture of sodium salts consists mainly of sodium chloride, sodium nitrate, sodium hydroxide, sodium sulfide, sodium sulfate and sodium metasilicate.■ VO ^^ W | SOLAR DYNAMICS LTD | MARKE R |
WO-1979001005-A1 | 1,979,001,005 | WO | A1 | EN | 19,791,129 | 1,979 | 20,090,507 | new | F24J3 | null | F03G6, F24J2 | F03G 6/06R2, F24J 2/12, F24J 2/18, F24J 2/32, R03G 6/00T150 | RADIATION COLLECTOR | A solar energy system (10) including a collector (12) for collecting and concentrating solar radiation, a receiver (14) associated with the collector for converting the radiation concentrated by the collector into thermal energy, a thermal energy accumulator (16), and a thermal energy transfer system (18) for transferring thermal energy from the receiver to the thermal energy accumulator is disclosed. The collector includes a primary reflector (30) for concentrating radiant energy directed at it and a secondary reflector (34) for directing to the receiver the radiant energy concentrated by the primary reflector. The primary reflector has a shell (54) made of reinforced fiber glass and a removable reflective liner (32 and 48). The receiver, situated at the vertex of the primary reflector, has an internally finned compound paraboloidal cavity (60) for receiving the radiation directed from the secondary reflector. | DescriptionRadiation CollectorTechnical FieldThe present invention relates generally to solar energy systems, and in one of its aspects, to a high temperature collector system using a salt mixture storage. Another aspect of the invention relates to a method and apparatus for tracking the movement of a radiation source such as the movement of the sun across the sky.Background ArtThe recovery of useful energy directly from solar radiation has been the subject of much' ork in recent years. Collector systems including collector systems using parabolic-shaped collectors are known. Various kinds of thermal, energy accumulators are known including those using mineral storage, oil and mineral storage and liquid storage. Salt eutectics, also known as salt eutectic mixtures, have also been used for thermal energy storage as shown in ϋ. S. Patent No. 3,709,209 issued to Schroder.Mineral storage is limited to sensible heat only since there is no realistic operating range wherein the heat of fusion might be utilized. Further, since there is air in the mineral media itself, expanding gases must be dealt with. Further, the transfer of thermal energy within the mineral media itself is slow.Oil and mineral storage of thermal energy is .not suitable for high temperatures due to the flammability of most oils. Additionally, oil and mineral storage systems pose drastic environmental problems in the event of either a fire or a spill. Liquid thermal energy storage systems normally have low boiling points and excessive vapor pressure and often present flammability problems.Salt eutectics overcome many of the problems presented by the other thermal storage systems, but usually have narrow thermal bandwidths and cannot be utilized at extremely high temperatures.Compound parabolic structures are known for light collectors as described by Winston, Light Collection within the Framework of Geometric Optics , J. Optical Soc. Am., Vol. 60, pp. 245-247 (1970). The structures described by Winston were, however, developed for compound parabolic troughs of such a nature that they can be used for solar radiation collection in a fixed position relative to the earth and not have to track the sun. The present invention, on the other hand, makes use of a compound paraboloidal geometry for a radiation absorbing receiver which has no exit aperture, substantially does not reflect and is not fixed relative to the earth.A sun tracking system is shown in ϋ. S. Patent No. 3,996,917 issued to Trihey which includes two pairs of light sensitive elements disposed on opposite sides of an optical axis so that the two elements of each pair will be exposed to a different degree of solar radiation when the optical axis is misaligned with the direction of the sun, and a shading element to increase the sensitivity of the tracker to small movements of the sun. The shading element is fixed in size and position relative to the light-sensitive elements and does not take into account the differences between sunny days where the solar image is small but intense and cloudy days when the solar image is large but less intense. Disclosure of InventionThe present invention- concerns a system for utilizing solar energy by collecting and concentrating solar radiation and converting the radiation concentrated into thermal energy and then storing that thermal energy at a high temperature. The solar energy system utilizes at least one- collector for collecting and concentrating the solar radiation and a receiver associated with the at least one collector for converting the radiation concentrated by the collector into thermal energy at a high temperature. The thermal energy is then transferred from the receiver to a thermal energy accumulator which includes a mixture of fusible salts. The salts are fused by the high temperature of the solar energy system so that during periods of reduced sunshine, the system can continue to supply thermal energy not only from the sensible heat of the salts but also from the salts giving up the heat of fusion as various salts in the mixture nucleate. The salts of the mixture are chosen in such a way that they nucleate at different temperatures, thus spreading the time over which significant energy can be extracted from the thermal energy accumulator and maintaining the mixture in a fluid state over a wide range of temperature. -One important feature of the invention is a collector for concentrating radiation from sub¬ stantially a single direction which is used as the collector for collecting and concentrating solar radiation. The collector includes a primary reflector including a concave substantially paraboloid-shaped reflecting surface for concentrating radiation and a secondary reflector for directing to the receiver the radiation concentrated by the primary reflector. The primary reflector forms an aperture substantially at the vertex of the substantially paraboloid-shaped reflecting surface, and the receiver is disposed outside of the primary reflector opposite the aperture whereby the radiation reflected from the secondary reflector is directed through the aperture to the receiver. The primary reflector also includes a removable reflective liner for lining the concentrating side of the reflector so that the reflecting surface can actually be removed and replaced rather than polished, thus simplifying maintenance of the collector. One embodiment of the solar energy system utilizes at least one heat pipe for transferring thermal energy from the receiver to the thermal energy accumulator. The at least one heat pipe includes a means for substantially stopping the transfer of thermal energy. According to another important feature of the invention, a radiation seeker is used as a sun-seeker, and as part of a control system, the sun-seeker can be used for guiding the collector. The sun-seeker includes three photosensitive elements disposed around a central axis and an adjustable aperture along the axis so that the elements are exposed to a different amount of solar radiation when the tracker is misaligned with the direction of maximum usable solar radiation and to the same amount of solar radiation when the radiation axis is aligned with the direction of maximum usable solar radiation. This arrangement also prevents the tracker from mistakenly tracking a bright cloud rather than the sun.The solar energy system also utilizes a control system which adjusts the position of the primary reflector with respect to its support and can stop the transfer of thermal energy from the receiver to the thermal energy accumulator as well as perform other system functions. The control system is responsive to the expected position of the sun and the position of the sun as tracked by the sun-seeker, as well as certain predetermined potentially dangerous conditions.The novel features which characterize the invention are defined by the appended claims. The foregoing and other objects, advantages and features of the invention will hereinafter appear, and for purposes of illustration of the invention, but not of limitation, an exemplary embodiment of the invention is shown in the appended drawings. » . Brief Description of DrawingsFigure 1 is a schematic diagram of the overall system;•Figure 2 is an elevational view of a collector according to this invention;Figure 3 is a plan view of a collector according to this invention with the collector oriented to receive radiation from straight overhead;Figure 4 is a sectional view of a collector, a receiver and part of a thermal energy transfer system utilized in the present invention;Figure 5 is a detail view taken from FIGURE 4;Figure 6 is a perspective view of a receiver and part of a thermal transfer system according to this invention;Figure 7 is a pictorial representation of a meridian view of a compound paraboloid of revolution;Figure 8 ' is a detail section view taken fromFigure 1; Figure 9 is an isometric view in partial section of a sun-seeker according to this invention;Figure 10 diagramatically shows a sun-seeker according to the present invention;Figure 11 is a schematic diagram of the overall system showing much of the major feedback and control flow of the control system; andFigure 12 is a schematic diagram of a commercial size power station utilizing the present invention.Best Mode for Carrying Out the Invention Referring now to the drawings, a solar energy system constructed according to the present invention is indicated generally by reference numeral 10. The solar energy system 10 includes at least one collector12 for collecting and concentrating solar radiation, a receiver 14 associated with said at least one collector12 for converting the radiation concentrated by the collector into thermal energy, a thermal energy accumulator 16, and a thermal energy transfer system 18O PIW1PO for transferring thermal energy from the receiver to the thermal energy accumulator. The thermal energy accumulator 16 comprises a mixture of fusible salts 20 wherein the nucleation temperature of at least one salt of the mixture differs from the nucleation temperature of at least one other salt of the mixture.One embodiment of solar energy system 10 further comprises a means 22 thermally coupled to the fusible salt mixture for producing electric potential from the thermal energy stored in fusible salt mixture 20. Means 22 for producing electric potential includes a working fluid 24, a heat exchanger 26 thermally coupled to the fusible salt mixture for transferring heat from fusible salt mixture 20 to working fluid 24, and a means 28 driven by working fluid 24 for producing electric potential.Collector 12 of this invention is generally a collector for concentrating radiation from substantially a single direction and directing the concentrated radiation to a receiver such as receiver 14. In this embodiment, collector 12 is used for concentrating solar radiation which is substantially from a single direction at any given moment and generally comprises a pivotal means for receiving solar radiation and directing the solar radiation to receiver 14. In this embodiment, collector 12 includes a pivotal joint 15 to allow the collector to pivot. Pivotal joint 15 also houses receiver 14.Collector 12 comprises a primary reflector 30 including a concave substantially paraboloid-shaped reflecting surface 32 for concentrating radiation, a secondary reflector 34 for directing to receiver 14 the radiation concentrated by a primary reflector 30, and a means for fixing the position of secondary reflector 34 with respect to primary reflector 30 wherein the secondary reflector reflects substantially all of the radiation reflected from the primary reflector. Preferably, secondary reflector 34 is a convex reflector positioned to reflect the radiation reflected from primary reflector 30 before the radiation passes through focus. In one preferred embodiment, secondary reflector 34 is a convex parabolic reflector with a diameter roughly 10 percent as large as that of primary reflector 30. Means for fixing the position of secondary reflector 34 with respect to primary reflector 30 includes three support elements 36 disposed peripherally to primary reflector 30 and secondary reflector 34. Support elements 36 include a means for adjusting the position of secondary reflector 34 with respect to primary reflector 30, the means in this case consisting of extensors 38.Primary reflector 30 forms an aperture 40 substantially at the vertex of paraboloid-shaped reflecting surface 32. Receiver 14 is disposed outside of primary reflector 30 opposite aperture 40 whereby the radiation reflected from secondary reflector 34 is directed through aperture 40 to receiver 14. The radiation reflected from secondary reflector 34 is preferably focused at a point interior to receiver 14.Referring now to Figures 2 through 5, collector 12 is used in conjunction with a support element 42. Collector 12 further comprises a base support 44 for pivotally mounting primary reflector 30, and a plurality of linear actuators which in this case consist of three hydraulic jacks 46 for adjusting the position of primary reflector 30 with respect to base support 44, the linear actuators being disposed from one another between primary reflector 30 and support element. 42.Primary reflector 30 comprises a removable liner 48, better shown in Figure 5, for lining the concentrating side of reflector 30, the liner having a reflective side for concentrating the radiation. When in place, the reflective side of liner 48 becomes reflecting surface 32 for concentrating radiation. Primary reflector 30 further comprises a means 50 for evacuating air from between liner 48 and the adjacent portion of the rest of primary reflector 30 whereby liner 48 is held in place by air pressure. A ring 52, preferably made of silicone or thermo resistant plastic, is also included in primary reflector 30 in this embodiment to aid in holding liner 48 in place and to assist in installing a new removable liner.Primary reflector 30 comprises a reinforced plastic shell 54 which forms a concave substantially paraboloid-shaped surface 56 for receiving removable liner 48. Rubber ring 52 grips outer edge 58 of reinforced plastic shell 54 and grips removable liner 48 in slit 59.. Thus, when replacing removable liner 48, a workman slides a new liner 48 into slit 59 and then establishes a vacuum underneath the liner by. means 50. Means 50, in one embodiment, includes a plurality of porous areas through which air can be evacuated while still providing support to liner 48. By means of this invention, maintaining a high quality reflecting surface for a collector becomes a simple matter which can be routinely performed by relatively unskilled labor. Maintaining the reflecting surface no longer requires elaborate cleaning or buffing operations. Removable liner 48 is made of metal coated plastic such as aluminized plastic, and secondary reflector 34 comprises a highly polished surface such as the mirrors used in high powered lasers, although suitable substitute materials such as an electroplated metal stamping might be found. Referring now to Figures 6 and 7, a preferred embodiment of receiver 14 forms a cavity 60 with an aperture 62 for receiving the collected and concentrated solar radiation into cavity 60. Aperture 62 is oppositely disposed to vertex aperture 40 formed by primary reflector 30. Receiver 14 further comprises a plurality of radiation absorptive and thermally conductive fins 64 projecting from the wall of cavity 60. The wall of cavity 60 formed by the receiver is generally a compound paraboloid of revolution. The generating compound parabola of this embodiment is composed of four parabolic sections 66, 68, 70 and 72 which intersect at intersection points 74, 76, and 78. The generating compound parabola is revolved around an axis of revolution 81 to generate the compound paraboloid surface which describes the wall of cavity 60. The extensions of the parabolic sections beyond the intersection points are shown for illustration only. The curve formed by the inner edge of one of fins 64 is geometrically similar to the generating compound parabola. The solar radiation directed into receiver 14 by secondary reflector 34 is preferably focused at a point 80 which is interior to cavity 60.Receiver 14 further comprises a means for increasing the radiation absorptive surface area of the cavity wall and plurality of fins 64. In this case the means includes surface roughness of the radiation absorptive surfaces. It can thus be seen, that due to its compound paraboloid of revolution shape along with the use of fins and surface roughness all aiding in .its radiation absorptive and thermally conductive characteristics, that receiver 14 is well suited for converting the radiation concentrated by collector 12 into thermal energy. Due to the nature and characteristics of the receiver, very little of the energy reradiated from the surface of the wall of cavity 60 and fins 64 will be lost from the receiver. The wall of cavity 60 and the plurality of fins 64 are preferably colored black to aid in radiation absorption. Receiver 14 is substantially enclosed in thermal insulation 65 for preventing loss of thermal energy. A preferred embodiment of thermal energy transfer system 18 comprises at least one heat pipe 82, heat pipe 82 including an evaporator section 84 thermally coupled to receiver 14 and a condensor sec ther ally coupled to thermal energy accumulator 16 by means of terminator 87. Terminator 87, in a preferred embodiment, comprises a ceramic material such as berrylium oxide. At least one heat pipe 82 comprises a liguid metal working fluid for high temperature applications.Thermal energy transport system 18 further comprises a thermally conducting coupling 88 thermally coupled to receiver 14 and the at least one heat pipe 82, wherein coupling 88 rotates freely about the at least one heat pipe 82 and coupling 88 rotates freely within base 90 of receiver 14. The axis of rotation 92 of coupling 88 is in a direction substantially perpendicular to the axis of rotation 94 of receiver 14. It can thus be seen that heat is transferred from receiver 14 to the at least one heat pipe 82, and receiver 14 pivots freely with respect to the at least one heat pipe 82 so that the collector heat pipe combination is free to track the sun. In one embodiment of thermal energy accumulator 16, mixture of fusible salts 20 comprises a mixture of sodium salts. The mixture of sodium salts consists mainly of sodium sulphate and at least one salt from the group of sodium sulfide, sodium chloride and sodium metasilicate. Preferably, the mixture of sodium salts consists mainly of sodium sulphate, sodium sulfide, sodium chloride and sodium metasilicate. Sodium sulphate has a relatively low fusion temperature of 31°C. Once the sodium sulphate has fused, the entire mixture can be kept in a flowable condition since, if the salts of the mixture are carefully chosen, the nonfused salts will remain in gelling pockets throughout the mixture. Once the entire mixture is brought to its normal operating temperature, all of the salts of the mixture will be in a liquid state. During periods when the energy received by the solar energy system from the sun is inadequate to keep up with the demands on the system by the system's energy output,W thermal energy accumulator 16 can continue to supply usable energy over a long period of time and considerable temperature range since mixture of fusible salts 20 can yield not only sensible heat, but can also yield the heat of fusion for each of the salts as each of the salts nucleates. Since at least one of the salts of the mixture remains in a liquid state throughout all of the useful operating temperatures of the' mixture, transfer of thermal energy within the mixture of fusible salts 20 itself and transfer of thermal energy from mixture of fusible salts 20 to heat exchanger 26 is facilitated. The mixture of fusible salts 20 of this embodiment can be kept at an average temperature between 1000°C and the boiling temperature of the entire mixture. In another embodiment of the present invention, mixture of fusible salts 20 is a mixture of sodium salts which consist mainly of sodium chloride, sodium nitrate, sodium hydroxide, sodium sulfide, sodium sulphate and sodium metasilicate. Referring now to Figure 1 and Figure 8, thermal energy accumulator 16 further comprises a refractory material lining 96 for substantially enclosing mixture of fusible salts 20, a plurality of metal plates 98 for supporting refractory material lining 96, and a plurality of structural members such as H-beam 100 external to metal plates 98 and engaging metal plates 98 for providing structural strength to thermal energy accumulator 16. A preferred embodiment of refractory material lining 96 comprises fused cast aluminum oxide although other suitable refractories are known in the art.Thermal energy accumulator 16 also comprises a reinforced concrete wall 102 substantially enclosing the structure made up of refractory material lining 96, plurality of metal plates 98 and the plurality of structural members such as H-beam 100. The structural members such as H-beam 100 act as spacers between plurality of metal plates 98 and reinforced concreteOMPI, fa wipo wall 102. This allows the use of an insulation such as alumina-silica insulation between plurality of metal plates 98 and reinforced concrete wall 102. As used here the term metal plates includes but is not limited to steel plates. Reinforced concrete wall 102 is preferably a steel-reinforced concrete wall. The term wall includes the floor and ceiling structure also. Reinforced concrete wall 102 is not necessary for systems that are sufficiently small. Referring again to Figure 1, one means for producing electric potential 22 includes a Rankine cycle power system which includes means 28 driven by working fluid 24 for producing electric potential. Means 28 includes a turbine 108 and a generator 106 driven by turbine 108 through gearing means 110. In this configuration, heat exchanger 26 acts as the boiler or heater for the Rankine cycle power system. For further efficiency, means 22 for producing electric potential can also include a second cycle, the second cycle including heat exchanger 112 and working fluid 114 in a heat exchange relationship with working fluid 24. Heat exchanger 112 thus acts as the condenser for the first cycle as in a normal binary cycle system. Pump 25 is included in the first cycle to recompress working fluid 24 and pump 115 is added in the second cycle to recompress working fluid 114 after working fluid 114 has been passed through a condenser 113.A preferred embodiment of means 22 for producing electric potential includes a relief valve 116 for releasing working fluid 24 in the event of excessive pressure in working fluid 24 caused by some malfunction in the overall system such as an overheating of mixture of fusible salts 20. Relief valve 116 should only be opened in extreme emergency since the release of working fluid 24 into the environment would normally be undesirable. Means 22 further includes normally open bypass valve 117 for bypassing turbine 108 during normal operating conditions with some percentage of working fluid 24 in its high pressure gas stage. Turbine 108 can immediately respond to increased load by closing normally open bypass valve 117. A preferred embodiment of solar energy system 10 also includes a control system. Referring now to Figure 11, the control system includes a means 118 for driving the plurality of linear actuators such as hydraulic jacks 46 whereby the control system adjusts the position of primary reflector 30 with respect to base support 44.The control system further comprises a means for tracking the expected direction of maximum usable solar radiation relative to the axis of substantially paraboloid-shaped reflecting surface 32 of the primary reflector which will also be referred to as the axis of the primary reflector. The tracking means comprises basically a calculator or table lookup for computing or storing information regarding the solar ephemeris. The calculations or lookup can be performed by cams or a computer. The tracking means is cooperatively coupled to means 118 for driving the plurality of linear actuators and is responsive to misalignments between the primary reflector and the expected direction of maximum usable solar radiation.The control system further comprises a means for sensing the true orientation of primary reflector 30 relative to base support 44, and a means for detecting a predetermined potentially damaging condition affecting the solar energy system. One embodiment of the means for sensing the true orientation of primary reflector 30 relative to base support 44 includes a plurality of linear displacement transducers 120 disposed between support element 42 and primary reflector 30. Each linear displacement transducer 120 measures the length of a cord 122 between a given point on support element 42 and a given point on primary reflector 30. One type of such linear displacement transducer includes a rotary encoder such as a shaft positioned encoder which is turned as cord 122 is pulled out by primary reflector 30 or drawn back by a spring element.- The location of the given points and the lengths of cord 122 give the true orientation of primary reflector 30. The orientation sensing means and the detecting means are cooperatively coupled to means 118 for driving the plurality of linear actuators such as hydraulic jacks 46 whereby the means 118 for driving the plurality of linear actuators is responsive to the predetermined potentially damaging condition whereby the control system adjusts the position of primary reflector 30 with respect to base support to lessen the effects of the predetermined potentially damaging condition and adjusts the position of the primary reflector for normal operation when the predetermined potentially dangerous condition has passed.One eπ-.bodiment of the means for detecting a predetermined potentially damaging condition affecting solar energy system 10 comprises a means for detecting potentially damaging wind strain on the collector. The means for detecting potentially damaging wind strain on the collector includes strain gauges 124 and data link 126 to transmit data from strain gauges 124 to the decision making portion of the control system, whereby the control system adjusts the position of primary reflector 30 with respect to base support 44 to lessen the effects of the wind strain. One embodiment of the means for detecting a predetermined potentially dangerous condition affecting solar energy system 10 includes a means 128 for detecting potentially damaging high temperature in mixture of fusible salts 20 whereby the control system adjusts the position of primary reflector 30 with respect to base support 44 to misalign primary reflector 30 and the sun in order to decrease the energy flow from the collector to mixture of fusible salts 20. This misaligning of primary reflector 30 and the sun prevents the further overheating of mixture of fusible salts 20 and allows means for producing electric potential 22 or other means for using the stored thermal energy to reduce the temperature within mixture of fusible salts 20. Means 128 for detecting potentially damaging high temperature in mixture of fusible salts 20 can also include means for detecting potentially damaging pressure, thermal loss or salt leakage.The control system further comprises a radiation seeker 130 used as a sun seeker.. Sun seeker 130 is cooperatively coupled to means 118 for driving the plurality of linear actuators, in this case hydraulic jacks 46. Seeker 130 includes at least three photosensitive elements 132 and a means for shading photosensitive elements 132, the means for shading comprising a substantially encircling wall 134 and a variable shading means 136 which forms aperture 138. In this embodiment of radiation seeker 130, the at least three photosensitive elements 132 consist of three roughly copla.nar photosensitive elements. The locus of points eguidistant from three photosensitive elements 132 defines a radiation axis so that three photosensitive elements 132 are substantially equally spaced from one another around the radiation axis, and aperture 138 is substantially concentric about the radiation axis, wherein the elements 132 are exposed to a different amount of radiation when the radiation axis is misaligned with the direction of maximum usable radiation and to the same amount of radiation when the radiation axis is aligned with the direction of maximum usable radiation. At least three photosensitive elements 132 are preferably somewhat angled in toward the radiation axis.Radiation seeker 130 is cooperatively coupled to means 118 for driving the plurality of linear actuators through the decision making portion of the syste and data link 140. The decision making portion of the control system includes differential amplifier 142 and comparators 143a, 143b and 143c. The voltage output 144 of differential amplifier 142 is the average of the output voltages of elements 130a, 130b and 130c. Each of the comparators will have a non-zero output whenever the voltage output of its associated element 130 exceeds the average voltage as indicated by output 144. The outputs 145 of comparators 143 are used to drive hydraulic jacks 46, and in this case, are part of the means for driving the plurality of linear actuators. Thus, means 118 for driving the plurality of linear actuators is responsive to misalignments between primary reflector 30 and the direction of maximum usable solar radiation. As used here, the term photosensitive is used in a broad sense of meaning not just light sensitive, but rather sensitive to all radiation in the range of interest. Similarly, how well radiation seeker 130 aligns with the direction of maximum usable radiation is dependent upon how sensitive photosensitive elements 132 are to radiation in the usable range of frequencies.Variable shading means 136 is responsive to the amount of available usable radiation whereby the size of aperture 138 is responsive to actual radiation conditions. When radiation seeker 130 is used to track the sun, the size of aperture 138 is responsive to the size of the solar image as affected by distance from the sun, clouds, etc. as well as other conditions, thus aiding in more accurately tracking the maximum usable solar radiation. Additionally, by varying the size of aperture 138 according to the amount of available usable radiation, radiation seeker 130 will track the actual solar image and not mistake a bright cloud for the image to be followed. The radiation of interest for solar energy system 10 is solar radiation, but the principals used in radiation seeker 130 work equally well for other forms of radiation. At least one heat pipe 82 includes a means 146 for substantially stopping the transfer of thermal energy from receiver 14 to thermal energy accumulator 16. The control system includes a means 148 for detecting a predetermined level of solar radiation cooperatively coupled to means 146 for substantially stopping the transfer of thermal energy whereby means 146 for substantially stopping the transfer of thermal energy is responsive to the predetermined level of solar radiation. Normally, the predetermined level of solar radiation is a level of solar radiation so low that it takes more energy to operate solar energy system 10 than is received by the system, so that there would be a net energy drain on the system to try to continue to operate. This situation would exist between a certain time in the evening and a certain time in the morning as well as on extremely overcast days. Means 146 for substantially stopping the transfer of thermal energy is also used to prevent reverse heat flow in heat pipe 82 which would drain heat from accumulator 16.Means. 128 for detecting a predetermined temperature within thermal energy accumulator 16 is also cooperatively coupled to means 146 for substantially stopping the transfer of thermal energy whereby means 146 for substantially stopping the transfer of thermal energy is responsive to the predetermined temperature within thermal energy accumulator 16. Thus, if the predetermined temperature is a dangerously high temperature, means 146 can be actuated to substantially stop the transfer of thermal energy from receiver 14 to thermal energy accumulator 16 so that the temperature in thermal energy accumulator 16 is not raised further.One suitable means 146 for substantially stopping the transfer of thermal energy is a magnetically operated butterfly valve within. at least one heat pipe 82, although other suitable means for thermally switching heat pipes are known. One embodiment of the control system also include a data link 150 for transmitting information regardin the pressure, temperature and leakage of working flui 24 within heat exchanger 26, data link 152 fo reporting the speed and torque of turbine 108, and dat link 154 for reporting the current and frequency o generator 106. The term data link is used throughou to refer to both digital and analog data. Data lin 150 is also another means for detecting a predetermine potentially damaging condition.The control system of this embodiment als includes a means 156 for controlling relief valve 11 responsive to data link 150 for reporting pressure, temperature and leakage of working fluid 24 within hea exchanger 26. Thus, dangerously high working flui pressure can be relieved by opening relief valve 116. The control system further comprises means 158 fo throttling the flow of working fluid 24.Solar energy system 10 further comprises retainin wall 168 which in cooperation with thermal energ accumulator 16 forms moat 170 for retaining salt spill or at least impeding the flow of released salts and, thus, preventing ecological havoc. In general, smal installations such as residential installations woul not have as much need for retaining wall 168 as woul large installations.Although a preferred embodiment of the inventio has been described in detail, it should be understoo that various changes, substitutions, and alteration can be made therein without departing from the spiri and scope of the invention as defined by the appende claims. In general, collector 12 is a means fo directing concentrated solar radiation to receiver 14. Thermal energy accumulator 16 in combination wit either means 22 for producing electric potential or an other means for utilizing the thermal energy fro thermal energy accumulator 16 make up one means fo utilizing thermal energy. In embodiments in which at least one collector 12 must substantially face a certain direction with respect to the sun, the embodiment of at least one collector 12 illustrated is only one pivotal means for receiving solar radiation and directing the solar radiation to receiver 14.In an alternative embodiment of at least one collector 12, primary reflector 30 comprises a substantially paraboloid-shaped reflecting surface and secondary reflector 34 comprises a hyperbolic reflecting surface, changing the diameter of secondary reflector 34 relative to the diameter of primary reflector 30 to approximately 50 percent.Many features and subcombinations of this invention are of utility and other applications are contemplated within the scope of the claims. For instance, radiation seeker 130 can also be used for surveying as in laser alignment of large pipelines now being done by conventional optical methods or for the precise guidance of telescopes. At least one collector 12 can be used to provide commercial or residential heat directly.Referring now to Figure 12, solar energy system 160 includes an array 162 of collectors 12, suitable for commercial power generation, to collect and concentrate solar radiation. A receiver 14 is associated with each of said collectors for converting the radiation concentrated by the collectors into thermal energy. Thermal energy transfer system 18 transfers thermal energy from receivers 14 to thermal energy accumulator 16. Solar energy system 16O further comprises a means 22 thermally coupled to mixture of fusible salts 20 within thermal energy accumulator 16 for producing electric potential from the thermal energy stored in the fusible salt mixture. Solar energy system 160 further comprises a cooling tower 164 for cooling working fluid 24 used by solar energy system 160, and a maintenance building 166.OMPI Thus, it will be appreciated that the present solar energy system solves the problems of many collector type systems of the past. First, there is no need to suspend a boiler or any liquid carrying element at the focal point of the primary reflector. Secondly, the receiver which converts radiation into thermal energy is situated at the base of the primary reflector, near the thermal energy transfer system, rather than at the focal point of the primary reflector. Further, the receiver itself does not need to transfer any liquid medium to the thermal energy transfer system, although the' receiver could be filled with such medium to be heated in certain applications. Additionally, a preferred embodiment of the system is one in which the only liquid transfer is the liquid metal of the liquid metal heat pipe which is highly efficient and of high reliability. Still further, the thermal energy accumulator not only yields sensible heat, but also yields the heat of fusion of the salts in the mixture over a wide range of temperatures while still remaining in a liquid state. Besides these advantages, the primary collector of the system ' can be maintained in good condition by simply replacing the reflective liner. Other advantages of the solar energy system of this invention are obvious from the description and the appended claims.Although a preferred embodiment of the invention' has been described in detail, it should be understood that various changes, substitutions and alterations can be made therein without departing from the spirit and scope of the invention as defined by the appended claims.BUKO | Claims1. A collector for concentrating radiation from substantially a single direction and directing the concentrated radiation to a receiver, the collector comprising, in combination: a primary reflector including a concave substantially paraboloid-shaped reflecting surface for concentrating radiation; a secondary reflector for directing to a receiver the radiation concentrated by the primary reflector; and a means for fixing the position of the secondary reflector with respect to the primary reflector wherein the secondary reflector reflects substantially all of the radiation reflected from the primary reflector.2. A collector according to Claim 1, wherein the primary reflector forms an aperture substantially at the vertex of the substantially paraboloid- shaped reflecting surface and the receiver is disposed outside of the primary reflector opposite the aperture whereby the radiation reflected from the secondary reflector is directed through the aperture to the receiver.3. A collector according to Claim 2 to be used in conjunction with a support element, wherein the collector further comprises: a base support for pivotally mounting the primary reflector; and a plurality of linear actuators for adjusting the position of the primary reflector with respect to the base support, wherein the linear actuators are disposed from one another between the primary reflector and the support element. 4. A collector according to Claim 3 wherein the plurality of linear actuators consists of three linear actuators.5. A collector for concentrating radiation from substantially a single direction comprising a primary reflector for concentrating the radiation, the primary reflector comprising, in combination: a removable liner for lining the concentrating side of the reflector, the liner having a reflective side for concentrating the radiation; and a means for evacuating air from between the liner and the adjacent portion of the rest of the primary reflector whereby the liner is held in place by air pressure.6. A collector according to Claim 5 to be used in conjunction with a support element, wherein the primary reflector forms a concave substantially paraboloid-shaped surface for receiving the removable liner, the collector further comprising: a base support for pivotally mounting the primary reflector; and a plurality of linear actuators for adjusting the position of the primary reflector with respect to the base support, wherein the linear actuators are disposed from one another between the primary reflector and the support element.7. A collector according to Claim 6 wherein the primary reflector further comprises a reinforced plastic shell wherein the reinforced plastic • shell forms the concave substantially paraboloid-shaped surface for receiving the removable liner.■BUR_ O PA - WI 8. A collector according to Claim 7 wherein the reinforced plastic shell comprises a fiberglass reinforced plastic shell.9. A collector according to Claim 7 to be used in conjunction with a receiver of the concentrated radiation, the collector further comprising, in combination: a secondary reflector for directing to the receiver the radiation concentrated by the primary reflector; and a means for fixing the position of the secondary reflector with respect to the primary reflector wherein the secondary reflector reflects substantially all of the radiation reflected from the primary reflector.10. A collector according to Claim 8 wherein the primary reflector forms an aperture substantially at the vertex whereby when the receiver is disposed outside the primary reflector opposite the aperture, the radiation reflected from the secondary reflector is directed through the aperture to the receiver.11. A method of concentrating radiation and directing the concentrated radiation to a receiver, comprising in combination: reflecting the radiation to be concentrated to a smaller area than the original reflecting area, thus concentrating the radiation; and reflecting the concentrated radiation towards the receiver. | SOLAR DYNAMICS LTD | MARKE R |
WO-1979001006-A1 | 1,979,001,006 | WO | A1 | EN | 19,791,129 | 1,979 | 20,090,507 | new | G01J1 | null | F03G6, F24J2, G01S3 | F03G 6/06R2, F24J 2/12, G01S 3/786B, R03G 6/00T150 | RADIATION SEEKER | A solar energy gathering system includes a radiation seeker (130) which tracks the movement of the sun, the seeker includes three photosensitive devices (132a, 132b, and 132c) positioned below an adjustable aperture (138). When seeker (13a) is used to track the sun, the size of the aperture (138) is responsive to the size of the solar image as affected by clouds and other conditions. By varying the size of aperture (138) according to the amount of available radiation, radiation seeker (130) will track the actual solar image and not mistake a bright cloud for the image to be followed. | Description Radiation SeekerTechnical FieldThe present invention relates generally to solar 5 energy systems, and in one of its aspects, to a high temperature collector system using a salt mixture storage. Another aspect of the invention relates to a method and apparatus for tracking the movement of a radiation source such as the movement of the sun across10 the sky.Background ArtThe recovery of useful energy directly from solar radiation has been the subject of much work in recent years. Collector systems including collector systems15 using parabolic-shaped collectors are known. Various kinds of thermal energy accumulators are known including those using mineral storage, oil and mineral storage and liquid storage. Salt eutectics, also known as salt eutectic mixtures, have also been used for20 thermal energy storage as shown in ϋ. S. Patent No. 3,709,209 issued to Schroder.Mineral storage is limited to sensible heat . only since there is no realistic operating range wherein the heat of fusion might be utilized. Further, since there25 is air in the mineral media itself, expanding gases must be dealt with. Further, the transfer of thermal energy within the mineral media itself is slow.Oil and mineral storage of thermal energy is not suitable for high temperatures due to the flammability30. of most oils. Additionally, oil and mineral storage systems pose drastic environmental problems in the event of either a fire or a spill. Liguid thermal energy storage systems normally have low boiling points and excessive vapor pressure and often present flammability problems.Salt eutectics overcome many of the problems presented by the other thermal storage systems, but usually have narrow thermal bandwidths and cannot be utilized at extremely high temperatures.Compound parabolic structures are known for light collectors as described by Winston, Light Collection within the Framework of Geometric Optics , J. Optical Soc. Am., Vol. 60, pp. 245-247 (1970). The structures described by Winston were, however, developed for compound parabolic troughs of such a nature that they can be used for solar radiation collection in ■ a fixed position relative to the earth and not have to track the sun. The present invention, on the other hand, makes use of a compound paraboloidal geometry for a radiation absorbing receiver which has no exit aperture, substantially does not reflect and is not fixed relative to the earth.A sun tracking system is shown in U. S. Patent No. 3,996,917 issued to Trihey which includes two pairs of light sensitive elements disposed on opposite sides of an optical axis so that the two elements of each pair will be exposed to a different degree of solar radiation when the optical axis is misaligned with the direction of the sun, and a shading element to increase the sensitivity of the tracker to small movements of the sun. The shading element is fixed in size and position relative to the light-sensitive elements and doe's not take into account the differences between sunny days where the solar image is small but intense and cloudy days when the solar image is large but less intense. Disclosure of InventionThe present invention concerns a system for utilizing solar energy by collecting and concentrating solar radiation and converting the radiation concentrated into thermal energy and then storing that thermal energy at a high temperature. The solar energy system utilizes at least one collector for collecting and concentrating the solar radiation and a receiver associated with the at least one collector for converting the radiation concentrated by the collector into thermal energy at a high temperature. The thermal energy is then transferred from the receiver to a thermal energy accumulator which includes a mixture of fusible salts. The salts are fused by the high temperature of the solar energy system so that during periods of reduced sunshine, the system can continue to supply thermal energy not only from the sensible heat of the salts but also from the salts giving up the heat of fusion as various salts in the mixture nucleate. The salts of the mixture are chosen in such a way that they nucleate at different temperatures, thus spreading the time over which significant energy can be extracted from the thermal energy accumulator and maintaining the mixture in a fluid state over a wide range of temperature.One important feature of the invention is a collector for concentrating radiation from sub¬ stantially a single direction which is used as the collector for collecting and concentrating solar radiation.' The collector includes a primary reflector including a concave substantially paraboloid-shaped reflecting surface for concentrating radiation and a secondary reflector for directing to the receiver the radiation concentrated by the primary reflector. The primary reflector forms an aperture substantially at the vertex of the substantially paraboloid-shaped reflecting surface, and the receiver is disposed outside of the primary reflector opposite the aperture whereby the radiation reflected from the secondary reflector is directed through the aperture to the receiver. The primary reflector also includes a removable reflective liner for lining the concentratingOMP1 <$ wipo ,^ εide of the reflector so that the reflecting surface can actually be removed and replaced rather than polished, thus simplifying maintenance of the collector. One embodiment of the solar energy system utilizes at least one heat pipe for transferring thermal energy from the receiver to the thermal energy accumulator. The at least one heat pipe includes a means for substantially stopping the transfer of thermal energy. According to another important feature of the invention, a radiation seeker is used as a sun-seeker, and as part of a control system, the sun-seeker can be used for guiding the collector. The sun-seeker includes three photosensitive elements disposed around a central axis and an adjustable aperture along the axis so that the elements are exposed to a different amount of solar radiation when the tracker is misaligned with the direction of maximum usable solar radiation and to the same amount of solar radiation when the radiation axis is aligned with the direction of maximum usable solar radiation. This arrangement also prevents the tracker from mistakenly tracking a bright cloud rather than the sun.The solar energy system also utilizes a control system which adjusts the position of the primary reflector with respect to its support and can stop the transfer of thermal energy from the receiver to the thermal energy accumulator as well as perform other system functions. The control system is responsive to the expected position of the sun and the position of the sun as tracked by the sun-seeker, as well as certain predetermined potentially dangerous conditions.The novel features which characterize the invention are defined by the appended claims. The foregoing and other objects, advantages and features of the invention will hereinafter appear, and for purposes of illustration of the invention, but not of limitation, an exemplary embodiment of the invention is shown in the appended drawings. Brief Description of DrawingsFigure 1 is a schematic diagram of the overall system;Figure 2 is an elevational view of a collector according to this invention;Figure 3 is a plan view of a collector , according to this invention with the collector oriented to receive radiation from straight overhead;Figure 4 is a sectional view of a collector, a receiver and part of a thermal energy transfer system utilized in the present invention;Figure 5 is a detail view taken from FIGURE 4;Figure 6 is a perspective view of a receiver and part of a thermal transfer system according to this invention;Figure 7 is a pictorial representation of a meridian view of a compound paraboloid of revolution;Figure 8 is a detail section view taken from Figure 1; Figure 9 is an isometric view in partial section of a sun-seeker according to this invention;Figure 10 diagramatically shows a sun-seeker according to the present invention;Figure 11 is a schematic diagram of the overall system showing much of the major feedback and control flow of the control system; andFigure 12 is a schematic diagram of a commercial size power station utilizing the present invention. Best Mode for Carrying Out the Invention Referring now to the drawings, a solar energy system constructed according to the. present invention is indicated generally by reference numeral 10. The solar energy system 10 includes at least one collector 12 for collecting and concentrating solar radiation, a receiver 14 associated with said at least one collector 12 for converting the radiation concentrated by the collector into thermal energy, a thermal energy accumulator 16, and a thermal energy transfer system 18 for transferring thermal energy from the receiver to the thermal energy accumulator. The thermal energy accumulator 16 comprises a mixture of fusible salts 20 wherein the nucleation temperature of at least one salt of the mixture differs from the nucleation temperature of at least one other salt of the mixture.One embodiment of solar energy system 10 further comprises a means 22 thermally coupled to the fusible salt mixture for producing electric potential from the thermal energy stored in fusible salt mixture 20. Means 22 for producing electric potential includes a working fluid 24, a heat exchanger 26 thermally coupled to the fusible salt mixture for transferring heat from fusible salt mixture 20 to working fluid 24, and a means 28 driven by working fluid 24 for producing electric potential.Collector 12 of this invention is generally a collector for concentrating radiation from substantially a single direction and directing the concentrated radiation to a receiver such as receiver 14. In this embodiment, collector 12 is used for concentrating solar radiation which is substantially from a single direction at any given moment and generally comprises a pivotal means for receiving solar radiation and directing ' the solar radiation to receiver 14. In this embodiment, collector 12 includes a pivotal joint 15 to allow the collector to pivot. Pivotal joint 15 also houses receiver 14.Collector 12 comprises a primary reflector 30 including a concave substantially paraboloid-shaped reflecting surface 32 for concentrating radiation,- a secondary reflector 34 for directing to receiver 14 the radiation concentrated by a primary reflector 30, and a means for fixing the position of secondary reflector 34 with respect to primary reflector 30 wherein the secondary reflector reflects substantially all of the radiation reflected from the primary reflector. Preferably, secondary reflector 34 is a convex reflector positioned to reflect the radiation reflected from primary reflector 30 before the radiation passes through focus. In one preferred embodiment, secondary reflector 34 is a convex parabolic reflector with a diameter roughly 10 percent as large as that of primary reflector 30. Means for fixing the position of secondary reflector 34 with respect to primary reflector 30 includes three support elements 36 disposed peripherally to primary reflector 30 and secondary reflector 34. Support elements 36 include a means for adjusting the position of secondary reflector 34 with respect to primary reflector 30, the means in this case consisting of extensors 38.Primary reflector 30 forms an aperture 40 substantially at the vertex of paraboloid-shaped reflecting surface 32. Receiver 14 is disposed outside of primary reflector 30 opposite aperture 40 whereby the radiation reflected from secondary reflector 34 is directed through aperture 40 to receiver 14. The radiation reflected from secondary reflector 34 is preferably focused at a point interior to receiver 14.Referring now to Figures 2 through 5, collector 12 is used in conjunction with a support element 42. Collector 12 further comprises a base support 44 for ' pivotally mounting primary reflector 30, and a plurality of linear actuators which in this case consist of three hydraulic jacks 46 for adjusting the position of primary reflector 30 with respect to base support 44, the linear actuators being disposed from one another between primary reflector 30 and support element 42.Primary reflector 30 comprises a removable liner 48, better shown in Figure 5, for lining the concentrating side of reflector 30, the liner having a reflective side for concentrating the radiation. When in place, the reflective side of liner 48 becomes reflecting surface 32 for concentrating radiation. Primary reflector 30 further comprises a means evacuating air from between liner 48 and the adjacent portion of the rest of primary reflector 30 whereby liner 48 is held in place by air pressure. A ring 52, preferably made of silicone or thermo resistant plastic, is also included in primary reflector 30 in this embodiment to aid in holding liner 48 in place and to assist in installing a new removable liner.Primary reflector 30 comprises a reinforced plastic shell 54 which forms a concave substantially paraboloid-shaped surface 56 for receiving removable liner 48. Rubber ring 52 grips outer edge 58 of reinforced plastic shell 54 and grips removable liner 48 in slit 59. Thus, when replacing removable liner 48, a workman slides a new liner 48 into slit 59 and then establishes a vacuum underneath the liner by means 50. Means 50, in one embodiment, includes a plurality of porous areas through which air can be evacuated while still providing support to liner 48. By means of this invention, maintaining a high quality reflecting surface for a collector becomes a simple matter which can be routinely performed by relatively unskilled labor. -Maintaining the reflecting surface no longer reguires elaborate cleaning or buffing operations. Removable liner 48 is made of metal coated plastic such as aluminized plastic, and secondary reflector 34 comprises a highly polished surface such as the mirrors used in high powered lasers, although suitable substitute materials such as an electroplated metal stamping might be found. Referring now to Figures 6 and 7, a preferred embodiment of receiver 14 forms a cavity 60 with an aperture 62 for receiving the collected and concentrated solar radiation into cavity 60. Aperture 62 is oppositely disposed to vertex aperture 40 formed by primary reflector 30. Receiver 14 further comprises a plurality of radiation absorptive and thermally conductive fins 64 projecting from the wall of cavity 60. The wall of cavity 60 formed by the receiver is generally a compound paraboloid of revolution. The generating compound parabola of this embodiment is composed of four parabolic sections 66, 68, 70 and 72 which intersect at intersection points 74, 76, and 78. The generating compound parabola is revolved around an axis of revolution 81 to generate the compound paraboloid surface which describes the wall of cavity 60. The extensions of the parabolic sections beyond the intersection points are shown for illustration only. The curve formed by the inner edge of one of fins 64 is geometrically similar to the generating compound parabola. The solar radiation directed into receiver 14 by secondary reflector 34 is preferably focused at a point 80 which is interior to cavity 60.Receiver 14 further comprises a means for increasing the radiation absorptive surface area of the cavity wall and plurality of fins 64. In this case the means includes surface roughness . of the radiation absorptive surfaces. It can thus be seen, that due to its compound paraboloid of revolution shape along with the use of fins and surface roughness all aiding in its radiation absorptive and thermally conductive characteristics, that receiver 14 is well suited for converting the radiation concentrated by collector 12 into thermal energy. Due to the nature and characteristics of the receiver, very little of the energy reradiated from the surface of the wall of cavity 60 and fins 64 will be lost from the receiver. The wall of cavity 60 and the plurality of fins 64 are preferably colored black to aid in radiation absorption. Receiver 14 is substantially enclosed in thermal insulation 65 for preventing loss of thermal energy. A preferred embodiment of thermal energy transfer system 18 comprises at least one heat pipe 82, heat pipe 82 including an evaporator section 84 thermally coupled to receiver 14 and a condensor section 86 ther ally coupled to thermal energy accumulator 16 b means of terminator 87. Terminator 87, in a preferre embodiment, comprises a ceramic material such a berrylium oxide. At least one heat pipe 82 comprises liquid metal working fluid for high temperatur applications.Thermal energy transport system 18 furthe comprises a thermally conducting coupling 88 thermall coupled to receiver 14 and the at least one heat pip 82, wherein coupling 88 rotates freely about the a least one heat pipe 82 and coupling 88 rotates freel within base 90 of receiver 14. The axis of rotation 9 of coupling 88 is in a direction substantiall perpendicular to the axis of rotation 94 of receive 14. It can thus be seen that heat is transferred fro receiver 14 to the at least one heat pipe 82, an receiver 14 pivots freely with respect to the at leas one heat pipe 82 so that the collector heat pip combination is free to track the sun. In one embodiment of thermal energy accumulato 16, mixture of fusible salts 20 comprises a mixture o sodium salts. The mixture of- sodium- salts consist mainly of sodium sulphate and at least one salt fro the group of sodium sulfide, sodium chloride and sodiu metasilicate. Preferably, the mixture of sodium salt consists mainly of sodium sulphate, sodium sulfide sodium chloride and sodium metasilicate. Sodiu sulphate has a relatively low fusion temperature o 31°C. Once the sodium sulphate has fused, the entir mixture can be kept in a flowable condition • since, i the salts of the mixture are carefully chosen, th nonfused salts will remain in gelling pockets throughout the mixture. Once the entire mixture i brought to its normal operating temperature, all of th salts of the mixture will be in a liquid state. Durin periods when the energy received by the solar energ system from the sun is inadequate to keep up with th demands on the system by the system's energy thermal energy accumulator 16 can continue to supply usable energy over a long period of time and considerable temperature range since mixture of fusible salts 20 can yield not only sensible heat, but can also yield the heat of fusion for each of the salts as each of the salts nucleates. Since at least one of the salts of the mixture remains in a liquid state throughout all of the useful operating temperatures of the mixture, transfer of thermal energy within the mixture of fusible salts 20 itself and transfer of thermal energy from mixture of fusible salts 20 to heat exchanger 26 is facilitated. The mixture of fusible salts 20 of this embodiment can be kept at an average temperature between 1000°C and the boiling temperature of the entire mixture. In another embodiment of the present invention, mixture of fusible salts 20 is a mixture of sodium salts which consist mainly of sodium chloride, sodium nitrate, sodium hydroxide, sodium sulfide, sodium sulphate and sodium metasilicate. Referring now to Figure 1 and Figure 8, thermal energy accumulator 16 further comprises a refractory material lining 96 for substantially enclosing mixture of fusible salts 20, a plurality of metal plates 98 for supporting refractory material lining 96, and a plurality of structural members such as H-beam 100 external to metal plates 98 and engaging metal plates 98 for providing structural strength to thermal energy accumulator 16. A preferred embodiment of refractory material lining 96 comprises fused cast aluminum oxide although other suitable refractories are known in the art.Thermal energy accumulator 16 also comprises a reinforced concrete wall 102 substantially enclosing the structure made up of refractory material lining 96, plurality of metal plates 98 and the plurality of structural members such as H-beam 100. The structural members such as H-beam 100 act as spacers between plurality of metal plates 98 and reinforced concreteOMPI wall 102. This allows the use of an insulation such as alumina-silica insulation between plurality of metal plates 98 and reinforced concrete wall 102. As used here the term metal plates includes but is not limited to steel plates. Reinforced concrete wall 102 is preferably a steel-reinforced concrete wall. The term wall includes the floor and ceiling structure also. Reinforced concrete wall 102 is not necessary for systems that are sufficiently small. Referring again to Figure 1, one means for producing electric potential 22 includes a Rankine cycle power system which includes means 28 driven by working fluid 24 for producing electric potential. Means 28 includes a turbine 108 and a generator 106 driven by turbine 108 through gearing means 110. In this configuration, heat exchanger 26 acts as the boiler or heater for the Rankine cycle power system. For further efficiency, means 22 for producing electric potential can also include a second cycle, the second cycle including heat exchanger 112 and working fluid 114 in a heat exchange relationship with working fluid 24. Heat exchanger 112 thus acts as the condenser for the first cycle as in a normal binary cycle system. Pump 25 is included in the first cycle to recompress working fluid 24 and pump 115 is added in the second cycle to recompress working fluid 114 after working fluid 114 has been passed through a condenser 113.A preferred embodiment of means 22 for producing electric potential includes a relief valve 116 for releasing working fluid 24 ,in the event of excessive pressure in working fluid 24 caused by some malfunction in the overall system such as an overheating of mixture of fusible salts 20. Relief valve 116 should only be opened in extreme emergency since the release of working fluid 24 into the environment would normally be undesirable. Means 22 further includes normally open bypass valve 117 for bypassing turbine 108 during( normal operating conditions with some percentage of working fluid 24 in its high pressure gas stage. Turbine 108 can immediately respond to increased load by closing normally open bypass valve 117. A preferred embodiment of solar energy system 10 also includes a control system. Referring now to Figure 11, the control system includes a means 118 for driving the plurality of linear actuators such as hydraulic jacks 46 whereby the control system adjusts the position of primary reflector 30 with respect to base support 44.The control system further comprises a means for tracking the expected direction of maximum usable solar radiation relative to the axis of substantially paraboloid-shaped reflecting surface 32 of the primary reflector which will also be referred to as the axis of the primary reflector. The tracking means comprises basically a calculator or table lookup for computing or storing information regarding the solar ephemeris. The calculations or lookup can be performed by cams or a computer. The tracking means is cooperatively coupled to means 118 for driving the plurality of linear actuators and is responsive to misalignments between the primary reflector and the expected direction of maximum usable solar radiation.The control system further comprises a means for sensing the true orientation of primary reflector 30 relative to base support 44, and a means for detecting a predetermined potentially damaging condition affecting the solar energy system. One embodiment of the means for sensing the true orientation of primary reflector 30 relative to base support 44 includes a plurality of linear displacement transducers 120 disposed between support element 42 and primary reflector 30. Each linear displacement transducer 120 measures the length of a cord 122 between a given point on support element 42 and a given point on primary reflector 30. One type of such linear displacement transducer includes a rotary encoder such as a shaft positioned encoder which is turned as cord 122 is pulled out by primary reflector 30 or drawn back by a spring element. The location of the given points and the lengths of cord 122 give the true orientation of primary reflector 30. The orientation sensing means and the detecting means are cooperatively coupled to means 118 for driving the plurality of linear actuators such as hydraulic jacks 46 whereby the means 118 for driving the plurality of linear actuators is responsive to the predetermined potentially damaging condition whereby the control system adjusts the position of primary reflector 30 with respect to base support to lessen the effects of the predetermined potentially damaging condition and adjusts the position of the primary reflector for- normal operation when the predetermined potentially dangerous condition has passed.One embodiment of the means for detecting a predetermined potentially damaging condition affecting solar energy s'ystem 10 comprises a means for detecting' potentially damaging wind strain on the collector. The means for detecting potentially damaging wind strain on the collector includes strain gauges 124 and data link 126 to transmit data from strain . gauges 124 to the decision making portion of the control system, whereby the c'ontrol system adjusts the position of primary reflector 30 with respect to base support 44 to lessen the effects of the wind strain. One embodiment of the means for detecting a predetermined potentially dangerous condition affecting solar energy system 10 includes a means 128 for detecting potentially damaging high temperature in mixture of fusible salts 20 whereby the control system adjusts the position of primary reflector 30 with respect to base support 44 to misalign primary reflector 30 and the sun in order to decrease the energy flow from the collector to mixture of fusible salts 20. This misaligning of primary reflector 30 and the sun prevents the further overheating of mixture of fusible salts 20 and allows means for producing electric potential 22 or other means for using the stored thermal energy to reduce the temperature within mixture of fusible salts 20. Means 128 for detecting potentially damaging high temperature in mixture of fusible salts 20 can also include means for detecting potentially damaging pressure, thermal loss or salt leakage.The control system further comprises a radiation seeker 130 used as a sun seeker. Sun seeker 130 is cooperatively coupled to means .118 .for driving the plurality of linear actuators, in this case hydraulic jacks 46. Seeker 130 includes at least three photosensitive elements 132 and a means for shading photosensitive elements 132, the means for shading comprising a substantially encircling wall 134 and a variable shading means 136 which forms aperture 138. In this embodiment of radiation seeker 130, the at least three photosensitive elements 132 consist of three roughly coplanar photosensitive elements. The locus of points equidistant from three photosensitive elements 132 defines a radiation axis so that three photosensitive elements 132 are substantially equally spaced from one another around the radiation axis, and aperture 138 is substantially concentric about the radiation axis, wherein the elements 132 are exposed to a different amount of radiation when the radiation axis is misaligned with the direction of maximum usable radiation and to the same amount of radiation when the radiation axis is aligned with the direction of maximum usable radiation. At least three photosensitive elements 132 are preferably somewhat angled in toward the radiation axis.Radiation seeker 130 is cooperatively coupled to means 118 for driving the plurality of linear actuators through the decision making portion of the control BUREX∑ΓOMPI ~ system and data link 140. The decision making portio of the control system includes differential amplifie 142 and comparators 143a, 143b and 143c. The voltag output 144 of differential amplifier 142 is the averag of the output voltages of elements 130a, 130b and 130c. Each of the comparators will have a non-zero outpu whenever the voltage output of its associated elemen 130 exceeds the average voltage as indicated by outpu 144. The outputs 145 of comparators 143 are used t drive hydraulic jacks 46, and in this case, are part o the means for driving the plurality of linea actuators. Thus, means 118 for driving the pluralit of linear actuators is responsive to misalignment between primary reflector 30 and the direction o maximum usable solar radiation. As used here, the ter photosensitive is used in a broad sense of .meanin not just light sensitive, but rather sensitive to al radiation in the range of interest. Similarly, ho well radiation seeker 130 aligns with the direction o maximum usable radiation is dependent upon ho sensitive photosensitive elements 132 are to radiatio in the usable range of frequencies.Variable shading means 136 is responsive to th amount of available usable radiation whereby the siz of- aperture 138 is responsive to actual radiatio conditions. When radiation seeker 130 is used to trac the sun, the size of aperture' 138 is responsive to th size of the solar image as affected by distance fro the sun, clouds, etc. as well as other conditions, thu aiding in more accurately tracking the maximum usabl solar radiation. Additionally, by varying the size o aperture 138 according to the amount of availabl usable radiation, radiation seeker 130 will track th actual solar image and not mistake a bright cloud fo the image to be followed. The radiation of interes for solar energy system 10 is solar radiation, but th principals used in radiation seeker 130 work equall well for other forms of radiation. At least one heat pipe 82 includes a means 146 for substantially stopping the transfer of thermal energy from receiver 14 to thermal energy accumulator 16. The control system includes a means 148 for detecting a predetermined level of solar radiation cooperatively coupled to means 146 for substantially stopping the transfer of thermal energy whereby means 146 for substantially stopping the transfer of thermal energy is responsive to the predetermined level of solar radiation. Normally, the predetermined level of solar radiation is a level of solar radiation so low that it takes more energy to operate solar energy system 10 than is received by the system, so that there would be a net energy drain on the system to try to continue to operate. This situation would exist between a certain time in the evening- and a certain time in the morning as well as on extremely overcast days. Means 146 for substantially stopping the transfer of thermal energy is also used to prevent reverse heat flow in heat pipe 82 which would drain heat from accumulator 16.Means 128 for detecting a predetermined temperature within thermal energy accumulator 16 is also cooperatively coupled to means 146 for substantially stopping the transfer of thermal energy whereby means 146 for substantially stopping the transfer of thermal energy is responsive to the predetermined temperature within thermal energy accumulator 16. Thus, if the predetermined temperature is a dangerously high temperature, means 146 can be actuated to substantially stop the transfer of thermal energy from receiver 14 to thermal energy accumulator 16 so that the temperature in thermal energy accumulator 16 is not raised further.One suitable means 146 for substantially stopping the transfer of thermal energy is a magnetically operated butterfly valve within at least one heat pipe 82, although other suitable means for thermally switching heat pipes are known. One embodiment of the control system also includes a data link 150 for transmitting information regarding the pressure, temperature and leakage of working fluid 24 within heat exchanger 26, data link 152 for reporting the speed and torque of turbine 108, and data link 154 for reporting the current and frequency of generator 106. The term data link is used throughout to refer to both digital and analog data. Data link 150 is also another means for detecting a predetermined potentially damaging condition.The control system of this embodiment also includes a means 156 for controlling relief valve 116 responsive to data link 150 for reporting pressure, temperature and leakage of working fluid 24 within heat exchanger 26. Thus, dangerously high working fluid pressure can be relieved by opening relief valve 116. The control system further comprises means 158 for throttling the flow of working fluid 24.Solar energy system 10 further comprises retaining wall 168 which in cooperation with thermal energy accumulator 16 forms moat 170 for retaining salt spills or at least impeding the flow of released salts and, thus, preventing ecological havoc. In general, small installations such as residential installations would not have as much need for retaining wall 168 as would large installations.Although a preferred embodiment of the invention has been described in detail , it should be understood that various changes, substitutions, and alterations can be made therein without departing from the spirit and scope of the invention as defined by the appended claims. In general, collector 12 is a means for directing concentrated solar radiation to receiver 14. Thermal energy accumulator 16 in combination with either means 22 for producing electric potential or any other means for utilizing the thermal energy from thermal energy accumulator 16 make up one means for utilizing thermal energy. In embodiments in which at least one collector 12 must substantially face a certain direction with respect to the sun, the embodiment of at least one collector 12 illustrated is only one pivotal means for receiving solar radiation and directing the solar radiation to receiver 14.In an alternative embodiment of at least one collector 12, primary reflector 30 comprises a substantially paraboloid-shaped reflecting surface and secondary reflector 34 comprises a hyperbolic reflecting surface, changing the diameter of secondary reflector 34 relative to the diameter of primary reflector 30 to approximately 50 percent.Many features and subcombinations of this invention are o-f utility and other applications are contemplated within the scope of the claims. For instance, radiation seeker 130 can also be used for surveying as in laser alignment of large pipelines now being done by conventional optical methods or for the precise guidance of telescopes. At least one collector 12 can be used to provide commercial or residential heat directly.Referring now to Figure 12, solar energy system160 includes an array 162 of collectors 12, suitable for commercial power generation, to collect and concentrate solar radiation. A receiver 14 is associated with each of said collectors for converting the radiation concentrated by the collectors into thermal energy. Thermal energy transfer system 18 transfers thermal energy from receivers 14 to thermal energy accumulator 16. Solar energy system 160 further comprises a means 22 thermally coupled to mixture of fusible salts 20 within thermal energy accumulator 16 for producing electric potential from the thermal energy stored in the fusible salt mixture. Solar energy system 160 further comprises a cooling tower 164 for cooling working fluid 24 used by solar energy system 160, and a maintenance building 166. Thus, it will be appreciated that the present solar energy system solves the problems of many collector type systems of the past. First, there is no need to suspend a boiler or any liguid carrying element at the focal point of the primary reflector. Secondly, the receiver which converts radiation into thermal energy is situated at the base of the primary reflector, near the thermal energy transfer system, rather than at the focal point of the primary reflector. Further, the receiver itself does not need to transfer any liguid medium to the thermal energy transfer system, although the receiver could be filled with such medium to be heated in certain applications. Additionally, a preferred embodiment .of the system is one in which the only liguid transfer is the liquid metal of the liquid metal heat pipe which is highly efficient and of high reliability. Still further, the thermal energy accumulator not only yields sensible heat, but also yields the heat of fusion of the salts in the mixture over a wide range of temperatures while still remaining in a liguid state. Besides these advantages, the primary collector of the system can be maintained in good condition by simply replacing the reflective liner. Other advantages of the solar energy system of this - invention are obvious from the description and the appended claims.Although a preferred embodiment of the invention has been described in detail, it should be understood that various changes, substitutions and alterations can be made therein without departing from the spirit and scope of the invention as defined by the appended claims. | Clai s1. A radiation seeker having a radiation axis, the seeker comprising in combination: at least three photosensitive elements substantially equally spaced from one another around the radiation axis; and means for shading the photosensitive elements, wherein the shading means forms an aperture substantially concentric about the radiation axis, the elements being exposed to a different amount of radiation when the radiation axis is misaligned with the direction of maximum usable radiation, and to the same amount of radiation when the radiation • axis is aligned- with the direction of maximum usable radiation.2. A radiation seeker according to Claim 1 wherein the shading means is responsive to the amount of available usable radiation, whereby the size of the aperture is responsive to actual radiation conditions.3. A radiation seeker according to Claim 1 wherein the at least three photosensitive elements consist of three photosensitive elements.4. A radiation seeker according to Claim 3 wherein the shading means is responsive to the amount of available usable radiation, whereby the size of the aperture is responsive to actual radiation conditions. 5. A sun seeker having a radiation axis, the sun seeker comprising in combination: at least three photosensitive elements substantially equally spaced from one another around the radiation axis; and means for shading the photosensitive elements, wherein the shading means forms an aperture substantially concentric about the radiation axis, the elements being exposed to a different amount of solar radiation when the radiation axis is misaligned with the direction of maximum usable solar radiation, and to the same amount of solar radiation when the radiation axis is aligned with the direction of maximum usable solar radiation.6. A sun seeker according to Claim 5 wherein the shading means is responsive to the amount of available solar radiation, whereby the size of the aperture is responsive to actual solar radiation conditions.7. A sun seeker according to Claim 5 wherein the at least three photosensitive elements consists of three photosensitive elements.8. A sun seeker according to Claim 7 wherein the shading means is responsive to the amount of available solar radiation, whereby the size of the aperture is responsive to actual solar radiation conditions.1 JROMPSΛ?~ WIP φ?N | SOLAR DYNAMICS LTD | MARKE R |
WO-1979001013-A1 | 1,979,001,013 | WO | A1 | EN | 19,791,129 | 1,979 | 20,090,507 | new | C09J7 | B05D5, B05D3 | C09J7, C09J133, H01B3 | C09J 133/08+C4, C09J 7/02F2D, H01B 3/44F | CROSS-LINKED PRESSURE-SENSITIVE TAPE ADHESIVE OF A COPOLYMER OF ALKYL ACRYLATE AND COPOLYMERIZABLE ACID | Pressure-sensitive tape adhesive comprising a copolymer of alkyl acrylate and copolymerizable acid such as acrylic acid, which adhesive includes a small amount of Cr<s3+>s ion which crosslinks the acid groups to afford solvent-resistance while retaining good pressure-sensitive adhesive qualities. The adhesive has excellent electrical insulating properties. | DescriptionCROSS-LINKEDPRESSURE-SENSITIVETAPEADHESIVEOFA COPOLYMEROFALKYLACRYLATEANDCOPOLYMERIZABLEACID^chnical_Pield The invention concerns a pressure-sensitive adhesive tape, the adhesive layer of which is a copolymer of alkyl acrylate and copolymerizable acid. The tape is normally produced in the form of a wide sheet which may be slit to narrow widths and wound upon itself for convenient storage and shipment.B c££ro_urd t_ ϋ. S. Patent No. Re.24,906 concerns pressure-sensitive tape adhesive consisting essentially of a copolymer of alkyl acrylate and a minor proportion of copolymerizable monomer such as acrylic acid. That acrylate copolymer provides excellent adhesion and holding power and experiences no observable deterioration even after years of storage in tape form.For uses requiring improved internal strength at high temperatures and/or resistance to organic solvents, the acrylate copolymer adhesive may be crosslinked. U. S. Patent No. 2,973328β teaches crosslinking it using an organic peroxide prior to coating and applying somewhat greater heat than would be necessary merely to dry the coating. However, the crosslinking is difficult to control. U. S. Patent No. 2,925,174 teaches crosslinking the acrylate copolymer by reaction with a polyfunctional compound such as a polyamine, a polyol or a polyepoxide.- The resultant tapes tend to be deficient in immediate adhesion, usually called wet-grab , or if tailored to provide good wet-grab, to be deficient in internal strength at ambient temperatures.U. S. Patent No. 3* 84,423 incorporates a third copolymerizable monomer, glycidyl acrylate or methacryla to crosslink the acrylate copolymer. However, the gradu crosslinking of the adhesive during storage of the tape gradually reduces its tackiness so that after some month the tape may no longer be useful for its intended purposes. U. S. Patent No. 3,740,366 concerns a class of pressure-sensitive adhesives which is much broader than and includes the acrylate copolymer of Re. 24,906. It says that if such adhesives are crosslinked by a compatible polyvalent metal compound, the shear strength is improved without loss of tackiness and that the adhesive coating becomes resistant to alkaline solutions Among the large number of polyvalent metal compounds suggested in the patent is chromium acetate.While the pressure-sensitive tape adhesives of U. S. patents No. 2,925,174; 3,284,423 and 2,973,286 provide good electrical insulating properties, those of the work ing examples of No. 3,740,366 do not because they are coated from emulsions which necessarily contain dis¬ persing agents such as the sodium salts of the higher fatty acid sulfates. Not only are those dispersing agents harmful to electrical insulating properties, but they also tend to corrode metal conductors to be insulated. The polymerization initiators used in No. 3,740,366 such as ammonium or potassium persulfate are likewise harmful to electrical insulating properties.No. 3,740,366 does suggest that the polymers could be prepared in organic solutions. However, almost all of the named polyvalent metal compounds would tend to cause a solution of an acrylate copolymer to get before it could be coated out, unless the solution were so dilute as to be commercially impractical. To be commercially practical, a tape-coating solution should contain at least 15% solids and preferably more than 20%.Disclosu e of InventionThe present invention concerns what is believed to be the first crosslinked acrylate copolymer of the type disclosed in Re. 24,906, the crosslinking of which is easy to control and provides all of the following properties: good solvent resistance good wet-grab good internal strength at high temperatures unchanging properties during prolonged storage good electrical insulating properties. Like the crosslinked pressure-sensitive adhesives of patent Nos. 2,973,286 and 2,925,174,' the tape adhesive of the present invention comprises an acrylate copolymer of monomers(a) acrylic acid ester of non-tertiary alcohol, the molecules of which have from 1-14 carbon atoms, the average being about 4-12 carbon atoms, at least a major proportion of said molecules having a carbon-to-carbon chain of at least 4 carbon atoms terminating at the hydroxyl oxygen atoms, said chain containing at least about 1/2 the total number of carbon atoms in the alcohol molecule, said acrylic acid ester being further characterized as being per se polymerizable to a sticky, stretchable elastic adhesive polymer mass, andIjυREZ∑rOMPI wipo Λ, (b) at least one copolymerizable monoethylenic monom selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid, the total copolymerizable monomer (b) comprising about one-half to ten percent by weight of the total of said monomers (a) and (b). Best results have been attained using acrylate copolymers having inherent viscosities within the range of 1.2 to 1.6, although values of 1.0 or somewhat lower should also be useful. The pressure-sensitive tape adhesive of the present invention includes Cr-* ion in an amount up to 0.2 per¬ cent by weight of the acrylate copolymer. To provide significant improvements in internal strength and solven resistance, at least 0.002 weight percent of Cr 3+ ion should be present, and preferably at least 0.005 percent when the acid content of the acrylate copolymer is above three percent. Above about 0.05 percent Cr 3+ ion, the adhesive may have less wet-grab than is desirable for most uses. The adhesive layer of a tape of the present inven¬ tion should be free from emulsifying agents and hence coated from solution, since it is not known how to ob¬ tain uniform coatings from emulsions without using dis¬ persing agents which would be harmful to electrical insulating properties. In order to combine the Cr 3+ ion with the acrylate copolymer, it should be added to the coating solution as a compound which is soluble in the acrylate copolymer. Such compounds which have been used in the practice of this invention include chromium octoate, chromium acetate, chromium oleate, chromium neodecanoate and chromium naphthenate. While the manner in which the Cr 3+ ion achieves the crosslinking is not clearly understood, it is believed that it forms an ionic or salt bridge between acid groups. The cross¬ linking appears to proceed to virtual completion at times and temperatures that would have been used to drive off the solvent in the absence of any cross¬ linking agent. The degree of insolubility attained is surprisingly high in view of the fact that the number of Cr 3+ ions may be only about 1/100 of the number of carboxylic acid groups in the copolymer. While there is only minor benefit in doing so, the novel adhesive may be combined with a small amount of a highly reactive polyfunctional epoxide. However, to avoid noticeable loss of wet-grab, the amount of the epoxide should be less than that used in U. S. Patent No. 2,925,174, i.e., less than 0.4 equivalent of the epoxide and preferably less than 0.1 equivalent of the epoxide per acid equivalent of the acrylate copolymer. It is believed that the Cr 3+ ion catalyzes reaction between the epoxy groups and the acid groups of the acrylate copolymer in addition to bridging others of the acid groups. When the adhesive includes epoxide, some crosslinking continues during storage at room temperature, whereas in the absence of epoxide, no continuing crosslinking has been noticeable. As in 2,925,174, the polymerizable mixture of non- tertiary alkyl ester monomer (a) and the copolymerizable acid monomer -(b) may include small amounts of other copolymerizable monomers such as ethyl acrylate, vinyl chloride, vinyl acetate, various methacrylic esters, butadiene, isoprene, diallyl phthalate and acrylamide in such limited amounts as do not produce drastically altered properties. In preparing the acrylate copolymer, best results for the present invention are obtained if the amount of the copolymerizable acid monomer (b) is within the range of 1 to 6 percent of the total weight of the copolymeriz able monomers. Below 1%, the resultant adhesive tends to have lower internal strength whereas above 6%, it tends to have reduced wet-grab.In the absence of additives, adhesive layers of the invention are highly transparent. Inert fillers and pigments may be added for such purposes as to provide color and/or opacity, or to increase firmness. If the tape is to be exposed to certain solvents, the backing and primer coating should also be resistant to those solvents. Backing members which are resistant to most common solvents include biaxially-oriented polyethylene terephthalate, glass cloth, polytetrafluoroethylene, polyimide and metal foils.The need for low-adhesion backsizes or low-adhesion liners with the novel pressure-sensitive adhesive tapes to allow the tape to be unwound more readily from roll form depends to a large extent on the specific adhesive formulation, since relatively larger percentages of the copolymerizable acid monomer (b), e.g., about 6-10 per¬ cent of the acrylate copolymer, provide adhesives which tend to become tenaciously bonded to another surface on prolonged contact therewith, while acrylate copolymer adhesives produced with smaller percentages of the monomer (b) are more easily removed.Tapes of the present invention were tested as follows :lϊ^ Solubility A strip of the tape is immersed in a bottle of acetone. After 3 days at room temperature, the tape is removed and placed in an oven at 65°C overnight, cooled and weighed to determine the loss. In some cases, the same test is performed after holding a roll of the tape in an oven for 9 hours at 65°C.Electrical Corrosion Test Cellulose acetate cloth is wrapped around a non- conductive panel and two #32-gauge (0.2-mm diameter) copper wires are wrapped over the cloth so as to be spaced 0.63 cm. The tape to be tested is' adhered by its own adhesive to the cloth over the wires and rolled down firmly with a rubber roller. The test specimen Is suspended in a sealed container maintained for 20 hours at 49°C and 95 relative humidity while 250 volts DC is applied across the wires. The breaking strength of the positive wire is measured and compared either to an untested piece of the wire or to the negative wire. The latter is preferred because the negative wire Is never corroded by the test and tends to have the same breaking strength as the positive wire before testing, assuming the two specimens were adjacent in the original spool.Shear Strength at 65°CThe test tape is slit to 1.27-cm width and adhered at the edge of a stainless steel plate by its own adhe¬ sive coating to provide a bonded area 1.27 cm square. The tape is pressed into contact with the plate under the weight of 4 passes of a 2040-gram hard-rubber roller and held in an oven at 65°C for 10 minutes before testing at that temperature. With the steel plate in the vertical position, a 500-gram mass is suspended from the adhesive tape and the time to failure is noted. When the test is discontinued without failure, the time until discontinuance is reported with a greater than ( > ) sign.Peelback Adhesion Test At 21°C the test tape is adhered by its own adhesive to a stainless steel plate using four passes of a 2040- gram hard-rubber roller and allowed to dwell for 10 minutes. The free end of the tape is then peeled back at an angle of l8θ° at the rate of 30 cm/minute.Best Mode for Carrying Out the Invention In the following examples, all proportions are by weight, as are proportions disclosed above except where noted-.Example 1 A copolymer of 98 parts of isooctyl acrylate and 2 parts acrylic acid was prepared as described in Re.24,906 using ethyl acetate and heptane in 1:2 ratio as solvents and azobisisobutyronitrile as catalyst. The inherent viscosity of the copolymer was 1.51. The product solu¬ tion contained 24.4% solids and had a coatable viscosity of 5500 cps at 25°CAdded to the product solution was a pigment dispersion comprising titanium dioxide plus a minor proportion of polyterephthalate aldazine which had been ball milled overnight in solvents. The resultant composition (here called Composition A ) comprised: Part_s_Product solution 100Pigment 3-9Antloxidant 0.1 Ethyl alcohol 3-8Ethyl acetate 8.0Toluene 3-6To biaxially-oriented polyethylene terephthalate film having a thickness of 25 micrometers was applied a solu- tion of butadiene/acrylonitrile rubber, liquid bisphenol- A-type epoxy resin and polyamide resin followed by strongly irradiating the ultra-thin dried coating with ultraviolet light as dis'closed in U. S. Patent No. 3,188,266 to provide an adhesion-promoting primer coat- ing. To lengths of this primed film were applied coat¬ ings of Composition A, some containing various amounts > of chromium octoate and a diepoxide, namely, 3, -epoxycyclohexylmethyl-(3,4-epoxy)cyclohexane carboxyl- ate, as indicated in Table A. The coatings were dried in an air-circulating oven at times and temperatures suffi¬ cient merely to drive off the solvents, and the resultant tapes were wound upon themselves in roll form. The dried coating weight of the pressure-sensitive adhesive coating in each case was about 10 grains per 24 square inches (42 grams per square meter). Test results were as reported in Table A.-£UREΛ >OMPI TABLE t- iTest ResultsParts per IOC ) parts Solubility in Shear strength coj)θl mer of acetone (%) at 65°C Peelback adhesion at after 9 hrs.3+ Diei£oxide_ _RT_ a _6_ C Minutes (N/cm of width)0 0 60 52 1 4.60 .10 72 38 0 4.1 1.00275 0 39 35 15 3.8 HO10 .0055 0 33 32 >1100 3.8 1.0066 .05 39 33 220 3.8.0066 .20 38 19 >1100 3.9.00825 0 31 28 >1100 3.8.0110 0 27 25- >1100 3.715 .01375 0 27 24 >1100 3.7.0165 0 24 22 >1100 3.8Example _2Tapes similar to those of Example 1, except excluding pigment, were tested with results as shown in Table B. BUREAU OMPI TABLE BTest Results100 parts Solubility in Shear strength ιer of acetone (%) at 65°C Peelback adhesion at after 96 hrsCr 3+ DiejDOxide RT at 65°C Minutes (N/cm of width)0 0 80 62 0.3 3. .7 .011 0 31 •26 >1100 3, .2 \-> .011 .10 ro29 20 >1100 3. .110 .022 0 21 20 lOO 3. .1 .033 0 16 15 >1100 2, .8Example_3 Tapes were prepared as in Example 1 except using a copolymer of 94 parts isooctyl acrylate and 6 parts acrylic acid. Test results are reported in Table C.'BU EACTOMP1 TABLE CTest ResultsParts per 100 parts Solubility in Shear strength ___2.__2.°.l.yul _2.£ acetone (%) at 65°C Peelback adhesion at after 96 hrs.Cr 3+ Diep_oxide RT at 65°C Minutes (N/cm of width)0 0 100 99 0 4.4 , .00165 .02 95 92 7 4.6 H4= .00165 .08 100 45 12 5.0 110 .00275 0 90 69 11 4.8 .0055 0 51 47 160 5.0 .0066 .02 45 40 >3000 5.0 .0066 .08 41 30 >3000 4.7.00825 0 40 38 >3000 4.715 .0440 0 12 12 >3000 — A number of the tapes of the above examples have been subjected to the Electrical Corrosion Test. In every case the breaking strength of the positive wire after the test was equal to the original breaking strength within the 2% accuracy of the test, indicating no measurable degree of corrosion.A number of the tapes of the above examples were tested for electrical insulating resistance under ASTM D 1000/76. In every case the value exceeded 10 megohms, the limit of the testing instrument. | Claims1. A pressure-sensitive adhesive tape, the adhesive layer of which comprises a copolymer of (a) acrylic acid ester of non-tertiary alcohol, the molecules of which have from 1-14 carbon atoms, the average being about 4-12 carbon atoms, at least a major proportion of said molecules having a carbon-to-carbon chain of at least 4 carbon atoms terminating at the hydroxyl oxygen atoms, said chain containing at least about one-half the total number of carbon atoms in the molecule, said acrylic acid ester being per se polymeriz- #able to a sticky, stretchable elastic adhesive polymer mass, and (b) at least one copolymerizable monoethylenic monomer selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid, -the total copolymerizable monomer (b) comprising about one-half to ten percent by weight of the total of said monomers(a) and (b), characterized by the feature that: the adhesive layer includes Cr 3+ ion n an amount up to 0.2 percent of the weight of the copolymer.2. A pressure-sensitive adhesive tape as defined in claim 1, further characterized by the feature that: tthhee aammoouunntt ooff CCrr3 3++ iioonn ii;s 0.002 to 0.05 percent of the weight of the copolymer.3- Method of making a pressure-sensitive adhesive tape comprising the steps of (1) dissolving in solvent a copolymer of (a) acrylic acid ester of non-tertiary alcohol, the molecules of which have from 1-14 carbon atoms, the average being about 4-12 carbon atoms, at least a major proportion of said molecules having a carbon-to-carbon chain of at least 4 carbon atoms terminating at the hydroxyl oxygen atoms, said chain containing at least about 1/2 the total number of carbon atoms in the molecule, said acrylic acid ester being per se polymerizable to a sticky, stretchable elastic adhesive polymer mass, and (b) at least one copolymeriz¬ able monoethylenic monomer selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid, the total copolymerizable monomer (b) comprising about one-half to ten percent by weight of the total of said monomers (a) and (b) to provide a solution of coatable viscosity, (2) coating the solu¬ tion onto a solvent-resistant backing member and (3) drying the coating, characterized by the feature that in step (1) a Cr 3+ salt is dissolved in an amount pro¬ viding up to 0.2 percent of the weight of the copolymer.4. Method as defined in claim 3, further charac- terized by the feature that the Cr 3+ salt is chromium octoate, chromium acetate, chromium oleate, chromium neodecanoate and/or chromium naphthenate.5. Method as defined in claims 3 or 4, further characterized by the feature that in step (1) also dissolved is a polyfunctional epoxide in an amount providing less than 0.1 epoxide equivalent per acid equivalent of the copolymer of monomers (a) and (b).'BURE ΓOMPI | MINNESOTA MINING & MFG; MINNESOTA MINING & MFG CO | DIAMOND J |
WO-1979001019-A1 | 1,979,001,019 | WO | A1 | EN | 19,791,129 | 1,979 | 20,090,507 | new | B08B7 | B06B1, F28G7, F23J3 | B06B1, B08B7, B08B17, F23J3, F28G7 | B08B 7/02, F28G 7/00 | A METHOD IN SONIC CLEANING | A method in sonic cleaning of a space (13) wherein there is a tendency of a coating being formed on the surfaces thereof. By controlled relative phase shift of pressure waves emitted from two mutually spaced locations (A, B) an amplified pressure wave is produced, which scans the space said amplified pressure wave providing an effective loosening of the coating by acting on the surfaces of the space (13). | A METHOD IN SONIC CLEANINGInternal spaces of furnaces, heat exchangers and similar apparatuses with gas flowing therethrough such as hot flue gases or waste gases from chemical processes, tending to form a dust coating on the surfaces of the space generally should be kept free from coatings formed by ashes or soot because such coatings are heat insulat¬ ing, can change the flow pattern in the space and also can cause increased corrosion of existing metal surfaces. In order to prevent the unfavourable operating condi¬ tions thus associated with an increasing coating in the actual 'space, from arising it has become more and more common to use so-called sonic cleaning, i.e. to use gas-carried pressure waves with tone or infrasonic frequency in order to physically affect the dust of the coating because this is a cheap cleaning method as compared with e.g. sweeping by means of steam.In sonic cleani ng, vibration energy is supplied usually as pressure waves from a high-power sound emitter which is mounted in a wall with some external air cooling, and is distributed to different parts of the space, e.g. the narrow spaces between a plurality of boiler tubes in a boiler installation. A high sound pressure level is required in order to obtain a satis¬ factory cleaning. However, problems may be involved in distributing the vibration energy to all parts of the space which is often of complicated form, considering the occurence of sound shadow although there is obtained in most cases a surprisingly uniform distribution of the pressure waves due to reflection of the sound in the space to be cleaned.As far as large boiler installations are concerned where the space to be cleaned has walls with a length of 10 to 15 m the pressure wave may be attenu- ated too much to reach effectively all nooks of the space and to provide an effective cleaning of portions of the space which are remote from the sound emitter. It is not possible to locate sound emitters in this space proper due to the fact that vital parts of the sound emitter cannot stand existing high temperature and also due to the fact that the flow pattern in the space can be disturbed by objects mounted therein such as a sound emitter mounted between the tubes of a nest of boiler tubes.The range can be extended by increasing the acoustic power generated by the sound emitter in order to increase the sound pressure level but in this respect there are technical limitations because the construction of the sound emitter will be e ry compli¬ cated and expensive if a substantial increase of the power is required. Moreover, the production of acoustic power generally is relatively expensive.A better alternative of increasing the acoustic range could be to concentrate the pressure wave emitted by the sound emitter to different portions of the space to be cleaned but no practicable method has been avail¬ able so far in order to achieve by simple means such a concentration of the sound from a sound transmitter of the type commonly used in sonic cleaning.The object of the invention is to provide by simple means a concentration of the pressure wave to different portions of the space to be cleaned also when these por¬ tions are located at a great distance from the. pressure wave generator, and more particularly by using conven¬ tional pressure wave generators operating in the frequency and power ranges now commonly applied in sonic cl eani ng .To achieve this object as well as additional objects and advantages of the invention, which in part will be set forth in the following description and in part will be obvious from the description, the invention provides a method in sonic cleaning of a space where¬ in there is a tendency of a coating being formed on the surfaces thereof, characterized in that pressure waves are emitted from at least two mutually spaced locations in the space, and in that an amplified pressure wave is produced by controlled phase shift of the pressure wave emitted from one location in relation to the pressure wave emitted from the other location, said amplified pressure wave scanning the space.By applying this method it is possible to control by rather uncomplicated means the main direction of the emitted pressure wave, the power or intensity thereof in said direction being substantially increased.The invention will be described in more detail below reference being made to the accompanying drawing in whichFIG. 1 diagrammatical ly illustrates how the 'wave from two synchronous sound emitters can be induced to change the direction thereof by a relative phase shift of the pressure waves emitted from the two sound emitters; andFIG. 2 discloses an arrangement of two pneumatically operated sound emitters for providing said phase shi ft.Referring to FIG. 1, there are shown therein two sound emitters A and B spaced a distance a^ from each other. The sound emitters in this case are parallel to each other but this is not necessary; the directions of the sound emitters also can converge or diverge. It is also possible to arrange the sound emitters opposite to each other. If it is assumed that the two sound emitters generate sound waves comprising a single frequency component only, having the wave length λ, and if it is also assumed that these frequency components are fully synchronized and without phase shift, the wave front will propagate in the direction A/B - Al/Bl. If a phase shift φ is introduced between the pressure wave from the sound emitter B in relation to the pressure wave from the sound emitter A the direction of the wave front will be changed and the wave front will have the direction A/B - A2/B2. If the angle between the directions A/B - Al/Bl and A/B - A2/B2 is designated θ (generally measured from the perpendicular of the line A/B connecting the sound emitters) there is obtained the relationshipa s i n 0 = — • λ = kλ s i n θ 2π where k is a constant which can be expressed ask = φ 2τr sin θ The angle Θ is obtained from the expressionsin Θ = Ψ2τr kBy cyclically changing the phase shift angle φ an instantaneous in-phase addition of the two pressure waves (at φ = 0) is obtained and also a continuous change of the angle of the direction of the combined wave at the maximum power or intensity. Thus, there is obtained a scanning pressure wave, i.e. a pressure wave moving forwards and backwards, which can be utilized in order to cover the several portions of a space of a furnace, heat exchanger or similar apparatus at maximum power or intensity also when the space hasf OMPI large dimensions and/or complicated form. The two sound emitters can be located in a wall of this space or in adjacent or opposite walls at a place where they can be mounted easily. At in-phase addition of the pressure waves the total sound pressure amplitude will be twice as large, which means that the power, or intensity of the pressure wave will be increased by about 6 db. It is assumed that the amplitudes of the two sound emitters are equal . In an addition other than the in-phase addition, e.g. of two frequencies which are not adjacent to each other, there is obtained an increase of the power or intensity of about 3 db only.FIG. 2 discloses a practical embodiment of an apparatus for working the method according to the invention for sonic cleaning of a space as described with reference to FIG. 1. In this case the two sound emitters are of the pneumatic type and comprise a membrane housing 1 OA and 10B, respectively, and an acoustic horn 11A and 11B, respectively. The emitters are mounted in a wall 12 of the space 13 to be cleaned, and pressurized air at the pressure Pα is supplied through a conduit 14. Synchronism of the two pneumati¬ cally operated sound transmitters A and B can be obtained by spacing these sound emitters such a distance <_ that they interact by so-called external coupling via the acoustic horns 11A and 11B. If the distance a_ is related to the wave length λ so that a = k • λ where k is the constant referred to above, it has been found convenient in practice to choose a value of k which is less than 1 e.g. 0.7 but the distance is not critical; k can range between e.g. 0.5 and 1. The oscillating air column of the horns and the membrane mechanism the oscillation of which is controlled by the resonance conditions of the horns thus can be influenced by the pressure oscillations externally of the horns. Though synchronism can be obtained in this manner the phase position is not determined thereby. The relative phase shift can be mastered only if the chambers behind the membranes in the membrane housings 10A and 1OB are interconnected by means of an acoustic wave guide, and in FIG. 2 this connection is provided by a conduit 15 so that a stable phase position will appear at a defi¬ nite length of this conduit. This method of combining an external acoustic coupling and a coupling which is bound to a conduit provides the possibility to control the phase shift from e.g. T. radianes (synchronization in opposition) to a value sliding cyclically from π to 0 (in-phase synchronization). Sliding of this type can take place if the length of the conduit 15 is somewhat shorter or longer than the optimum length for a stable phase position. The sliding can be controlled in a desired manner if there is maintained behind the membranes during operation of the sound emitters a pressure P. which is lower than the pressure P existing at the supply side of the membranes. For this purpose, pressurized air can be supplied to the conduit 15 and the pressure in this conduit and the chambers behind the membranes can be adjusted to a desired value Pb by means of a regulator 16.However, a desired pressure in the conduit 15 and the chambers behind the membranes in the membrane housings 10A and 10B can also be obtained by arranging a connection for pressurized air in one or both of the sound emitters between the supply side of the membrane< and the chamber at the rear side of the membrane, e.g. by providing an opening in the membrane, so that pressurized air is supplied from the supply side of the sound emitters, the pressure in the conduit I5 and the chambers behind the membranes being adjusted by con- trolled discharge of air through the pressure regulator 16.If a = λ i.e. k = 1, sine Θ = ■ - at the phase shift ■ϊ for the fundamental frequency (first harmonic) of a sound wave comprising several harmonics. In that case sine Θ for the fundamental frequency will be 0.25 corre¬ sponding to an angle Θ = 14.5°. For the second harmonic the phase shift would be π corresponding to sine 0 = 0.5 and an angle Θ = 30°. Thus, in dependence of the harmonics the pressure wave propagates as several separate lobes.Scanning comprising a continuously repeated move¬ ment from one side to the other of the amplified pressure wave can be obtained also in another manner, viz. if the frequencies of the sound emitters differ from each other to a minor extent, e.g. by 1 Hz, so that there is obtained a beat frequency of the pressure waves. Then, the phase shift will continuously vary between negative ' and positive values and the waves will be in-phase, i.e. there will be no phase shift, for a short moment only of each beat cycle. It should be noted that the significant increase of the power and intensity of the pressure wave by in-phase addition will have time to affect the dust coating in the space 13 also at these relatively short but repeated instances when the amplified scanning pressure wave passes a location in the space.The sound emitters can also consist of sound emitters of other types such as electric sound emitters. In that case the phase shift or phase change in order to obtain the periodical scanning of the amplified pressure wave can be obtained electronically by applying methods known in the art.In this connection it should be noted that as pressure wave generators it is possible to use sound emitters for audible sound in the approximate frequencyBUREAU OMPI f . -l range 20 - 20,000 Hz as well as devices e.g. pulsators for non-audible sound, infrasound, in the approximate frequency range 2 - 20 Hz. Excellent practical results have been obtained at frequencies in the range extend¬ ing from 60 to 800 Hz.In the embodiment disclosed herein, only two sound emitters are provided but the method according to the invention can be applied by using more than two sound emitters.In sonic cleaning by applying the method according to the invention the cleaning may be performed either while the gas with dust entrained therein passes through the space to be cleaned or during a period when the gas flow is interrupted. This latter procedure provides the advantage that the loosened dust cannot be withdrawn with the gas.The method of sonic cleaning according to the invention can be applied not only in furnaces, heat exchangers or similar apparatuses through which gas is flowing at least intermittently, but also in cold stores wherein ice deposits on cooling coils and cooling-coil batteries and also on the walls cause problems by reduc¬ ing the efficiency of the cooling installation.A further field wherein the method according to the invention can be applied is in spray dryers wherein the powder produced by condensing a liquid can have a tendency of adhering to the walls and the devices in the spray drying compartment.When the pressure wave generators are of the pneumatic type an antistate agent can be supplied to the space 13 together with the drive fluid (pressurized air) in order to prevent the loosened dust from being attracted to the cleaned surfaces again due to electro¬ static forces. | CLAIMS1. A method in sonic cleaning of a space (13) wherein there is a tendency of a coating being formed on the surfaces thereof, c h a r a c t e r i z e d in that pressure waves are emitted from at least two mutually spaced locations (A, B) in the space (13), and in that an amplified pressure wave is produced by controlled phase shift of the pressure wave emitted from one location (A) in relation to the pressure wave emitted from the other location (B), said amplified pressure wave scanning the space.2. A method according to claim 1 wherein pneumatic pressure wave generators (A, B) are used for generating pressure waves in dependence of the displacement of a movable valve member, c h a a c ¬ t e r i z e d in that a pressure acting on the valve member is controlled.3. A method according to claim 2 wherein pressure wave generators of the membrane type are used, c h a r a c t e i z e d in that a connection is maintained by an acoustic wave guide (15) between the pressure wave generators (A, B) at the rear side of the respective membranes.4. A method according to claim 3, c h a r a c - t e r i z e d in that an adjusted pressure is main¬ tained in the wave guide (15) and at the rear side of the membranes by the supply of pressurized fluid to the wave guide (15).5. A method according to claim 3, c h a r a c - t e r i z e d in that an adjusted pressure is main¬ tained in the wave guide (15) and at the rear side of the membranes by the supply of pressurized fluid from the supply side of the membranes through a passage between the two sides of the membranes and controlled discharge of pressurized fluid from the wave guide (15) 6. A method according to claim 1, c h a r a c ¬ t e i z e d in that the pressure wave generators are operated at different frequencies to provide a beat frequency.7. A method according to any of claims 1 to 6, c h a r a c t e z e d in that the frequency of the pressure waves is within the frequency range of audible sound.8. A method according to any of claims 1 to 6, c h a r a c t e r i z e d in that the frequency of the pressure waves is within the frequency range of infrasound.'BUREATJOVPI | HOLM B; KOCKUMS AUTOMATION; KOCKUMS AUTOMATION AB | HOLM B |
WO-1979001020-A1 | 1,979,001,020 | WO | A1 | EN | 19,791,129 | 1,979 | 20,090,507 | new | G03C1 | G03C3, G03C1 | G03C1, G03C8 | G03C 1/053, G03C 1/06, G03C 1/95, G03C 8/02, G03C 8/08 | PHOTOSENSITIVE ELEMENTS | Photosensitive elements particularly suitable for use in diffusion transfer photographic film units which include a plurality of essential layers including at least one photosensitive silver halide layer having associated therewith a dye image-forming material which is diffusible during processing as a function of the point-to-point degree of silver halide exposure to actinic radiation and a layer adapted to receive image-forming material diffusing thereto and means for applying an aqueous processing composition. The silver halide layer comprises gelatin and inert particles which are compatible with gelatin, non-swelling in alkali and substantially non-film forming, wherein said inert particles are equal to or less than the silver halide grains in average diameter and wherein the silver halide grains are 2.5 microns or less in average diameter. Preferably, the inert particles are derived from a polymeric latex. In a particularly preferred embodiment, the photosensitive silver halide layer comprises a first and second photosensitive silver halide layer in contiguous relationship. | PHOTOSENSITIVE ELEMENTS 'BACKGROUND OF THE INVENTIONDiffusion transfer photographic products and pro¬ cesses are known to the art and details relating thereto can be found in U. S. Patents Nos. 2,983,606; 3,415,644; 3,415,645; 3,415;646; 3,473,925; 3,482,972; 3,551,406; 3,573,042; 3,573,043; 3,573,044; 3,576,625; 3,576,626; 3,578,540; 3,569,333; 3,579,333; 3,594,164; 3,594,165; 3,597,200; 3,647,437; 3,672,486; 3,672,890; 3,705,1843,752,836; 3,857,865; all of which are incorporated here their entirety. Essentially, diffusion transfer photographic products and processes involve film units having a photo- sensitive system including at least one silver halide layer, usually integrated with an image-providing material. After photoexposure, the photosensitive system is developed to establish an imagewise distribution of a diffusible image- providing material, at least a portion of which is trans- ferred by diffusion to an image-receiving layer capable of mordanting or otherwise fixing the transferred image-pro¬ viding material. In some diffusion transfer products the transfer image is viewed by reflection after separation of the image-receiving element from the photosensitive system. In other products, however, such separation is not required and instead the transfer image-receiving layer is viewed against a reflecting background usually provided by a dispersion of a white reflecting pigment, such as, for example, titanium dioxide. The latter type of film unit is generally referred to in the art as integral negative-positive film units and are described, for example, in the above-mentioned U. S. Patents Nos. 3,415,644 and 3,594,165.It is known in the art to incorporate polymeric latices into gelatin silver halide emulsion layers to increase the flexibility of the silver halide layer, thus eliminating the occurrence of fog due to stresses set up in the film unit containing the aforementioned silver halide layer.U. S. Patent No. 2,772,166 discloses gelatin silver halide emulsions which also contain a hydrosol resulting from the emulsion polymerization of a mixture^ styrene, acrylonitrile or a vinylidene chloride with an alkyl acrylate or alkyl ethacrylate and acrylic acid. The described hydrosol is used in the range of 1 to 10% of the gelatin. U. S. Patent No. 2,835,582 is directed to mix¬ tures of gelatin and polymeric hydrosols in silver halide layers wherein the hydrosol is prepared by polymerizing at least .one monoethylenically unsaturated monomer in the presence of an ampholytic surface active agent. Among th suitable monomeric materials are mentioned methylmeth- acrylate and styrene. It is a requirement that the poly¬ meric materials be film formers and the essence of the invention resides in the presence of the ampholytic sur¬ face active material to provide its enhanced compatibilit with gelatin.U. S. Patent No. 3,157,510 is directed to gelat silver halide emulsions which also include a dispersion o minute particles of a water insoluble soft acrylate polym resin at a level of about 5 to 40% by weight of gelatin. U. S. Patent No. 3,325,286 is directed to gelat silver halide emulsions which include an aqueous dispersi of a polymeric vinyl compound and .at least one anionic dispersing agent specified in the patent. The emulsion layer also requires a polyoxyethylene' compound as defined in the patent. One of the polymeric materials recited is a homopolymer of an α-hydrocarbon substituted acrylic aci ester.U. S. Patent No. 3,547,650 is directed to gelat silver halide emulsions which include an aqueous dispersi of a polymeric vinyl compound dispersed with a mixture of specified organic phosphates. One of the polymerized vin compounds recited comprises a homopolymer of an α-hydrocarbon substituted acrylic acid ester.U. S. Patent No. 3,772,032 is directed to a gelatin silver halide emulsion which includes a polymeric latex prepared by emulsion polymerization in the presence of at least 5% by weight of an emulsifying agent to reduc the stress sensitivity of the emulsion. This patent stat Λ, that employing the specified emulsifying agent at a level of at least 5% by weight,, no fog is found in emulsions employing large amounts of methyl ethacrylate in the latex whereas normally the presence of even 50% of methylmethacrylate in the latex results in intolerable increases in fog. ϋ. S. Patent No. 3,773,517 is directed to gelatin- silver halide emulsion which include a polymer latex pre¬ pared by copolymerization of a monomer yielding a water insoluble homopolymer and a monomer yielding a water soluble polymer. The patent requires the polymerization to occur in the presence of a specified alkylaryl polyether phosphate surface active agent. One of the monomers which would produce a water insoluble homopolymer is an alk lmethacrylate.U. S. Patent No. 3,418,132 is directed to a photo¬ graphic film unit which, in one embodiment, is particularly suited for rapid access processing by virtue of the incorporation of inert particles into at least one layer of the photographic element. The inert particles include starch, barium sulfate, calcium carbonate, synthetic resins etc. The inert particles are in the range of 7 to 15 microns'.Film units containing contiguous silver halide emulsion layers sensitive to the same spectral region are known to the art as shown by the following representative patents.U. S. Patent No. 3,505,068 is directed to a photographic element which contains overlying silver halide emulsions wherein the first emulsion is a regular silver haloiodide emulsion and the second contains grains which have an iodide-free shell and a silver iodide core.U. S. Patent No. 3,663,228 is directed to a photographic film unit having a plurality of silver halide emulsion layers divided into sets with each set of a different speed while the layers in each set have the same speed but are responsive to different spectral regions. Color filters are disposed between the layers. U. S. Patent No. 3,695,882, is directed to a photosensitive element comprising a support carrying two emulsions, each containing a non-diffusing color coupler. Each emulsion lias a different speed and different silver halide-coupler molar ratio. U. S. Patent No. 3,846,135 is directed to a synergistic increase in the sensitivity of two superposed silver halide layers when the lower layer is less sensiti than the upper layer and has a maximum density of at lea 1.5 compared to .a maximum density of at least 0.9 for the upper layer. The lower layer is about 5 to 15U thick. U. S. Patents Nos. 3,960,558 and 4,003,744 dis¬ close diffusion transfer film units which employ split silver halide emulsions having dye image-forming material associated therewith and which, in fact, contain dye image-forming material in one of said contiguous layers. U. S. Patent No. 3,632,342 is directed to a photographic element comprising a support carrying at lea one layer containing a high contrast silver halide emulsi layer containing an acrylic latex material and an additio silver halide layer containing a hydrophilic colloid whic is free of latex micelles. It is stated that discrete micelles are preferred but that coalescing may occur. Copolymers of hydrophilic and hydrophobic monomers are disclosed.A, SUMMARY OF THE INVENTIONThe photographic film unit of the present inven¬ tion comprises at least a first photosensitive silver halide emulsion layer having associated therewith a dye image-forming material, preferably a dye developer which is soluble and diffusible in alkali as a function of the exposure and development of the silver halide emulsion layer, and a polymeric layer dyeable by said dye image- providing material wherein said dyeable polymeric layer is at least in superposed relationship with said photo¬ sensitive element after exposure of said element and during processing of the exposed photosensitive silver halide emulsion, that is, during contact of said emulsion with the aqueous alkaline processing composition; and wherein said photosensitive silver halide emulsion layer comprises photosensitive silver halide grains disposed in a mixture of gelatin and inert particles which are substantially non- swelling in alkali, compatible with gelatin, and substan¬ tially non-film forming or non-coalescing; which particles are equal to or less than the silver halide grains in average diameter and wherein the silver halide grains are 2.5 microns or less in diameter.Preferably the film units of the present inven¬ tion are integral negative-positive film units of the types described, for example, in U. S. Patents Nos.3,415,644 and 3,647,437, which patents are incorporated herein. Preferred inert particles are derived from polymeric latices which comprise homopolymers of methylmethacrylate or styrene. The term photosensitive silver halide emulsion layer as used herein, is intended to include a first and second photosensitive silver halide layer sensitive to the same portion of the spectrum and in contiguous relation¬ ship i.e., so-called split emulsions , which will be described below in greater detail.OMPI DETAILED DESCRIPTION OF THE INVENTIONThe present invention will be described with respect to dye developers as the dye image-forming materials although it will be understood that other dye image-forming materials may be employed in the present invention.Dye developers are well known in the art. A dy developer is a compound which contains a silver halide developing moiety and the chromophoric system of a dye. In multicolor processes, a dye developer providing an image dye of appropriate color is associated with each silver halide emulsion layer; for example, a cyan dye developer with a red sensitive silver halide layer; a magenta dye developer with a green sensitive silver halid emulsion layer; and a yellow dye developer with a blue sensitive silver halide emulsion layer. Unoxidized dye developer is insoluble in water but soluble and mobile in aqueous alkali. Oxidation of the dye developer as a result of development of exposed silver halide results in its immobilization, while unoxidized dye developer can diffuse to the dyeable image-receiving layer producing a positive image therein.To provide rapid transfer of the unoxidized dye developer and to avoid any unwanted interactions in the negative, it is preferred that the unoxidized dye develop pass through the associated silver halide emulsion layer as rapidly as possible consistent with development thereo Since gelatin swells to a considerable degree upon contac with the photographic processing composition and thus would be a factor in slowing dye developer transfer, it i desirable to form the silver halide emulsion layer with a minimum of gelatin. The minimum quantity of gelatin employed, however, is controlled to a great degree by the size of the silver halide grains. Thus, it is desirable to employ sufficient gelatin to retain the silver halide grains within the layer, that is, to prevent any projecti of the grains or portion of the grains through the gelati layer at the interface into contact with adjacent layers. Thus, it will be seen that larger size grains, as commonly employed for high speed emulsions, would require more gelatin than smaller grains at the same unit weight coverage to form a continuous layer without any projection of the grains into contact with adjacent layers.By means of the present invention it has now been found that the transfer of image-forming materials through gelatin-silver halide emulsion layers can be accelerated, while at the same time completely retaining the silver halide grains within the layer and without adversely affecting the photographic properties of the film unit. In fact, unexpected photographic advantages are achieved as evidenced by H & D curves showing a reduction in slope, increased toe extent and enhanced dynamic range.As stated above, these advantages are achieved by disposing in the gelatin-silver halide layer inert particles which are substantially non-swelling in aqueous alkali; which are compatible with gelatin to avoid coagula¬ tion within the layer; which possess a refractive index sufficiently close to that of gelatin to avoid undue light scattering; which are substantially non-film forming (film forming would further inhibit dye transfer) and which are sufficiently hard to retain their physical identity as individual particles in the presence of aqueous alkali and thus provide a non-swelling, sizeable mass to bulk the gelatin layer.Inert particles suitable for use in the present invention include starch, barium sulfate, calcium carbonate, cellulose esters such as cellulose acetate propionate, cellulose esters such as ethyl cellulose, gloss, synthetic resins such as polyvinyl acetate, polycarbonates, homo and copolymers of styrene, inorganic oxides such as zinc oxide, silica, titanium dioxide, magnesium oxide and aluminum oxide, as well as hardened gelatin grains, calcium sulfate, barium carbonate and the like.As stated above, the preferred inert particlesOMPP for use in the present invention are polymethylmeth- acrylate and polystyrene and are provided for the film unit by disposing polymethylmethacrylate latex or polystyrene latex in the emulsion. The film forming and hardness characteristics of polymers are properties associated with the glass tr sition temperature of the polymer. Thus, the Tg of the polymer should be above the temperature at which the polymer is dried. Preferably, the Tg is above 35 C, mo preferably, above 60 C. In a particularly preferred embodiment, the Tg is above 100°C.It should be understood that the polymer late may be a homopolymer or a copolymer provided that the comonomers do not modify the copolymer to the extent th the required properties are not retained.The inert particles should be no larger than silver halide grains with which they are associated. I the present invention the maximum average diameter of t silver halide grains is 2.5 microns or less and prefera less than 2.0 microns. Thus, the maximum average diamet of the inert particles is 2.5 microns. The lower limit the particles is determined by the fact that one should avoid packing of the particles such as would impede dye transfer. Preferably, inert particles not less than 0.0 microns in diameter would be employed.In a particularly preferred embodiment the ine particles leave an average diameter which is 10-15% of t average diameter of the silver halide grains associated therewith. The quantity of polymer latex to be employed be readily determined for any given silver halide emulsi For a given silver halide grain size, as the quantity of gelatin decreases, the polymer gelatin ratio goes up to keep the layer dimensions the same. Sufficient gelatin must be present to keep the layer intact and prevent dus of the polymer particles. Preferably, a ratio (weight basis) of 0.5 to 1 to 10 to 1 polymer latex (solids) to gelatin is employed. Particularly preferred is a 1 to 1 ratio for fine grains (less than about ± 4 ) and 6 to 1 for coars grains (greater than about 1.3^ ) . Thus, in a preferred embodiment, the average mean diameter of the fine grains is less than about 1 and the large grains, greater than 1.3^ .. As stated above, the novel photosensitive silver halide layer of the present invention may comprise a first and second photosensitive silver halide layer in contiguous relationship and which are responsive to substantially the same spectral range. Thus, in an alternative embodiment, the diffusion transfer photographic film unit of the present invention comprises a plurality of layers which include a first photosensitive silver halide emulsion layer comprising silver halide grains of a first mean particle size and a second photosensitive silver halide emulsion layer compris- ing silver halide grains of a second mean particle size; said first and second silver halide emulsion layers being in contiguous relationship with the first silver halide layer being distal to the exposure surface of the film unit with respect to the second silver halide layer; said first and second silver halide layers being free of dye image- forming material but. having associated therewith a dye image-forming material which is diffusible as function of the point-to-point degree of silver halide exposure to actinic radiation, and a layer adapted to receive image- forming material diffusing thereto and means for applying an aqueous processing composition therebetween; wherein at least one of said silver halide layers comprise gelatin and inert particles as defined above. If inert particles are employed in only one layer it is in the layer containing the larger silver halide grains. The intrinsic speed of the second silver halide emulsion layer is greater than that of the first silver halide emulsion layer.However, when the thickness of the gelatin associated with the layers falls to about 50% or less of the mean volume diameter of the grains, the coated layers do not retain their integrity but rather combine, inter¬ mixing the grain sizes, so that the resulting combinedOMPI WIPO silver halide layer functions as if a single layer of blended grain sizes were coated, thus losing all the benefits achieved in a layered structure and introducing the drawbacks of the single layered, low gelatin system. it is believed that the advantages of this inv tion result, at least in part, by maintaining better sep tion of the development process of the individual grains well as separation of the by-products of development by virtue of incorporating the above-described inert partic By employing such inert particles in the layers, the lay retain their integrity with the differently sized silver halide particles retained in their own separate and dis¬ tinct layer.As stated above, the intrinsic speed of the second silver halide layer, i.e., the layer closest to t exposure surface, possesses a higher intrinsic speed tha the first silver halide layer. Preferably, the speed di ference is at least about 2 stops and may range up to ab 8 stops. In a particularly preferred embodiment, the difference is about 5 stops.The polymeric latices preferred for employment the present invention may be prepared by known technique The following non-limiting example illustrates the prepa tion of a latex preferred for use in the present inventiExample AWater 118 1.Methyl methacrylate 51 ]<_q _Potassium persulfate 0.15 kg.Ascorbic acid 0.01 kg.Dowfax 2Al 20% solution 1.275 k(dodecyldiphenyl oxide disulfonate sodium salt, sold by Dow Chemical Co., Midland, Michigan)A reactor was charged with 102 1. of demineral ized water and the Dowfax 2A1 and heated under nitrogen to 83 C whereupon 7.65 kg. of methyl methacrylate was ad gJ and mixed until the temperature returned to 83°C. After 5 min. at 83°C, 4.93 kg. of initiator solution (0.15 kg. of potassium persulfate and 14.79 kg. water) was added. After the exother , the temperature was reduced to 85 C and the remaining methyl methacrylate was added at a rate of about 361 g/min. and the remaining initiator solution at a rate of about 111 g/min. At the end of the monomer and initiator addition, the temperature was maintained at 85°C for 10 min. and then the ascorbic acid was added. The resulting latex had a 30% solids and the latex parti¬ cles had an average diameter of about a 0.12^.The following non-limiting examples illustrate the present invention:EXAMPLE 1 (Control)A photosensitive element was prepared by coating, in succession, on a gelatin subbed, opaque polyethylene terephthalate film base, the following layers.1. a layer comprising the cyan dye developerdispersed in gelatin and coated at a coverage of about2 2747 mgs/ of dye, about 1554 mgs/m of gelatin, about2270 mgs/m of 4 '-methylphenylhydroquinone, and about REX^ 270 mgs/m of 2-phenyl benzimidazole;2. a red-sensitive gelatino silver iodobromid emulsion layer comprising a 50/50 blend of 1.05/^and2 1.5Λ.grains coated at a coverage of about 1280 mgs/m of silver and about 768 mgs/m 2 of gelatin;3. an interlayer coated at a coverage of abou 22500 mgs/m of a 60-30-4-6 tetrapolymer of butylacrylate, diacetone acrylamide, styrene and methacrylic acid, and about 77 mgs/m 2 of polyacrylamide;4. a layer comprising the magenta dye develop dispersed in gelatin and coated at a coverage of about646 mgs/m 2 of dye and about 426 mgs/m2 of gelatin and abo2 229 mgs/m of 2-phenylbenzimidazole;5. a green-sensitive gelatino silver iodobrom2 emulsion layer coated at a coverage of about 753 mgs/m o2 silver' and about 347 mgs/m of gelatin;6. an interlayer containing the tetrapolymer referred to above in layer 3 at a coverage of about 1369 mgs/m 2, about 24 mgs/m2 of polyacrylamide, and about275 mgs/m succindialdehyde;7. a layer comprising the yellow dye developer dispersed in gelatin and coated at a coveraσe of about2 n 968 mgs/m of dye and about 450 mgs/m of elatin and about2208 mgs/m of 2-phenyl benzimidazole;8. a blue-sensitive gelatino silver iodobromide2 emulsion layer coated at a coverage of about 1280 mgs/m of silver, about 743 mgs/m 2 of gelatin, and about 204 mgs/m2 of 4'-methylphenylhydroquinone;9. an overcoat layer coated at a coverage of about 484 mgs/m 2 gelatin and 43 mgs/m2 of carbon black.An image-receiving element was prepared by coat¬ ing the following layers in succession on a 4 mil polyethy¬ lene terephthalate film base, said layers respectively comprising:1. as a polymeric acid layer, the partial butyl ester of polyethylene/maleic anhydride copolymer at a 2 coverage of about 28,000 mgs/m ;2. a timing layer containing about a 75:1 ratio of a 60-30-4-6 copolymer of butylacrylate, diacetone acrylamide, styrene and methacrylic acid and polyvinyl^^— WeightPotassium hydroxide 5.25N-phenethyl-α-picolinium 1.27 bromide (50% solution in water)Sodivim carboxymethyl hydroxethyl cellulose 2.0 (Hercules Type 420H)Titanium dioxide 37.46-methyl uracil 0.7 bis-(β-aminoethyl) -sulfide 0.022Benzotriazole 5.48Colloidal silica aqueous 0.55 dispersion (30% Si02)N-2-hydroxyethyl-N,N',N'-tris- 0.75 carboxymethyl-ethylene diamine4-aminopyrazolo (3, 4d) pyrimidine 0.256-benzylamino-purine 0.41Polyethylene glycol 0.45 (molecular weight 4,000)Water 44.26EXAMPLE 2A second film unit was prepared as described above except that layer 2, the green-sensitive silver halide2 emulsion layer additionally contained 120 mgs/ft2 (1292 mgs/m •) (solids) of a polymethylmethacrylate latex having an average particle size of about 0.125 and layer 6 was reduced in coverage by 40%.The film units were processed in the following manner:The film unit was exposed with white light to a multicolor target and the processing composition was spread between the two elements in a layer approximately 0.0028 thick in the dark.The following sensitometer data (green light reflection data in neutral column) was obtained in the resulting multicolor reflection prints: ' f0 EAOMPI * TABLE 1Control ExampleSlope 1.61 1.31Toe Extent 34 48Dynamic Range 17 231.5 Speed 2.11 2.160«45 Speed • 1.46 1.34From the foregoing it can be seen that a 30 un reduction in slope is achieved; an increase in toe exten of about 14 units as well as an increase in dynamic rang of more than 5 units. The loss indicated in the other properties is not considered significant; i.e., the advantages far outweigh the slight decrease recorded in D and speed which, in fact, may be within experimenta error. It should be understood that these enhanced phot graphic results are obtained at the same time the magent dye transfer is accelerated. .EXAMPLE 3 To illustrate the rapid dye transfer achieved the novel invention the following structures were prepar2A. On a polyester base was coated 25 mgs/ft(269 mgs/m 2) of the cyan dye of Example 1; 50 mgs/ft2(538 mgs/m 2) of gelatin and 2 mgs/ft2 (21.5 mgs/m2) of succinaldehyde.B. Structure A was overcoated with 180 mgs/f(1938 mgs/m 2) of derivatized gelatin. C. Structure A was overcoated with 180 mgs/f2 (1938 mgs/m ) of inert gelatin.D. Structure A was overcoated with a mixture gelatin (40 mgs/ft 2) (431 mgs/m2) and polymethylmethacryl2 _> latex (160 mgs/ft ) (1722mgs/m ) (0.125^average diameteThe processing composition described above was spread between the above structures and the superposed dye- image-receiving sheet described in Example.1 in a thickness of 28 mils. The density of dye deposited in the receiving sheet was measured as a function of time. The resulting data are set forth below: TABLE 2DensityOvercoat Coverage mgs/ft 2 mgs/m2 3 300 sseecc.. 1 min . 1.5 min. 3 min. 5 rain.A None 0 0.88 1. 16 1.26 1.82 1.94 B Derivatized gelatin 180 0.29 0. 65 0.84 1.06 1.27 C Inert gelatin 180 0.68 0.87 1.00 1.24 • 1.37D Gelatin 40 Polymethylmethacrylate 160 .81 1. 10 1. 25 1.46 1.55 The above table illustrates the adverse effect gelatin has on dye transfer. The table also shows that a layer with a greater coverage than the gelatin layer but composed of gelatin and latex particles provides transfer rates approaching that obtained with no overcoat at all, especially in the initial time period.The following non-limiting example illustrates a particularly preferred film unit of the present invention:EXAMPLE 4 (Control)A photosensitive element was prepared by coating, in succession, on a gelatin subbed, opaque polyethylene terephthalate film base, the following layers:1. a layer comprising the cyan dye developer' dispersed in gelatin and coated at a coverage of about2 2747 mgs/m ' of dye, about 1554 mgs/m of gelatin, about2270 mgs/m of 4'-methylphenylhydroquinone, and about2 270 mgs/m of 2-phenyl benzimidazole;2. a red-sensitive gelatino silver iodobromide2 emulsion layer coated at a coverage of about 1280 mgs/m2 of silver and about 768 mgs/m of gelatin;2500 mgs/m diacetone acrylamide, styrene and methacrylic acid, and2 about 77 mgs/m of polyacrylamide;4. a layer comprising the magenta dye devel dispersed in gelatin and coated at a coverage of about646 rags/m 2 of dye and about 426 mgs/m2 of2 gelatin and about 229 mgs/m of 2-phenylbenzimidazole;5. a green-sensitive silver halide emulsion unit consisting of a first layer of 0.6Z(.average mean diameter grains coated at a level of about 366 mgs/m 2 o2 silver and about 161 mgs/m of gelatin and a second lay of 1.4- β average mean diameter grains coated at a level about 387 mgs/m 2 silver and about 186 mgs/m2 of gelatin with a speed difference between said first and second layer of about 5 stops;6. an interlayer layer containing the tetrapolymer referred to above in layer 3 at a coverage of about 1369 mgs/m 2, about 24 mgs/m2 of polyacrylamide2 and about 75 mgs/m succindialdehyde;7. a layer comprising the yellow dye develo dispersed in gelatin and coated at a coverage of about9G8 mgs/m 2 of dye and about 450 mgs/m2 of gelatin and about2 208 mgs/m of 2-phenyl benzimidazole; 8. a blue-sensitive gelatino silver iodobromide emulsion layer coated at a coverage of about 1280 mgs/m2 of silver, about 743 mgs/m of gelatin, and about 2042 mgs/m of 4'-methylphenylhydroquinone;9. an overcoat layer coated at a coverage of about 484 mgs/m 2 of gelatin and 43 mgs/m2 of carbon black.EXAMPLE 5 A second film unit was prepared as described except that in layer 5 each green-sensitive silver halide emulsion layer additionally contained 4 times the coverage of gelatin of a polymethylmethacrylate latex having an average particle size of about 0.125 _and layer 6 was reduced in coverage by 40%.The film units of Examples 4 and 5 were pro¬ cessed in the following manner, using the image-receiving element and processing composition described in Example 1. The film unit was exposed to white light and the processing composition was spread between the two elements in a layer approximately 0.0028 thick in the dark.The following sensitometer data (green light reflection data in neutral column) was obtained in the resulting multicolor reflection prints: TABLE 1Example 3 ExamplControlSlope 1. . 71 1.Toe Extent 37 51 Dynamic Range 17. , 150 28. 1.5 Speed 2 . , 21 2. 0.45 Speed 1. 55 1.From the foregoing it can be seen that a sligh increase in Dmax, a 51 unit reduction in slope, an incre in toe extent of about 14 units as well as an increase i dynamic range of almost 12 units are achieved. The loss indicated in the other properties is not considered sign cant; i.e., the advantages far outweigh the slight decreases recorded in speed. It should be understood th these enhanced photographic results are obtained at the same time the dye transfer is accelerated and silver hal layer integrity maintained.It should be noted that the interlayer (layer adjacent the silver halide emulsion layer containing the inert particles was reduced in coverage by 40%. This is an additional and unexpected advantage of the present invention which further enhances dye transfer.A film unit similar to Example 5 was prepared except th?t the polymer latex employed was a 90/10 methylmethacrylate/hydroxypropyl acrylate copolymer. Up exposure and processing similar advantageous results wer obtained. 0 | 1. A photosensitive element for use in a diffusion transfer film unit which comprises a support carrying at least one photosensitive silver halide layer having a dye image-forming material associated therewith, wherein said silver halide layer comprises gelatin and inert, particles which are substantially non-swelling in aqueous alkali, compatible with gelatin and substantially non-film forming; said inert particles being less than or equal to the silver halide grains in average diameter; said silver halide grains being 2.5 microns or less in average diameter.2. The element of claim 1 wherein said photo¬ sensitive silver halide layer comprises, a) a first photosensitive silver halide layer distal to the exposure surface of said element and com¬ prising silver halide grains possessing a first mean particle size; b) a second photosensitive silver halide layer having a second mean particle size; said second photosen- sitive layer having a higher intrinsic speed than said first photosensitive silver halide layer; said first and second photosensitive silver halide layers being in contiguous relationship; said inert particles being dis¬ posed in at least said second silver halide layer; _ 3. The element of claims 1 or 2 wherein the inert particles .are derived from a polymeric latex.4. The element of claim' 3 wherein said polymer is polymethylmethacrylate.5. The element of claim 3 wherein said polymer is polystyrene.6. The element of claims 1 and 2 wherein the inert particle to gelatin ratio (by weight) is about 0.5 to- 1 to 10 to 1.7. The element of claim 6 wherein said inert particle to gelatin ratio is about 1 to 1.8. The element of claim 6 wherein said inert particle to gelatin ratio is about 6 to 1. 9. The element of claims 1 and 2 wherein sai dye image-forming material is a dye developer.10. The element of claim 2 wherein the averag mean diameter of said silver halide grains is said first photosensitive silver halide layer is less than about 1 micron and wherein the average mean diameter of said gra in said second photosensitive layer is greater than abou 1.3 microns.11. The element of claim 2 wherein the speed difference between said first and second photosensitive silver halide layers ranges from about 2 to about 8 stop12. The element of claim 11 wherein said spee difference is about 5 stops.13. A diffusion transfer film unit comprising support carrying at least one silver halide emulsion lay having a dye image-forming 'material associated therewith and a dyeable receiving layer adapted to receive a dye image diffusing thereto after photoexposure and processi of said silver halide emulsion layer; wherein said silve halide emulsion comprises gelatin and inert particles wh are substantially non-swelling in aqueous alkali, compat with gelatin and substantially non-film forming; said in particles being less than or equal to the siiver halide grains in average diameter; said silver halide grains be 2.5 microns or less in average diameter.14. The film unit of claim 13 which includes first and second photosensitive silver halide layer, sai first photosensitive silver halide layer being distal to the exposure surface of said element and comprising silv halide grains possessing a first mean particle size; sai second photosensitive silver halide layer having a secon mean particle size; said second photosensitive layer hav a higher intrinsic speed than said first photosensitive silver halide layer; said first and second photosensitiv silver halide layers being in contiguous relationship; s inert particles being disposed in at least said second silver halide layer.15. The film unit of claims 13 or 14 wherein said inert particles are derived from a polymer latex.16. The film unit of claim 15 wherein said polymer is polymethylmethacrylate.17. The film unit of claim 16 wherein said polymer is a methylmethacrylate/hydroxypropylmethacrylate copolymer.18. The film unit of claim 15 wherein said polymer is polystyrene.19. The film unit of claim 15 wherein said polymer to gelatin ratio is about 0.5 to 1 to 10 to 1.20. The film unit of claim 19 wherein said polymer to gelatin ratio is about 1 to 1.21. The film unit of claim 19 wherein said polymer to gelatin ratio is about 6 to 1. 22. The film unit of claim 13 wherein said dye image-forming material is a dye developer.23. The film unit of claim 13 which includes a rupturable container of processing composition adapted to discharge its contents between a predetermined pair of layers.24. The film unit of claim 23 wherein said dye¬ able receiving layer is adapted to be superposed over the silver halide emulsion layer subsequent to photoexposure and adapted to be separated therefrom after processing. 25. The film unit of claim 18 which is a perman¬ ent laminate and wherein the image is viewable in said receiving layer without separation of said receiving layer from said film unit.26. The film unit of claim 14 wherein the mean particle size of said grains in said first photosensitive silver halide layer is less than about 1.0/{and the mean particle size of said grains in said second photosensitive silver halide layer is at least 1.3/»_,27. The film unit of claim 14 wherein the speed difference between said first and second photosensitive silver halide layers is about 2 to 8 stops.28. The film unit of claim 27 wherein said speed difference is about 5 stops.JJ EOMPIΛ. WIPO -*• 29. A photographic film unit which comprises, in combination: a photosensitive element having a diffusion transfer image-receiving element affixed at least one edg thereof, said photosensitive element comprising a support carrying: a) a red-sensitive silver halide unit having associated therewith a cyan dye developer; b) a green-sensitive silver halide unit havin associated therewith a magenta dye developer; c) a blue-sensitive silver halide unit having associated therewith a yellow dye developer; wherein at least one of said silver halide units comprises gelatin a inert particles which are substantially .non-swelling in aqueous alkali; compatible with gelatin and substantially non-film forming; wherein said photosensitive and said image-receiving elements are adapted to be superposed wit the support layers outermost; said inert particles being less than or equal to the silver halide grains in average diameter; said silver halide grains being 2.5 microns or less average diameter.30. The film unit of claim 28 wherein at least one of said silver halide units comprises,1. a first photosensitive silver halide layer distal to the exposure surface of said film unit and com¬ prising silver halide grains possessing a first mean particle size;2. a second photosensitive silver halide laye having a second mean particle size; said second photosen- sitive layer having a higher intrinsic speed than said fi photosensitive silver halide layer; said first and second photosensitive silver layers being in contiguous relation ship; said inert particles being disposed in at least sai second silver halide layer. 31. The film unit of claims 28 and 29 wherein said inert particles are derived from a polymer latex.32. The film unit of claim 30 including a rup- turable container retaining an aqueous alkaline processin- QO composition and adapted to discharge its contents inter¬ mediate said superposed photosensitive and image-receiving elements.33. The film unit of claims 28 and 29 wherein the support layer of said image-receiving element is trans¬ parent.34. The film unit of claim 33 in which said unit is a composite structure comprising said photosensitive element and said image-receiving element permanently affixed to the other in superposed relationship, the support layers of each of said elements being outermost.35. The film unit of claim 28 wherein said poly¬ mer latex is disposed in said green-sensitive silver halide unit. 36. The film unit of claim 30 wherein said poly¬ mer is polymethylmethacrylate.37. The film unit of claim 30 wherein said poly¬ mer is polystyrene.38. The film unit of claim 28 wherein said poly- mer to gelatin ratio (by weight) is about 0.5 to 1 to 10 to 1.39. The film unit of claim 38 wherein said polymer to gelatin ratio is about 1 to 1.40. The film unit of claim 38 wherein said poly- mer to gelatin ratio is about 6 to 1.41. The film unit of claim 29 wherein the mean particle size of said grains in said first photosensitive silver halide layer is less than about l.O ^and the mean particle size of said grains in said second photosensitive silver halide layer is at least 1.342. The film unit of claim 40 wherein the speed difference between said first and second photosensitive silver halide layers is about 2 to 8 stops.43. The film unit of claim 41 wherein said speed difference is about 5 stops.44. A photosensitive element for use in a diffusion transfer film unit which comprises a support carrying:- E ^-OMPI a) a first photosensitive silver halide layer distal to the exposure surface of said element and com¬ prising silver halide grains possessing a first mean particle size; b) a second photosensitive silver halide laye having a second mean particle size; said second photosen¬ sitive layer having a higher intrinsic speed than said fi photosensitive silver halide layer; said first and second photosensitive silver halide layers being in contiguous relationship and having associated therewith a dye image forming material which is diffusible during processing as a function of the point-to-point degree of silver halide exposure to actinic radiation; said first and second phot sensitive silver halide layers comprising gelatin and ine particles' which are substantially non-swelling in aqueous alkali, compatible with gelatin, and substantially non- film forming; said inert particles being equal to or less than the silver halide grain in average diameter; said silver halide grains being 2.5 microns or less in average diameter.45. A photographic diffusion transfer film uni comprising a support carrying at least one photosensitive element comprising a first and second photosensitive silv halide layer and a dyeable receiving layer adapted to receive a dye image diffusing thereto after photoexposure and processing of said photosensitive element, said first photosensitive silver halide layer being distal to the exposure surface of said element and comprising silver halide grains possessing a first mean particle size; said second photosensitive silver halide layer having a second mean particle size; said second photosensitive layer havi a higher intrinsic speed than said first photosensitive silver halide layer; said first and second photosensitive silver halide layers being in contiguous relationship and having associated therewith a dye image forming material which is diffusible during processing as a function of th point-to-point degree of silver halide exposure to actini radiation; said first and second photosensitive silver halide layers comprising gelatin and inert particles which are substantially non-swelling in alkali, compatible with gelatin, and substantially non-film forming; said inert particles being less than or equal to the silver halide grains in average diameter; said silver halide grains being 2.5 microns or less in average diameter.46. A photographic film unit which comprises, in combination: a photosensitive element having a diffusion trans- fer image-receiving element affixed at least one edge thereof, said photosensitive element comprising a support carrying: a) a red-sensitive silver halide unit having associated therewith a cyan dye developer; b) a green-sensitive silver halide unit having.associated therewith a cyan dye developer; c) a blue-sensitive silver halide unit having associated therewith a yellow dye developer; wherein at least one of said silver halide units comprises: 1) a first photosensitive silver halide layer distal to the exposure surface of said film unit and com¬ prising silver halide grains possessing a first mean particle size;2) a second photosensitive silver halide layer having a second mean particle size; said second photosen¬ sitive layer having a higher intrinsic speed than said first photosensitive silver halide layer; said first and second photosensitive silver hlaide layers being in contiguous relationship and having associated therewith a dye image forming material which is diffusible during processing as a function of the point-to-point degree of silver halide exposure to actinic radiation; said first and second photo¬ sensitive silver halide layers comprising gelatin and inert particles which are substantially non-swelling in alkali, compatible with gelatin, and substantially non-film forming; said inert particles being less than or equal to the silver halide grains in average diameter; said silver halide grains being 2.5 microns or less in average diameter wherein saidOMPI ° photosensitive and said image-receiving elements are adapted to be superposed with the support layers outer- most. sTξJ O J | POLAROID CORP | KLIEM P |
WO-1979001027-A1 | 1,979,001,027 | WO | A1 | XX | 19,791,129 | 1,979 | 20,090,507 | new | G02B27 | A61B3 | A61B3, G02B21 | A61B 3/14, G02B 21/00M4A5M, S02B 21/00M4A5M | SCANNING MICROSCOPIC APPARATUS | A scanning optical system for incrementally generating a composite image of a strip-scanned object. A light beam (12) is swept by a first rotating mirror (17) across the object (21) to scan-illuminate the same. Imaging light from the object is then projected to an intermediate image station across which it is swept by a second rotating mirror (23). A stationary aperture (S2) at the intermediate image station transmits or reflects, at any instant, only a desired incremental image of the scanned object. This desired incremental image is in turn relayed to a final image plane by reflection from a third rotating minor (28) so as to synchronously lay down on the image plane a composite of the instantaneous increments. | Scanning Microscopic Apparatus BACKGROUND OF THE INVENTION This invention relates generally to apparatus and method for microscopic examination of a predetermined object field or plane within biological tissue. In examining microscopic specimens of some thickness, the desired image is often obscured by light scattered from within the volume of the sample itself. This is particularly true of specimens examined by inci¬ dent or reflected light, that is, when the illumination and viewing are from the same side of the specimen.The light scattering within the volume of the speci¬ men above and below the plane of interest is reduced if only a small region is illuminated. The scattered light is further reduced if the illuminating light directed onto the object field follows a different path through the scattering medium than does the imaging light propa¬ gating from the object field.A specific problem is the examination of the endo- thelial cell layer on the inner surface of the cornea of the human eye. These cells are responsible for maintain¬ ing the proper water content of the cornea, to prevent swelling and opacification of the cornea. To examine these cells it has been found effective to illuminate a narrow strip of cells using half the aperture of a microscope objective and to use the other half of the aperture for viewing the cell layer.The problem addressed by the present invention is the relatively small area which can be viewed or photo¬ graphed by this method. The strip is typically only about 100 Um wide and perhaps 400 μ m long. Even within this narrow strip the image quality is not uniform, generally being partially obscured by scattered light on one side. If a larger area is to be studied, it must be photographed sequentially in strips, which are thenplaced together as a composite. Previous solutions to this problem have included a synchronized translation of the tissue and of the recording film. This solution is suitable for study of excised tissue but is not satisfactory for the living e Another solution suitable for in vitro studies employs two dimensional scanning of a microscope objective. A third suggested solution has employed a rotating Nipkow disc. While these dolutions have shown some success fo in vitro studies of excised tissue, they have not been successful in studies on living human eyes. The princi pal reason is the fact that the living human .eye is in nearly constant motion, with only short intervals of ti between small rotational movements, called saccades. Therefore, any scanning of such a subject must be done in an elapsed time which is short compared to the time between saccades. Further- solutions to the small field problem wer proposed by U.S. patent no. 3,547,512 to Baer. The Baer arrangement employs an assembly of two slits and a mirr which oscillate as a unit about a specific axis of rota tion. The motion of each slit must be equal to or grea thanthe width of the image which is produced. Uniform illumination must be provided over an area equal to the area of the image which is produced. Another solution employs one or more pairs of-.appropriately spaced slits located on a disc which rotates in its plane. This als requires a fairly large moving element and uniform illu mination over an area the size of the final image. SUMMARY OF THE INVENTION It is an object of this invention to provide appa ratus and methods for illuminating and viewing a strip within a specimen and scanning the strip in a direction transverse to its long dimension so that a two dimensio image is produced. The illuminating and imaging light beams pass through different portions of the aperture o the microscope objective or other imaging lens, so as t minimize the scattered light from out-of-focus portions of the specimen. The moving part is a mirror of one, two, or three plane faces, which may be of small dimension. Since the moving part is small, it can more readily be scanned rapidly, so that an image is produced in a time short compared to the time between eye saccades. For example, a mirror in the form of a 1 cm cube in one version of this instrument, is oscillated at 500 Hertz, so that a flash lamp of 1/1000 sec duration, properly synchronized, illuminates a full scan of the mirror in one direction. A further object is to permit an improved image by allowing the slit to be narrower than is presently used in so called specular or endothelial microscopes. In the invention the slit width can be selected for the best image quality, providing only that adequate light is avail- able to produce the image or photographic exposure.It is also an object to provide an instrument which can be used to view and photograph the endothelial cell layer either in vivo or in vitro.Finally, a general object is to provide an instru- ment which will permit examination of a predetermined plane, within a scattering or transparent medium, of an object which is illuminated and viewed from the same side.The present invention is effective to scan a strip of illumination across the desired object plane, to synchronously scan a slit-shaped viewing aperture across the same object plane, and finally to reconstruct an image thereof by scanning the image of the slit-shaped viewing aperture across a film plane or eyepiece image plane. The scanning is accomplished by three reflections from mirror surfaces which are rotating or oscillating in a rotary motion. To say it another way, the invention makes use of three reflections from a rotating mirror. The mirror may consist of one, two, or three plane faces. Alterna¬ tively, two or three synchronously rotating mirrors may be used. An illuminated stationary slit is imaged on the desired plane in the specimen. The slit image is scanned by the first reflection from the rotating mirror to illu¬ minate the specimen. Image light reflecting and returning from the specimen is reflected a second time by the rota- ting mirror and imaged on a second slit, which is also stationary. This second slit serves to select only that portion of the object or specimen plane which is illuminat by the first slit and to eliminate or mask out all extra¬ neous light, as from light scatteringcenters elsewhere in the specimen. Continuing, image light propagating from the second slit is reflected a third time from the rotatin mirror and.brought to a focus at the image plane. The effect of the third reflection is- to scan the slit image across the image plane in synchronism with the scan of the illuminated slit in the specimen.In the description which follows the word rotating is intended to mean either continuously rotating or rota¬ ting in as oscillatory manner. In addition, the eye is shown as the specimen to be examined by this system... This is only exemplary of an environment and use of this inven¬ tion. It should be kept in mind that the- system is equally useful in examining other biological specimens and sundry other objects in which the desired detail may be obscured by scattered light from within the volume of the specimen. BRIEF DESCRIPTION OF THE DRAWING FIGURES Figure 1 is a simplified plan diagram of the presen ly preferred exemplary embodiment of this invention, utilizing a three facet rotating mirror. Figs. IA, IB, 1C and ID are schematic of views take respectively in directions IA, IB, 1C and ID in Fig. 1. Fig. 2 is a schematic illustration of the illumina¬ ting and imaging light from a relatively large slit width. Fig. 3 is an illustration, similar to Fig. 2, of illuminating and imaging light from a relatively narrow slit. O Fig. 4 is a simplified plan view of a relay system which may be used in conjunction with the embodiment shown in Fig. 1.Fig. 5 is a simplified plan diagram of a second exem- plary embodiment of this invention, utilizing a single plane rotating mirror. Fig. 6 is an elevation diagram of a portion of the apparatus in Fig. 5.Fig. 7 is a simplified plan diagram of a third exem- plary embodiment of this invention, utilizing a rotating mirror with two reflecting facets.Fig. 8 is a plan diagram of an optional image re¬ construction system, which can be utilized in connection with a portion of the apparatus shown in Figs. 1, 5 or 7. Fig. 9 is a plan diagram of a fourth exemplary em¬ bodiment of the invention, in which three synchronously rotating mirrors are used.Fig. 10 illustrates an alternate method of image reconstruction which eliminates the need for a third reflection from the rotating mirror. An array of detectors is placed behind the second slit, and the output of the detectors is utilized to generate a television type display.Fig. 11 illustrates a fifth exemplary embodiment of the invention, in which a pinhole source and aperture are used. In addition, three wavelength dispersing prisms are used, first to spread the light from the pinhole source into a slit shaped spectrum, next to reco bine the wavelengths at the pinhole, and third, to spread the wave- lengths into a slit shaped spectrum which is then scanned across the image plane.Figs. 11A, 11B, 11C and 11D are schematic of views taken respectively in directions 11A, 11B, 11C and 11D in Fig. 11. DETAILED DESCRIPTION OF THE ILLUSTRATED EMBODIMENTReferring first to Fig 1, a light source S gene¬ rates an illumination light bundle 12 which is collected by a condenser lens LI and passes through a slit SI. Slit SI is preferably of variable width. A collimating lens L2 collimates the light from slit SI, and directs it through an aperture 16 to a reflecting facet 17 of a . rotatable mirror Ml. After reflection from facet 17 the light bundle 12 is incident on an objective lens 13, a microscope objective, which focusses the image of slit SI on a desired object plane 20 within the volume of a spe¬ cimen or object 21. It is to be noted that illumination light is directed at the object plane 20 through only about half of the aperture of lens L3. Light which is reflected or scattered at the desir object plane in the specimen is shown as an image light ray bundle 22, which is collimated by the objective lens L3 and directed to a reflecting facet 23 of mirror Ml. After reflection from facet 23, the image light bundle 22 is focussed by a relay lens L4 at a stationary slit S2. The imaging light bundle 22 which has been chosen for illustration is that which propagates from the illuminate portion of the desired object plane 20, within the speci¬ men 21, to the stationary slit S2 via the optics consist- ing of objective lens L3, reflector facet 23 and relay lens L4. Other light from the illuminated portion of plane 20 may be scattered in other directions, and will not be collected and imaged by the optics and will there¬ fore not contribute to the image. And light rays scatter from other portions of the specimen will not in general pass through slit S2. Slit S2 is preferably of variable width, so as to match the width of the image of slit SI.Since the object plane 20 is imaged onto the plane of slit S2 the two planes are said to be conjugate. Thus the slit S2 is conjugate to a slit shaped region of plane 20. The microscope is adjusted so that this slit shaped region is coincident with the image of slit Si at the desired object plane 20 in the specimen. Both slit images are scanned across the selected plane 20 in the specimen as the mirror Ml rotates.The function of slit S2 is to pass only image light from the narrow strip in the specimen illuminated by the image of slit SI. The jaws of the slit S2 are blackened so that light fnom other regions of the specimen which strikes the jaws and not the slit S2 will not be reflected back into the system. Mirror M2, adjacent to the station¬ ary slit S2, reflects the light which has passed through slit S2 back through the slit S2, through lenses L5 and L4 to the third reflector facet 28 of rotating mirror Ml. A projection lens L6 projects an image of slit S2 on the image plane F at which a recording film is preferably disposed. Because of the reflection from the rotating mirror this final image of the slit S2 is scanned across the film. . Lens- L5 is a field lens, the function of which is to image the aperture which precedes the lens onto the aperture which follows the lens1. In this case, the field lens L5 is effective to image facet 23 of rotating mirror Ml onto facet 28. This assures that light from the entire illuminated length of the slit S2 will be transmitted to the final image plane.It is understood that for visual observation an eye¬ piece may be used to view the image plane F, in addition to or instead of a recording film. Or, for electro-optic display, an image sensor could be substituted for the film. The term image sensor is used to signify any of the several types of television camera tubes or solid state detector arrays used for the purpose of converting an optical image to an electrical signal.OΛ.PI fa WIPO In this diagram it has been assumed that objective lens L3 is a microscope objective which is infinity cor¬ rected. That is, the optics have been designed so that aberrations are minimized when light from a point in the object plane emerges from the objective as a bundle of parallel rays. Such infinity corrected objectives are sold by several manufacturers. If a non-infinity correct objective is used, the system can easily be adapted by techniques known to those skilled in the art. For examp a negative lens of proper focal length can be inserted i the space between rotating mirror Ml and the objective lens L3. Or a system with fewer lenses can be construct by placing slits SI and S2 at the proper tube length fro objective lens L3, thus eliminating the need for lenses L2 and L4.While for illustrative purposes a filament has been shown as the light source in Fig. 1, it is necessary to use a flash lamp for photography of the living eye to eliminate any blurring due to motion of the eye during exposure. The flashlamp should be located at the positi of the source (filament) in Fig. 1. In many cases, it is convenient to utilize both a continuous source such as a filament and a flash source. One commonly used method is to image the continuous source onto the flashlamp in such a way that light from the source will pass through the transparent flashlamp and then into the rest of the optical system.Fig. 2 and 3 illustrate schematically how unwanted stray light can be generated by scattering within the volume of the specimen, such as a cornea, and how the use of a narrow slit minimizes the problem. In Fig. 2 a 100 micrometer slit image width is assumed, and an illu mination bundle of NA = 0.33. In the cornea, a ray with NA = 0.33 will be at an angle A with respect to the axis, where sin A = 0.33/n and n, the index of refraction of t cornea equals 1.37. 31 is the first surface of the corne 32, the second. 33 is the 100 micrometer wide image of slit SI on the second surface of the cornea 32. Slit image 33 is also the part of object plane 20 under obser¬ vation (being imaged) at any instant. For aid in under- standing 33 may also be thought of as object strip 33.Rays 34 and 35 represent the outer limits of the illumina¬ ting bundle, ray 34 being the NA 0.33 ray illuminating the left edge of the slit image, and ray 35 being the NA 0.0 ray illuminating the right edge of the slit image. The shaded area between rays 34 and 35 represents the volume of the cornea or specimen which is illuminated and which can scatter light back into the objective lens. Imaging ray 36 represents the principal image forming ray from the center of the slit image or object strip 33. For purposes of illustration ray 33 has been shown at an angle of 7° to the axis, which corresponds to a ray in the middle of the NA .33 bundle in the cornea, i.e., at NA 0.165. It is to be noted that this ray travels almost the entire thickness of the cornea in the illuminated volume. At any point along this ray in this illuminated volume, light scattered in the same general direction as the imaging ray 36 can contribute to stray light in the image. In other words, any point in the illuminated volume which also lies within the image light bundle can become a source of unwanted light scatter in the image bundle.For comparison, Fig. 3 shows at 43 a 20 micrometer wide image of slit Si. Rays 44 and 45 are the outer limits of the illuminating bundle in this case. Imaging ray 46 is the same as imaging ray 36 in Fig. 2. It is to be noted that the path-.of imaging ray 46 is through only a small portion of the illuminated volume. Therefore, the scattered light from the illuminated volume using a 20 micrometer slit width will be much reduced compared to that from the 100 micrometer wide slit. Fig. 2 also illustrates one reason for unequal image quality over the width of a 100 micrometer wide slit. Image forming light from the left part of image 33 must pass through an illuminated volume of the cornea which is relatively thick. Therefore the corresponding portion of the image will exhibit a large amount of veiling glare light. On the other hand, image forming light from the right portion of slit image 33 travels through a relatively thin illuminated volume. The corresponding portion of the image will be relatively free of stray light. Thus one side of the slit image will exhibit more veiling glare superimposed on the image detail than will the other side.Scanning provides two benefits. First, this non- uniformity of image quality is removed by the scanning. Second, scanning permits the use of a narrow slit, which gives an image with less scattered light than does the wide slit.In Fig. 4 a relay system is shown, the purpose of which is to accomplish the precise control over the illumination ray bundle as described in connection with Figs 2 and 3. If the rotating mirror Ml is located some distance from objective lens L3 as shown in Fig. 1, the rays will pass through different portions of objective lens L3 as the mirror rotates. In Fig. 4 lenses 51 and 52 act together as a unit power afocal telescope which images the apex of mirror Ml on the lens L3 as represented by the phantom lines. Then as mirror Ml rotates the reflected rays will always pass through the same portion of lens L3. TO'jbe precisely accurate the preceding state- ment must be modified in two respects. First, the mirror would have to rotate about its apex rather that its center. Second, if lens L3 is a thick lens, as will be the case for a microscope objective, the mirror apex should be imaged on the second principal plane of lens L3. The second condition can be accomplished by proper focussing of the mirror and lens L3 relative to the afocal telescope. The first condition may be accomplished by design of the mirror rotating mechanism. But in the case of a small mirror and small <angular rotation the mirror may rotate about the center of gravity for example with little deliterious effect.The fact that lenses 51 and 52 constitute an afocal telescope means that parallel rays 12 from mirror Ml are again parallel as they impinge on objective lens L3. Similarly parallel rays 22 emerging from lens L3 will again be parallel as they are incident on mirror Ml.Fig. 5 illustrates the use of a single rotating plane mirror Ml to perform the simultaneous illumination and image scanning. Light 61 from source S is collected by condenser lens Ll and passes through slit Si. Colli- mating lens L2 reimages source S on a portion of objective lens L3. Slit SI is imaged by the combined action of lenses L2 and L3 onto the desired plane, C. .Light 62 returning from this plane is collimated by the objective lens L3 andi. sthen incident on a portion of mirror Ml adjacent to the portion thereof reflecting the illuminating beam 61.After reflection from mirror Ml the light is inci¬ dent on mirror M2 at position 63. Relay lens L4 then brings the light to focus at stationary slit S2, which serves the same function as slit S2 in Fig. 1.After the^light passes through slit S2 it is reflected by mirror M3, again passes slit S2 and field lens L5. Field lens L5 serves the same function as field lens L5 in Fig. 1, except that in this case lenses L5 and L4 together image the left portion of objective lens L3 on mirror M4. Since mirror M4 is then conjugate to objective lens L3, it defines the portion of the lens L3 through which the image forming rays pass. Alternatively M4 may be a larger mirror with an adjacent aperture stop.OMPI P It is to be noted that in this arrangement the illumination and image forming rays are constrained to pass through different portions of lens L3; this functio is accomplished by imaging the source S and the mirror M4 on different portions of lens L3, at S1 and M4' res¬ pectively. It may be necessary in some instances to employ a relay system such as shown in Fig. 4 to keep the bundles passing through the same portion of the lens L3 for all positions of the mirror. Fig. 6 is an elevation diagram of a portion of Fig. 5, illustrating the path of the light from mirror Ml to mirrors 4 and M5, through lens L6 and to the film F. Thus rays 66 pass above mirror Ml. This is illustrated schematically in Fig. 5 by showing the rays as dashed lines.Alternatively, mirror M4 could reflect the light directly to ..a camera directed perpendicular to the plane of the paper or mirror M4 could reflect the light directly to a viewing system. Other arrangements are possible in which a single plane mirror can be used to accomplish the desired functions: namely scanning of an image of the illuminate slit, stabilization of the scanned slit image, isola¬ tion by means of a slit, and final scanning to reconstru the composite image. The common factor is to have three reflections from a rotating mirror. To minimize pro¬ blems with stray light it is preferable to use separate areas of the mirror for each reflection.Fig. 7 illustrates a scheme in which a mirror with two facets is utilized to accomplish the desired functio Again there are three reflections, two from the first facet and one from the second facet. Light 71 from the source S is collected by condenser lens LI, passes through slit Si. Colli ating lens L2 collimates light from the slit Si, directing it to a portion of rotating mirror Ml. After reflection the light is focused by objec¬ tive lens L3 to an image of slit SI in the specimen. The rotary motion of the mirror Ml causes the slit image to scan across the desired plane in the specimen. Light 72, reflected or scattered by detail in the specimen, is col- limated by lens L3 and directed to a portion of mirror Ml adjacent to the portion used for the incident light 71. After reflection from mirror Ml, the light is incident on mirrors M2 and M3 which direct the light to lens L4, located on the reverse side of mirror Ml. Lens L4 focuses the slit image onto slit S2, which serves the same func¬ tion as slit S2 in Fig. 1. Mirror M4 reflects the light back through slit S2 and thence to the lens L4 and to the second facet 73 of mirror Ml. Field lens L5 serves to image mirror M3 onto mirror Ml after reflection of the light at mirror M4.After reflection from the second facet 73 of mirror Ml the image forming bundle 74 is focused by lens L6 to the film plane F. Alternatively an eyepiece or TV camera tube could be substituted at the film plane.The light source in Figs. 1, 5 and 7 is shown in sim¬ plified form. In many cases it is desirable to add a con¬ denser and an aperture stop, to provide a better control¬ led light source. To those skilled in the art it will be apparent that the second and third reflections need not be from the same mirror as the first reflection, but may be from synchronously rotating mirror or mirrors. Fig. 8 illus¬ trates an alternative to a portion of Fig. 5. Consider Fig. 8 as positioned atop Fig. 5. Lens L5 and slit S2 are the same as in Fig. 5 but mirror M3 of Fig. 5 has been removed. In Fig. 8 after passing through the slit S2 the light passes to lens L6, reflects from the rotating mirror M3, and is focused by lens L7 on the film F. Mirror M3 must rotate synchronously with mirror Ml. This can be accomplished by a number of techniques. One method is to use essentially identical oscillating mirrors Ml and M3, and to drive them from the same source of AC power. Experience indicates that certain such mirrors are more easily synchronized if they are driven at a frequency which is substantially different from their resonant frequency. Care must be taken to assure that the sense of rotation of mirror M3 is correct, so that the image on the film is properly reconstructed. Fo example, if Fig. 8 is combined with Fig. 5, when mirror Ml is rotating clockwise mirror M3 must also be rotating clockwise.There are two distinct advantages to this system in¬ volving two rotating mirrors. First the crowding of optical elements and optical paths around mirror Ml is eased. Second, the slit S2 will be absolutely opaque to all light except that which passes between the jaws. In Fig. 5, the jaws of the slit must be blackened to prevent unwanted light from being reflected back toward lens L4. While blackening can be reaspnably effective, it is not possible to achieve total blackness or zero reflection. And methods which approach 100% efficiency are often more involved than a simple slit mechanism.The camera can be removed still farther from the rotating mirror, etc., by employing a fiber optics bundle. The bundle could consist of a single row of fibers, with the receiving end of the row placed immediately behind the slit S2 in Figs. 1, 5, 7 or 8. The other end (the emitting end) of the row of fibers is positioned at the first focal plane of lens L6 in Fig. 8, so that the image is reconstructed by the scanning of mirror M3.A preferred arrangement would be to employ a bundle of fibers consisting of several rows of fibers and a slit wide enough to expose several rows. The placement of the ends is exactly the same as for the single row discussed above. The advantages are that the image will have a more even illumination, and the resolution will be improved over that obtained with a single row of fibers, other conditions being equal.It will be apparent to those skilled in the art that other arrangements may be used to accomplish the same purpose as that illustrated in Fig. 8. For example, instead of using a rotating mirror to produce the scanning action, it is possible to focus the slit S2 directly on an image plane by means of an image relay system consis- ting of one or more lenses and to move this image relay system'άn synchronism with the illumination scan. The. The image plane referred to above may be the final image plane or an intermediate relay image plane. Second, the recording medium (e.g. film) can be located immediately behind the slit and can be moved synchronously with the illumination scan. A third arrangement is to utilize a flexible image transmitting bundle of optical fibers, the entrance end of the bundle located directly behind slit S2, and the exit end of the bundle arranged to scan across an image plane in synchronism with the illu¬ mination scan.In Fig. 9 three synchronized rotating mirrors are used. This permits the use of separate objective lenses L3 and L4 for the illumination and image formation res- pectively, which will further improve the separation between illumination and viewing rays within the specimen. It will also eliminate another source of stray light in systems which utilize a single microscope objective, such as L3 in Fig. 1, namely interreflections between lens elements, which can result in some illumination light being reflected.into the image forming path.As in previous examples, light from the source is collected by condenser lens Ll, passes through slit SI and is collimated by lens L2. The light is then reflected rotating mirror Ml, and is focused by objective lens L3 at the object plane P. As mirror Ml rotates clockwise the image of slit SI will scan across the plane P from right to left.As was discussed in connection with Fig. 1, there will be in plane P a slit shaped area which is conjugate to slit S2. The position of slit S2 is adjusted so that its conjugate image at plane P is coincident with the . image of slit SI. As mirror M2 rotates, the conjugates of slits SI and S2 remain coincident as they scan across plane P.Light passing through slit S2 is collimated by lens L6, reflected from rotating mirror M3 and brought to focus by lens L7 on image plane of film plane F. Mirror M3 rotates synchronously with, but in the opposite direction to mirrors Ml and M2. The dashed line connect¬ ing mirrors Ml, M2 and M3 illustrated how this synchro¬ nized rotation could be accomplished. Film F can be replaced by an eyepiece, for visual observation of the image. A precaution necessary in the system of Fig. 9 is to tilt lenses L3 and L4 in order to have the illumination and viewing scans coincide within the specimen. The amount of the tilt can be found by employing the Scheimpflug condition. According to this principle, to image a given object plane onto a given image plane, one extends these planes until they intersect. The inter¬ section will define a straight line. The plane of the objective lens must then be oriented so as to contain the same straight line. If the object is at optical infinity, as is the slit Si in Fig. 9, then the plane of the lens must be parallel to the image plane. Thus in Fig. 9, the plane of lens L3 and L4 is parallel to the specimen.In general the magnification of each lens L3 and L4 will vary across the selected plane in the specimen. Therefore the size of the field must be limited to that area in which the illumination slit image and the viewing slit image overlap.Fig. 10 illustrates another method for reconstruct- ing the final image, utilizing a television type scan instead of the scanning mirror. In Fig. 10A, S2 is the slit S2 of Figs. 1, 5, 7, or 9. Immediately behind the slit is a linear array of detectors, as shown at Dl, D2, etc., in Fig. 10. The signal from each detector is displayed as a line or narrow band on the final display, illustrated in Fig. 10B The display, C, could be a cathode ray tube.It should be noted that in all previously described configurations the resolution achieved is not determined by the width of the slit SI or S2. That is, in the plane of slit S2 there is an image of plane P, with two dimensional image detail. The slit S2 passes a rectangu¬ lar shaped portion of this image. The image detail per¬ pendicular to the- long dimension of the slit as well as that parallel to the long dimension are preserved in the final reconstructed image. By contrast, in the system illustrated in Fig. 10, no image detail within the width of the slit S2 is preserved. That is, detector Dl essentially integrates all light striking it, and produces a signal proportional to the total light it receives, regardless of any image detail within the breadth of the slit or the length of the detector element. Therefore, the system illustrated in Fig. 10 will have a resolution which is limited by the width of the slit in the horizontal direction, and by the center-to-center spacing between detectors in the vertical direction.In some applications, the signals from detectors Dl, D2, etc., may be fed directly to a computer for analysis. This could be useful in cases in which the image is to be modified by any one of several image enhancing techniques. or the image detail is to be automatically counted and size distribution determined.If the detectors Dl, D2, etc. are sufficiently narrow, it will not be necessary to place a slit adjacent to the detectors. In this case the optical system will be arranged to image slit Si directly onto the detector array.Figs. 2 and 3, as has been described, illustrate the advantage in using a narrow slit and in separating the illumination and viewing light rays within a volume of scattering medium. A further advantage is obtained if a pinhole is used instead of a slit. A Nipkow disc accomplishes this type of scanning, but it requires great precision in fabrication. A relatively simple modifica- tion of the systems of Figs. 1, 5, 7 or 9 can be used to accomplish this purpose. As shown in Fig. 11 a pinhole PI is used in place of the slit SI, also a pinhole P2 in place of slit S2. A wavelength dispersing prism Wl is placed between the source pinhole PI and the objective lens L3. It is oriented so that it produces a spectrum, R, fanning out in a direction perpendicular to the page. That is, the spectrum is in the form of a slit with the same position and orientation as the slit image in Fig. 1 extending lengthwise perpendicular to the page. This means that a given small area of the specimen 0 will be illuminated by a single wavelength, or more precisely a narrow band of wavelengths, say in the red portion of the spectrum. Another small area along the specimen will be illuminated by another narrow band of wavelengths, say in the green.The light which returns from the specimen 0 passes through lens L3, reflects from mirror Ml as before, and then passes through dispersing prism W2. If prism W2 is oriented parallel to prism Wl, light from the spectrum will be recombined to form a white light image of the pinhole PI at pinhole P2. After reflection from mirror M2 the light will pass through lens L4 and be dispersed by prism W3 and be reflected again from rotating mirror Ml. Thus a spectrum will be formed which will scan across the film plane F. The image will be reconstructed, in one dimension by the wavelength dispersion and in the other dimension by the scanning action.If the image is recorded on black and white film, the spectrum will of course not be apparent. However, if recording in color is desired, it can be accomplished as follows. The pinholes PI and P2 can be moved synchronous¬ ly and slowly along the direction of the slit in Figs. 1, 5, 7, 8 and 9. Then during one scan of the mirror a given point in the object 0 may be illuminated with > orange light, and then yellow, and so on through the spectrum. Therefore the final image will be built up of many scans, each containing different color information, so that when all scans are complete each image point will have received light from the entire spectrum. Fig. 11A illustrates the appearance of the pinhole aperture Pi in Fig. 11. Fig. 11B illustrates the appearance of the spectrum in the selected plane of the specimen, 0. Closely spaced lines indicate the blue end of the spectrum, widely spaced lines the red end of the spectrum. Fig. 11C illustrates the appearance of the pinhole aperture P2 in Fig. 11. The image of pinhole PI as reconstructed by prism W2 and lens L4 is super¬ imposed on this pinhole aperture P2. The dashed lines in Fig. 11D illustrate the instantaneous appearance of the spectrum which is formed in the film plane F of Fig. 11. The rectangle in Fig. llD represents the entire composite image, which is formed by the scanning of the spectrum in the horizontal direction.Fig. 11 represents only one embodiment of this principle of two dimensional image slicing. One simplification is to use a single dispersing prism instead of prisms Wl and W2. The single prism is placed between the rotating mirror and the objective lens L3. The relay system in Fig. 4 provides two possible positions, the first between mirror Ml and lens 51, the other between lenses 52 and L3.Examples of variations which would be possible unde this invention are:In fluorescence microscopy, the illumination light will generally be of a shorter wavelength thaώ the fluorescence which is emitted by the object. The invention, can be used for fluorescence microscopy by adding filters which are known to those skilled in the art; an excitation filter in the illumination beam and a barrier filter in the image forming beam.For dark field microscopy, the illumination light will be incident on the object at an angle of incidence such that light specularly reflected from the object will not be received by the image forming optical system. Thi can be accomplished in a number of ways. The simplest ca be described with reference to Fig. 4. The image of the mirror apex is moved from the center of lens L3 to one side of lens L3 so that the image forming rays occupy the central portion of lens L3 and the illumination rays pass through the extreme outer portion of lens L3. For differential interference microscopy, a polarizer and a Wollaston type of prism of appropriate design can be placed in the optical path between the mirror Ml and objective lens L3, in Figs. 1 and 4. For certain types of light sources it would not be necessary to use the first slit, e.g., SI in Fig 1. For example a ribbon filament tungsten lamp has the form of a slit and so the filament could be placed at the positio of slit SI and the system would perform as desired. Or a laser may have a sufficiently narrow beam that a slit is not needed to restrict the size of the beam. In this case it may be necessary to spread the laser beam in the direction perpendicular to the plane of the diagram by means of a lens or combination of lenses in order to have a slit shaped illumination beam at the object. Certain light emitting diodes provide a slit shaped source of light and could be used at the position of slit SI.In the several configurations given here by way of example, the common features and the essential points remain; a) the separation of incident and reflected, light within the volume of the specimen by using a narrow slit of light, and b) laying down a composite im§ge of incrementally illuminated and imaged, slit-shaped portions of the specimen, such incremental images being substantially freed of stray light by means of an image field aperture in the middle of the imaging system. The various geometries shown all include these features. They differ only in matters relating to practical considerations of space, accessibility and the like, considerations not essential to the inventive concepts. | (received by the International Bureau on 8 October 1979 (08.10.79))1. A scanning optical system for producing an image of an object including a light source, means for directing illumination light from said source to said object including a rotatable first mirror surface, a second mirror surface which is rotatable synchronousl with said first mirror surface and which is adapted to reflect light emanating from said, object, means to focus said light from said object at an aperture and means for directing the light from said aperture to a final image plane, said means including reflection from a third mirror surface rotatable synchronous¬ ly with said first mirror surface and including means for imaging said aperture on said final image plane.2. A scanning optical system as defined in claim 1 in which said aperture is defined by the facet of a re lector element.3. A scanning optical system as described in claim 1 in which said aperture is a slit-shaped aperture in close proximity to a mirror, said mirror serving to reflect light incident thereon back through said slit-shaped aperture.4. A scanning optical system as defined in claim 1 in which said illumination light includes wavelengths capable of exciting fluorescence in the object, and said light from the object includes wavelengths generated by fluorescence in the object.5. A scanning optical system as defined in claim 1 in which said first, second and third mirror surfaces are portions of the same plane mirror surface.6. A scanning optical system as defined in claim 1 in which said first and second mirror surfaces are portions of the same plane mirror surface and said third mirror surface is rigidly mounted relative to said plane mirror surface and rotatable synchronously therewith.7. A scanning optical system as defined in claim 1 in which said first, second and third mirror surfaces are mounted on the same support on the same support means and are rotatable synchronously as a unit.8. A scanning optical system as defined in claim 1 in which said first and second mirror surfaces are disposed at an angle of approximately 90° with respect to each other, and said third mirror surface is disposed parallel to but displaced from said first mirror surface.9. A scanning optical system as defined in claim 1 in which said first, second and third mirror surfaces are separately mounted and are driven synchronously one with the other.1G. A scanning optical system as defined in claim 1 in which said mirror surfaces rotate continuously about an axis essentially parallel to said mirror surfaces.11. A scanning optical system as defined in claim 1 in which said mirror surfaces rotate in an oscillatory manner about an axis essentially parallel to said mirror surfaces. 12. A scanning optical system as defined in claim 1 in which said illumination light is directed to said object through a lens means different from the lens means used to image said object on said aperture.13. A scanning optical system as defined in claim Ii which said means for directing illumination light and said means to image said light from said object are arranged so that the illumination light and the imaging light are separated except at the plane of the object which is imaged at said aperture.14. A scanning optical system as defined in claim 1 in which an optical relay system is included between said first mirror surface and said object.15. A scanning optical system as defined in claim 1 in which said light source is a light emitting diode.16. A scanning optical system as defined in claim 1 in which said light source is a tungsten filament lamp.17. A scanning optical system for producing an image of an object, said system including a light source, a first aperture through which passes a portion of the light from said light source, said portion being designated as illumination light, means for directing said illumination light to said object including a rotatable first mirror surface, a second mirror surface rotatable synchronously with said first mirror surface and reflecting light emanating from said object, means to focus said light from said object at a second aperture through which a transmitted portion of said light from said object will pass, and means for directing said transmitted portion to a final image plane, said means including reflection from a third mirror surface rotatable sunchronously with said first mirror surface and including means for imaging said second aperture on said final image plane.18. A scanning optical system as defined in claim 17 in which the means for directing said illumination light to said object includes lens means to image said first aperture onto said object.19. A scanning optical system as defined in claim 17 in which said first aperture is followed by first lensmeans which images said first aperture on a selected plane of said object, said object is followed by second lens means which images said selected plane onto said second aperture, and arranged so that the image of said first aperture on the selected plane is re-imaged on said second aperture. 20. A scanning optical system as defined in claim 17 in which said light source is a flash lamp.21. A scanning optical system as defined in claim 17 in which said means for directing said illumination light includes a first dispersing prism oriented so as to ■ > disperse the wavelengths of said illumination light into a spectrum which is oriented approximately perpendicular to the scan direction produced by said rotatable first mirror surface, said means to focus said light from the object at a second aperture includes a second dispersing prism oriented approximately parallel to said first dispersing prism, and said lens means for focusing said second aperture on said final image plane includes a third dispersing prism oriented so that the spectrum produced is approximately perpendicular to the scan direction produced by reflection from said third mirror surface.22. A scanning optical system as defined in claim 1 in which said first aperture and said second aperture ar slit-shaped apertures. 23. A scanning optical system as defined in claim 1 in which said second aperture is defined by the facet of a reflector element.24. A scanning optical system as defined in claim 1 in which said second aperture is a slit-shaped aperture in close proximity to a mirror, said mirror serving to reflect light incident thereon back through said slit- shaped aperture.25. A scanning optical system as defined in claim 1 in which said illumination light includes wavelengths capable of exciting fluorescence in the object, and said light from the object includes wavelengths generated by fluorescence in the object.26. A scanning optical system as defined in claim 1 in which said first, second and third mirror surfaces ar portions of the same plane mirror surface.27. A scanning optical system as defined in claim 1 in which said first and second mirror surfaces are portions of the same plane mirror surface and said third mirror surface is rigidly mounted relative to said plane mirror surface and is rotatable synchronously therewith. 28. A scanning optical system as defined in claim 17 in which said first, second and third mirror surfaces are mounted on the same support means and are rotatable synchronously as a unit. 29. A scanning optical system as defined in claim 17 in which said first and second mirror surfaces are disposed at an angle of approximately 90 with respect to each other, and said third mirror surface is disposed parallel to but displaced from said first mirror surface. 30. A scanning optical system as defined in claim 17 in which said first, second and third mirror surfaces are separately, mounted and are electrically or mechanically • driven synchronously one with the other.31. A scanning optical system as defined in claim 17 in which said mirror surfaces rotate continuously about an axis essentially parallel to said mirror surfaces.32. A scanning optical system as defined in claim 17 in which said mirror surfaces rotate in an oscillatory manner about an axis essentially parallel to said mirror surfaces.33'. A scanning optical system as defined in claim 17 in which said illumination light is directed to said object through a lens or lenses different from the lens or lenses used to image said object on said second aperture.34. A scanning optical system as defined in claim 17 in which said means for directing said illumination light and said means to image said light from said object are arranged so that said illumination light and said light from said object are separated except at the plane of the object which is imaged at said second aperture.35. A scanning optical system as defined in claim -17 in which an optical relay system is used between said first mirror surface and said object. 36. A scanning optical system for producing an image of an object including a light source, means for direct ing slit shaped illumination light from said source to said objec including a rotatable first mirror surface.:, ,s Secon mirror surface which is rotatable synchronously with said first mirror surface and which reflects light emanating from the object, means to image said light fr said object onto an array of detectors and eJectrical circuitry for processing the signals from said array of detectors. 37. A scanning optical system as defined in claim in which said electrical circuitry includes a computer.38. A scanning optical system as defined in claim in which said electrical circuitry includes a display device. 39. A scanning optical system for producing an im of an object including: means to generate a narrow strip of light, illumination means to sweep scan said light strip across an object to scan-illuminate said object, projection means to project an image of saidΛ object and to sweep scan the same across an image stati said illumination means and.said projection means scanning in synchronism, a stationary aperture at said image station t transmit at any instant the image of a strip-illuminate increment of said object to the exclusion of the image of the surrounding area of said object, and image receiving means operating in synchronis with said illumination means and said projection means receive from said stationary aperture a composite image successive increments of βaid object, said composite i thus corresponding to the scan-illuminated whole of sai object.40. A scanning optical system as defined in clai in which said image receiving means is a moving imagefcjAU ORIGINAL f O image receptor disposed adjacent to said aperture.41. A scanning optical system as set forth in claim 39 in which said image receiving means includes an image relay system to relay images from said aperture to an image plane, and to sweep scan said relayed images across said image plane to lay down thereon a composite of successive increments of said object.42. A scanning optical system as set forth in claim 39 in which said image receiving means is an array of photodetectors.43. A scanning optical system as set forth in claim 39 in which said image receiving means is an image sensor, said image sensor being adapted to convert a light image to an electrical signal. 44. A scanning optical system as set forth in claim 39 wherein said image receiving means includes an array of optical fibers disposed adjacent to said aperture to transmit images therefrom to form said composite image. 45. A scanning optical system as defined by claim 44 further comprising means for scanning said array of optical fibers across said image receiving means in synchronism with means for sweep scanning said light strip across said object.46. The scanning optical system as defined by claim 44 wherein the exit end of said optical bundle is adapted to scan across an image plane in synchronism with said illumination scan. 47. A scanning optical system as defined by claim 44 wherein said array of optical fibers is a linear array.48. A method for microscopically examining a predetermined object field or plane to produce an image of said object field or plane comprising the steps of: a) directing slit shaped illumination from a light source to said field or plane by means including a first rotatable mirror surface; b) reflecting light emanating from said field or plane by means of a second rotating mirror surface synchronized with the rotation of said first mirror surface; and c) imaging said light emanating from said object field or plane after the reflection of step b) onto an array of detectors to produce electrical signals.49. The method as defined by claim 48 further comprising transmitting said signals to means for processing said signals from said array of detectors. 50. The method as defined by claim 48 further comprising the step of transmitting said signals from said array of detectors to means for processing said signals.51. The method as defined by claim 50 wherein said means are electronic means. 52. The method as defined by claim 51 wherein said electronic means for processing said signals comprises a computer.53. The method as defined by claim 51 wherein said electronic means further comprises a display device connected to said array of detectors and said method comprises displaying said image corresponding to said field or plane on said display device.54. The method as defined by claim 53 wherein said array of detectors is arranged behind a slit and said method comprises passing said reflected light through said slit prior to reaching said photodetector array.5,5. The method as defined by claim 48 wherein said object field or plane comprises biological tissue.56. The method as defined by claim 55 wherein said biological tissue comprises the endothelial cell layer on the inner surface of the cornea of .the human eye. 57. A method for microscopically examining a predetermined object field or plane to produce an image of said object field or plane comprising the steps of: a) generating a narrow strip of light; b) sweep scanning said light strip across said field or plane to scan illuminate said field or plane; c) projecting and sweep scanning in synchronism with said sweep scanning of step ( ) an image of said field or plane across an image station; d) transmitting the image of a strip- illu inated increment of said field or plane to the exclusion of the image of the surrounding ' area of said object from said image station through a stationary aperture means; and e) receiving a composite image of successive increments of said object field or plane corresponding to the scan illuminated whole of said field or plane on an image receiving means.58. The method as defined by claim 57 comprising receiving said composite image by means of a moving image receptor disposed adjacent to said aperture.59. The method as defined by claim 57 comprising receiving said composite image by using an image relay system for relaying said image from said aperture to an image plane; sweep scanning said relayed image across said image plane; and depositing a composite of successive increments of said image of said object field or plane on said image plane.60. The method as defined by claim 57 comprising receiving said composite image on an array of photodetectors.61. The method as defined by claim 57 comprising receiving said composite image on an image sensor adapted to convert a light image to an electrical signal.62. The method as defined by claim 57 comprising receiving said strip- illuminated increment on receiving means comprising an array of optical fibers acting as said aperture means and transmitting said composite image through said fibers to a third rotating mirror to reform said composite image.63. The method as defined by claim 62 further comprising reforming said composite image by scanning the output of said optical fibers across an image plane in synchronism with said illumination scan of step b) .64. The method as defined by claim 57 wherein said object field or plane comprises biological tissue.65. The method as defined by claim 64 wherein said biological tissue comprises the endothelial cell layer on the inner surface of the cornea of the human eye. 66. A method for producing an optical image of an object with a scanning optical system comprising the steps of: a) directing illumination from a light source to said object by reflecting said illumination from a first rotating mirror surface; b> reflecting light emanating from said object with a second rotating mirror surface, said f irst and second mirror surfaces rotating synchronously; c) focusing said light reflected from said second mirror surface at an aperture; and d) directing said light from said aperture to a final image plane by reflecting said light from a third rotating mirror surface rotating synchronously with said first mirror surface to produce an optical image of said object on said final image plane.67. The method as defined by claim 66 comprising oscillating each of said first, second and third .mirror surfaces about an axis substantially parallel to said mirror surfaces.68. The method as defined by claim 66 which comprises directing said illumination light onto said object through a lens means different from the lens means used to image said object on said aperture.69. The method as defined by claim 66 further comprising separating said illumination from said light source directed onto said object and said light emanating from said object except at the plane of the object which is imaged at the aperture.70. The method as defined by claim 66 wherein said aperture is a second aperture and said method further comprises passing said illumination from said light source through a first aperture prior to reflecting said illumination from said first mirror surface.-BU hATT O PI vfa W1PO . >, ? i > 71. The method as defined by claim 66 which comprises dispersing said illumination by passing said illumination through a first prism oriented so as to disperse the wavelengths of said illumination into a spectrum oriented perpendicular to the scan direction of said first rotatable mirror surface, focusing said reflected light with a second dispersing prism oriented approximately parallel to said first dispersing prism, and passing said light reflected from said third mirror surface through a third dispersing prism oriented whereby the resulting spectrum is approximately perpendicular to the scan direction of said third mirror surface.72. The method as defined by claim 66 wherein said object comprises biological tissue.73. The method as defined by claim 72 wherein said biological tissue comprises the endothelial cell layer on the inner surface of cornea of the human eye. | KOESTER C | KOESTER C |
WO-1979001029-A1 | 1,979,001,029 | WO | A1 | XX | 19,791,129 | 1,979 | 20,090,507 | new | C08L79 | C08L79 | C08J5, C08L79, C08L81 | C08L 79/04, C08L 79/06, C08L 79/08 | AROMATIC HETEROCYCLIC POLYMER ALLOYS AND PRODUCTS PRODUCED THEREFROM | Polymeric alloys of rod-like and coil-like aromatic heterocyclic polymers useful for the fabrication of high strength load bearing structural components. In one aspect of the invention, rod-like aromatic heterocyclic polymers are used as reinforcement in coil-like heterocyclic polymer matrices to provide composites at the molecular level that are analogous to chopped fiber composites. A representative example of the coil-like heterocyclic polymer consists essentially of repeating units having the following structural formulas: (FORMULA) wherein X is NR No, O or S, where o is phenyl, Ar' in (FORMULA) or //c and m is an integer having a value such that the polymer has an intrinsic viscosity of about 2 to 20 dl/g as determined in methanesulfonic acid at 30`C, and a representative example of the rod-like aromatic heterocyclic polymer consists essentially of repeating units having the following structural formulas: (FORMULA) wherein X is NR, No, O or S, where o is phenyl, Ar is //c or //c and n is an integer having a value such that the polymer has an intrinsic viscosity of about 5 to 30 dl/g as determined in methanesulfonic acid at 30` C. | AROMATIC HETEROCYCLIC POLYMER ALLOYS AND PRODUCTS PRODUCED THEREFROMTECHNICAL FIELD This invention relates to polymeric alloys of rod¬ like aromatic heterocyclic polymers and coil-like aromatic heterocyclic polymers. In one aspect it relates to a method for the preparation of composite films at the molecular level that are analogous to chopped fiber com¬ posites. In another aspect it relates to composite films prepared from para ordered, rod-like aromatic heterocyclic polymers embedded in an amorphous heterocyclic system. BACKGROUND ARTFiber-reinforced plastics currently being used in the fabrication of load-bearing structural components are light weight, durable and low cost. The fabrication of such components involves a complex stepwise procedure. The strength and durability of the composite is largely dependent upon the existence of an extensive, long lasting load- ransferring interface between the reinforcing fibers and the plastic matrix. A need exists for high strength reinforced composites and a method for their manufacture which possess at least the following desirable prerequi¬ sites: (1) non-reliance on fiber reinforcement for the attainment of high strength properties, (2) circumven¬ tion of the complexities of current composite fabrication procedures, and (3) elimination of any possibility of fiber-plastic interface problems.SUMMARY OF THE INVENTION Broadly speaking, the present invention resides in a polymeric alloy comprising a mixture of flexible coil- like heterocyclic polymer and a reinforcing amount of a rod-like aromatic heterocyclic polymer. It has been dis¬ covered that the stiff chain, rod-like polymers function as a reinforcement in coil-like polymer matrices. As a result a composite at the molecular level can thereby be readily fabricated that is analogous to chopped fiber composites.As intimated above, the role of the rod-like polymer molecules, individually and in-aggregate, is to reinforce the softer, more flexible matrix material, thereby im¬ proving the modulus and tensile strength of the composite mixture. Furthermore, the composite mixture can be in¬ duced to exhibit anisotropic properties by causing flow o the polymer mixture. Extensional flow causes the individ ual and aggregate stiff chain, rod-like polymer molecules to orient in the direction o'f flow, and as~a consequence o the orientation the mechanical properties are vastly im¬ proved.It is an object of this invention therefore, to pro- vide a polymer alloy of rod-like heterocyclic polymer and a coil-like amorphous heterocyclic polymer for use in the fabrication of high strength composites.Another object of the invention is to provide com¬ posite materials at the molecular level that are analo- gous to a chopped fiber composite.A further object of the invention is to provide a method for preparing composite films composed of rod-like aromatic heterocyclic polymers and analogous soft amor¬ phous matrices. DETAILED DESCRIPTIONIn one embodiment, the invention lies in a composite film comprising a coil-like heterocyclic polymer as a matrix and embedded in the matrix a reinforcing amount of a rod-like aromatic heterocyclic polymer. The film generally contains about 5 to 50 weight percent, prefer¬ ably 10 to 30 weight percent, of the rod-like polymer.O Λ. WIP In another embodiment, the invention resides in a method for fabricating the composite film. Initially, the rod-like polymer and the coil-like polymer are dis¬ solved in the indicated proportions in methanesulfonic acid. The amount of polymer so dissolved is such as to provide about 1 to 30 percent, preferably 1 to 5 per¬ cent, solution of the polymer mixture in the solvent. The polymer solution is then introduced into a mold after which the solvent is removed. Removal of the solvent can be accomplished by any suitable means. In a preferred procedure, the mold is placed in a sublimator which is thermostated at about -20 to -25°C. The sublimator is evacuated continuously with a vacuum pump while being heated at about 50 to 60°C to expedite removal of the methanesulfonic acid solvent. After leavipg the solution, the solvent solidifies on the cold surface of the sublim¬ ator. The film so formed is then removed from the mold and dried under reduced pressure, e.g., 10 microns or less, at about 75 to 125°C for about 12 to 36 hours. In order to optimize the strength properties of the composite mixture, it is often preferred to subject the stiff chain, rod-like reinforcement in the soft, flexible polymer matrix to uniaxial orientation. This uniaxial orientation of the film is accomplished by initially allowing residual casting solvent, which acts as a plas- ticizer, to remain in the polymer mixture constituting the film. The film is then stretched or elongated to provide the desired orientation. Elongation of the film can be carried out by well known procedures. In one pro- cedure, elongation for uniaxial orientation is conven¬ iently conducted with an Instron tensile tester at cross- head speeds of about 0.01 to 0.5 inch per minute, pre¬ ferably at slower rates of 0.01 to 0.02 inch per minute. During the orientation, the film is elongated or stret- ched by about 50 to 40 percent of its original length. The concentration of residual solvent (plasticizer) in the composite mixture ranges from about 1 to 30 weight percent, preferably about 15 weight percent. After orientation of the stiff chain rods in the uni axial direction of the composite mixture, residual solven is leached from the film by means of a low boiling non- solvent. Examples of non-solvents for the polymers that can be used include aliphatic alcohols and ketones, such as methanol, ethanol, propanol, isopropanol, acetone, methyleth lketone, and the like. Leaching of the solvent is carried out at a temperature ranging from room tempera ture to the reflux temperature of the non-solvent. Remov al of the solvent by leaching is generally completed in about 5 to 30 minutes after which the film is recovered and dried to remove any non-solvent.Even further enhancement of the physical properties of the composite film can be obtained if the leaching of the solvent is conducted while the film is under tension. Thus, the non-solvent is advantageously applied to the surface of the film while under tension during the uni¬ axial orientation procedure.In the foregoing discussion, the invention has been described primarily as it relates to composite films.However, the polymeric alloys of this invention are not limited to use in the fabrication of composites. For example, mixtures of the rod-like aromatic heterocyclic polymers and the coil-like heterocyclic polymers dissolv- ed in methanesulfonic acid can be used as a spinning dope The as-spun fibers can be elongated by well known methods to produce high strength, high modulus, thermally stable fibers.Rod-like aromatic heterocyclic polymers used in the practice of the present invention exhibit 'para' ordered geometry. Examples of such polymers, which are described in the literature, include those consisting essentially of repeating units having the following formulas: to the number of recurring units and has a value such that the polymers have an intrinsic Viscosity of at least 2 dl/g, preferably 5 to 30, inclusive, as determined in methanesulfonic acid at 30°C. Examples of other rod-like polymers that can be used include those disclosed by one of us in commonly assigned copending application U.S. Serial No. 811,345, filed on June 29, 1977. The disclo¬ sure of this application is incorporated herein by ref¬ erence.Flexible coil-like heterocyclic polymers used in combination with the rod-like polymers are also described in the literature. Examples of such polymers include those consisting essentially of repeating units having the above formulas, m is an integer equal to the number of recurring units and has a value such that the polymers have an intrinsic viscosity of at least 1 dl/g, prefer¬ ably 2 to 20, inclusive, as determined in methanesulfoni acid at 30°C.A more complete understanding of the invention can be obtained by referring to the following illustrative examples which are not intended, however, to be unduly limitative of the invention.EXAMPLE IA series of runs was conducted in which composite films were prepared in accordance with the present inven¬ tion. A control run was also carried out in which a fil was fabricated which did not contain a rod-like polymer. The rod-like and coil-like polymers used in the runs had the following formulas: One percent solutions containing mixtures of the rod¬ like polymer (PBT) with an intrinsic viscosity of 5.07 and the coil-like polymer (PPBT) with an intrinsic vis¬ cosity of 2.38 were prepared in methanesulfonic acid. In eachrun 10 milliliters of the solution was pipetted into a flat bottom film casting dish. The dish was then placed in a sublimater thermostated at 24°C. The sub¬ limator was evacuated with a vacuum pump and heated at 50 to 60°C to hasten the removal of the methanesulfonic acid. After the films had formed, they were dried at 100°C for 24 hours under reduced pressure (10 microns or less) . The films were cut into 0.25 inch strips andbroken in an Instron tensile tester. The amounts of polymers used and the results obtained in the tests are shown below in Table I.OMPI TABLE IRod(P: BT) Coil(PPBT) Tensile, Improve¬ Modulus Improve¬ wt % t % psi ment, % 105 psi ment, %— 100 2,699 1.92 —25 75 8,414 211 4.90 15550 50 3,580 33 2.59 3575 25 4,037 50 2.76 • 44EXAMPLE IIA series of runs were carried out in which composite films were prepared in accordance with the present invention and then subjected to uniaxial orientation. As in Example I, a control run was included. The rod-like and coil-like polymers used in the runs had the following formulas: Rod-like Polymer (PDIAB) Coil-like Polymer (AB-PBI)One percent solutions containing mixtures of the rod poly¬ mer (PDIAB) with an intrinsic viscosity of 2.64 and the coil polymer (AB-PBI) with an intrinsic viscosity of 18.0 were prepared in methanesulfonic acid. In each run, 10 milliliters of the mixture was pipetted into a flat bottom casting dish after which the dish was placed in a sublimator thermostated at -24°C. The sublimator was evacuated continuously with a vacuum pump and heated at 50 to 60°C to hasten the removal of the methanesulfonic acid. After the films had formed, they were dried at 100°C under reduced pressure (10 microns) to provide films with an acid content (residual plasticizor) of about 15 weight percent. The films were cut into 0.25 inch strips andO PI ,. WIPO « broken in an Instron tensile tester. The amounts of pol mers contained in the films and the test results are shown below in Table II.TABLE II od(PDIAB) Coil(AB-PBI) Tensile, Improve¬ Modulus Improv Wt % Wt % psi ment % Xl05psi ment,— 100 14,600 2.0010 90 17,954 23 8.20 31020 80 12,392 — 5.17 158EXAMPLE IIIFilm specimens prepared as described in Example II and having an acid content (residual plasticizer) of about 15 weight percent were subjected to uniaxial orientation. Thus, the specimens were elongated in an Instron tensile tester at a crosshead speed of 0.02 inch per minute.Thereafter, the oriented film specimens were broken in the tester. The amounts of polymers contained in the film composites and the test results are shown below in in Table III. TABLE III od(PDIAB) Coil(AB-PBI) Tensile, Improve- Mod lus Improv wt % wt % psi ment, % XlO^psi ment,— 100 20,730 3.1710 90 40,092 93 13.4 32320 80 23,509 13.4 6.24 97EXAMPLE IVFilm specimens prepared as described in Example II and having an acid content (residual plastici-zer) of about 15 weight percent were subjected to uniaxial orientation as described in Example III. While the film specimens were under tension in the Instron tester, methanol was applied to their outer surfaces in order to leach out the residual solvent in the films. Thereafter, the oriented film specimens were broken in the Instron teste The amounts of polymers contained in the film composites and the test results are set forth below in Table IV.O PI TABLE IVRθd(PDIAB) Coil (AB-PBI) Tensile, Impro-ve- Modulus Improve¬ wt % t % psi ment, % XI0 psi ment, %— 10Q 20,730 3.1710 90 53,500 154 14.1 34520 80 40,000 93 10.3 22530 70 35,000 69 12.8 304As seen from the data in the foregoing examples, the present invention provides high strength reinforced com- posites based on the formation of polymer alloys. Thus, instead of adding rein orcing fibers to a plastic in the conventional manner, strength is obtained as a result of molecular orientation of polymer chains within the plastic matrix itself. The improvement in physical properties obtained,by uniaxial orientation is demonstrated by the data shown in Table III although, as seen from the data in Table II, the non-oriented film composites containing residual acid plasticizer possess relatively good proper¬ ties. However, when the residual plasticizer is leached from the oriented film composite while under tension, the properties of the film composites are further enhanc¬ ed by an unexpected degree as seen from the data in Table IV.From the foregoing description, it is seen that the present invention provides a simplified procedure for fabricating composites. Thus, the .procedure eliminates many of .the complexities currently encountered in using fibers to reinforce plastic matrices. Also, by their very nature, the present composites are not subject to the fiber-plastic interface problems as are conventional fiber-reinforced plastics. Other objects and advantages of the invention will become apparent to those skilled in the art upon consideration of the disclosure.As will be evident to those sk.illed in the art, mod- ifications of the present invention can be made in view of the foregoing disclosure without departing from the spirit and scope of the invention.O PI ., IPO . | CLAIMS1. A polymeric alloy comprising a mixture of a flexible coil-like heterocyclic polymer and a reinforcin amount of a rod-like aromatic heterocyclic polymer.2. The polymeric alloy according to Claim 1 in ' which the mixture contains about 5 to 50 weight percent of the rod-like polymer.3. The polymeric alloy according to Claim 2 in whi the coil-like heterocyclic polymer consists essentially of repeating units having the following structural wherein X is NH, Nφ, 0 or S, where φ is phenyl, Ar' is integer having a value such that the polymer has an in¬ trinsic viscosity of about 2 to 20 dl/g as determined in methanesulfonic acid at 30°C; and the rod-like aromatic heterocyclic polymer consists essentially of repeating units having the following structural formulas:OMPI/,, W-FU a va ue suc t at t e po ymer as an ntr ns c v scos ty of about 5 to 30 dl/g as determined in methanesulfonic acid at 30°C.' 4. The polymeric alloy according to Claim 3 in which the coil-like heterocyclic polymer consists essentially of a:-the rod-like aromatic heterocyclic polymer consists essen¬ tially of repeating units having the following structural formula:5. The polymeric alloy according to Claim 3 in which the coil-like heterocyclic polymer consists essen¬ tially of repeating units having the following structural formula: rod-like aromatic heterocyclic polymer consists essen¬ tially of repeating units having the following structuralOMPI *. 1PO - - 12 -6. As an article of manufacture, a composite film comprising as a matrix a flexible, coil-like heterocycli polymer, and embedded in the matrix a reinforcing amount of a rod-like aromatic heterocyclic polymer.7. The composite film according to Claim 6 in whic the film contains about 5 to 50 weight percent of the ro like polymer.8. The composite film according to Claim 7 in whic the coil-like heterocyclic polymer consists essentially of repeating units having the following structural for¬ mulas: integer having a value such that the polymer has an in¬ trinsic viscosity of about 2 to 20 dl/g as determined in methanesulfonic acid at 30°C; and the rod-like aromatic heterocyclic polymer consists essentially of repeating*05 *AOMP , where is phenyl, Ar is an*3 n is an integer having a value such that the polymer has an intrinsic viscosity of about 5 to 30 dl/g as determined in methanesulfonic acid at 30°C.9. The composite film according to Claims 7 or 8 in which polymer chains of the rod-like aromatic heterocyclic polymer are uniaxially oriented.10. The composite film according to Claim 9 in.which the coil-like heterocyclic polymer consists essentially of repeating units having the following structural formula: the rod-like aromatic heterocyclic polymer consists essen¬ tially of repeating units having the following structural formula:11. The composite film according to Claim 9 in which the coil-like heterocyclic polymer consists essentially of repeating units having the following structural formula: the rod-like aromatic heterocyclic polymer consists essen¬ tially of repeating units having the following structural formula:x fREAΪT QMPI_ 12. A method for preparing a composite film which comprises the steps of: a. dissolving in methanesulfonic acid solvent a mixture of a flexible coil-like heterocyclic polymer and a rod-like aromatic heterocyclic polymer, the amount of polymers dissolved being sufficient to provide a 1 to 30 percent solution of the polymer mixture in the solvent and the polymer mixture containing about 5 to 50 weight percent of the rod-like polymer; b. introducing the polymer solution into a casting mold; c. removing solvent from the polymer solution, thereby forming a composite film in the mold; d. recovering the composite film from the mold; an e. .drying the recovered composite film.13. The method according to Claim 12 in which the coil-like heterocyclic polymer consists essentially of repeating units having the following structural formulas: s phenyl, Ar' is and m is an integer having a value such that the polymer has an intrinsic viscosity of about 2 to 20 dl/g as determined in methane- sulfonic acid at 30°C; and the rod-like aromatic heter- cyclic polymer consists essentially of repeating units having the following structural formulas: a value such that the polymer has an intrinsic viscosity of about 5 to 30 dl/g as determined in methanesulfonic acid at 30°C.14. The method according to Claim 13 in which the amount of solvent removed from the polymer solution in step c is such that residual solvent remains in the com¬ posite film, the concentration of the solvent being about 1 to 30 weight percent; the composite film containing residual solvent after being recovered from the mold is elongated, thereby subjecting polymer chains of the rod¬ like polymer to uniaxial orientation; and the residual solvent is leached from the uniaxially oriented composite film by contacting same with a non-solvent for the polymers.15.. The method according to Claim 14 in which the residual solvent is leached from the composite film by applying the non-solvent to the film while it is under tension during uniaxial orientation.16. The method according to Claim 15 in which the coil-like heterocyclic polymer consists essentially of repeating units having the following structural formula: the rod-like aromatic heterocyclic polymer consists essentially of repeating units having the following structural formula: 17. The method according to Claim 15 in which the coil-like heterocyclic polymer consists essentially of repeating units having the following structural formula: the rod-like aromatic heterocyclic polymer consists essen tially of repeating units having the following structural formula:OMPIWIPO | US COMMERCE | ARNOLD F; BENNER C; HELMINIAK T; HUSMAN G |
WO-1979001030-A1 | 1,979,001,030 | WO | A1 | EN | 19,791,129 | 1,979 | 20,090,507 | new | C08G63 | C08G63 | C08G63 | C08G 63/18, C08G 63/60 | POLYESTERS OF 4-CARBOXYBENZENEPROPIONIC ACID | Polyesters of 4-carboxybenzenepropionic acid and unsubstituted aromatic diols have excellent processability, heat resistance, light stability and exceptionally high mechanical properties. | POLYESTERS OF 4-CARBOXYBENZENEPROPIONIC ACID Technical FieldThis invention relates to new high molecular weight polyesters prepared from 4-carboxybenzenepro- pionic acid and unsubstituted aromatic diols.For commerical uses polyesters of improved mechanical properties are being sought, and in order to increase the mechanical properties it is usually neces¬ sary to increase the molecular weight of the polyesters. As the molecular weight is increased the melting point of the polyesters increases, resulting in polyesters that are difficult to process in present commercial equipment. To be useful commercially the polyesters must have excellent processability and excellent mech- anical properties. The polyesters must also be stable at elevated temperatures and for some uses good light stability is required. Background ArtHeat stability is an important property for many polyester applications. For example, if a poly¬ ester is used close to an automobile engine or in an electronic apparatus in which the parts become heated by hot vacuum tubes, it is. necessary that the poly¬ ester be stable under these conditions. German Offenlegungesschrift 2,530,820 dis¬ closes polyesters that are prepared from 4-carboxy- benzene-oxyacetic acid and unsubstituted diols. These polyesters apparently have desirable properties, but the polyesters are not sufficiently stable at elevated temperatures.Also, light stability is an important property for many polyester uses. Some polyesters, such as the polyesters prepared from terephthalic acid and bis- phenol A diacetate, are severely discolored when exposed to light for long periods of time.OMPI&Tr. W1P0 ^ Disclosure of InventionThe polyesters of this invention have excel lent mechanical properties and they can be processed in current commercial melt-processing equipment. Also these polyesters have better heat stability and light stability than prior art polyesters.The polyesters of this invention are prepare by polymerizing 4-carboxybenzenepropionic acid with a unsubstituted aromatic diol. When a linear unsubsti- tuted aromatic diol, such as hydroquinone, is used, th polyester is a liquid crystal polyester. When a non¬ linear unsubstituted aromatic diol, such as 4,4'-iso- propylidenediphenol, is used, the polyester is not liquid crystalline. Table I demonstrates the surprising improve¬ ment in heat stability that the polyesters of this in¬ vention have. In this table the heat or thermal stability of polyesters prepared by polymerizing 4-car boxybenzenepropionic acid with certain aromatic diols is compared with polyesters prepared by polymerizing 4-carboxybenzene oxyacetic acid and similar aromatic diols. Although 4-earboxybenzenepropionic acid differ from 4-carboxybenzene oxyacetic acid only by changing an oxygen atom to a-CH -group, a surprising increase in the heat or thermal stability is obtained by this slight change.Thermal stability of the polyesters in Table I was determined by thermogravimetric analyses (TGA) in nitrogen. The thermal properties of these polymers are summarized in Table I. The preparations of poly¬ esters 1, 3 and 5 are given in Examples 1, 4 and _5. Polyester 2 (I.V. 0.54) was similarly prepared but a melt temperature of 275°C. was used. Polyesters 4 and 6 were prepared by solid-state polymerization of pre- polymers (28θ°C, 0.1 mm) which had solidified in the melt at 300°C.O WI Polyester 1 of the invention is more thermally stable than polyester 2 of the prior art, polyester 3 is more stable than polyester 4, and polyester 5 is more stable than polyester 6. TABLE ITHERMAL STABILITYTemperature Temperature at Which 10% at Which 50%A-Carboxybenzene- A-Carboxybenzene- Weight Loss Weight Loss Weight Loββ Polyesters propionlc Acid oxyacέtlc acid at A00°C % Occurs, °C Occura, *C1 A,A'-l8oproρyli- dene diphenol 2.5 AA5 5002 A,A*-Isopropyli- dene diphenol 5.0 A15 A653 Hydroquinone 1.0 A50 530A Hydroquinone 13.0 390 A955 30 mole % tere- 0.0 A80 530 phthalic acid and hydroquinone6 30 mole X tere- 2.0 A30 A95The polyesters of this invention have an in¬ herent viscosity of at least 0.4 and preferably at least 0.8 and are prepared from 4-carboxybenzenepropionic acid and unsubstituted aromatic diols. The. acid portion of the polyesters can be modified with up to 50 mole percent of at least one aliphatic, alicyclic or aromatic dicarboxylic acid. These modifying acids include tere- phthalic acid, isophτj-halic acid, 2,6-naphthalenedicar- boxylic acid, cis or trans-l,4-cyclohexanedicarboxylic acid, 4,4'-oxydibenzoic acid, monochloroterephthalic acid, a dichloroterephthalic acid, methyl terephthalic acid, a dimethyl erephthalic acid and 4,4'-diphenyldi- carboxylic acid.The unsubstituted aromatic diol portion of the polyesters of this invention includes hydroquinone, 4,4'-isopropylidendiphenol, 4,4'-thiodiphenol, 4,4'- oxydiphenol, 4,4'-(2-norbornylidene) iphenol, 4,4'- (cyclohexylmethylene)diphenol, 4,4'-dihydroxybiphenyl, 1,4-naphthalenediol, 1,5-naphthalenediol and 2,β-naph- thalenediol.Also minor amounts of substituted hydroquin- ones such as chloro, bromo and methyl hydroquinone can be used so long as the thermal stability of the poly¬ esters of this invention is not adversely affected. The diacyl derivatives of the aromatic diols can be used to prepare the polyesters of this invention. The acetyl and propionyl derivatives are preferred, but the butyryl, isobutyryl, or benzoyl derivatives are examples of others which may also be used. By unsub-r stituted, we mean that no group such as alkyl, alkoxy, or halogen is attached to an aromatic ring of the aro¬ matic diol. The preferred diols are hydroquinone and 4,4'-isopropylidenediphenol.A polyester of this invention can be prepared from 4-carboxybenzenepropionic acid, a diacyl ester of'BUREAUOMPI y WIPO ; hydroquinone and a p-acyloxybenzoic acid and can be fined as a polyester having a fiber-forming molecula weight and having the following divalent radicals:(A) - — /•-CHsCHz-C-•=•(B) -0- ^ J and wherein the range o ra ca (C) is 10 to 90 mole pe cent, based on the sum of radicals (A) and (C). In preferred embodiment the range of radical (.C) is fro 30 to 80 mole percent.The polymers of the invention can be made techniques such as by acidolysis of the aromatic dio diacetate with the 4-carboxybenzenepropionic acid. reactants are heated at about 260 C. until most of t monocarboxylic acid has evolved. The temperature of melt is then increased to about 325 C. (up to 360 C. the higher-melting compositions), a vacuum of about millimeter is applied, and stirring is continued unt a high-melt viscosity polymer is obtained. If the p mer solidifies, its molecular weight may be increase to a sufficient value by., heating particles of the po πier in an inert atmosphere or under reduced pressure at a temperature just below the softening point of t polymer.Tough films of the polymers are obtained b pressing or by extrusion. Molding plastics having very high impact strength and heat-deflection temper tures are obtained by injection molding at about _ 350°C.In addition to plastics, the polyesters of this invention can be fabricated to give other types shaped objects such as foamed plastics, fibers, ilm extruded shapes and coatings . The compositions of this invention also may contain nucleating agents, fibers, pigments, glass fibers, asbestos fibers, antioxidants, stabilizers, plasticizers, lubricants, and other addi- tives.This invention is further illustrated by the following examples. The polyesters prepared in these examples were tested and found to have excellent mech¬ anical properties . All inherent viscosities were determined at25°C. in a 40/35/25 weight mixture of p-chlorophenol/ tetrachloroethane/phenol at a concentration of 0.1 g/100. ml. The melting points and glass transition tem¬ peratures were determined with a differential scanning calorimeter.The polyesters were dried in an oven at 100 C. overnight and injection molded to give 2-1/2 x 3/8 x 1/16-inch tensile bars and 5 x 1/2 x 1/8-inch flexure bars for testing. ASTM procedures were used for mea- suring the tensile strength and elongation (ASTM D1708), flexural modulus (ASTM D790), Izod impact strength (ASTM D256 Method A), and heat-deflection temperature (ASTM D648). EXAMPLE 1 This example illustrates the preparation of a polyester from 4-carboxybenzenepropIonic acid and bis- phenol A diacetate.A mixture of 77.6 g (.0.4 mole) 4-carboxyben- zenepropionic acid and 124.8 g O. mole) bisphenol A diacetate was placed in a 500 ml flask equipped with a stirrer, a short distillation column, and an inle.t for nitrogen. The flask was evacuated and purged three times with nitrogen before being lowered into a metal bath maintained at 110°C. The mixture was heated under a nitrogen atmosphere with stirring to a temperature of 260°C. at which point acetic acid began to distill rapidly from the flask. After the reaction mixture w heated with stirring at this temperature for about on hour, the temperature of the bath was increased to 300°C. for 30 minutes and then to 325°C. A vacuum of 0.5 mm of mercury was applied over a period of 15 min utes. After stirring was continued under 0.5 mm of mercury at 350°C. for about 20 minutes, a high melt viscosity, clear, light a er polymer was obtained. The polymer had an inherent viscosity of 0.89 and a glass transition temperature of 147°C. A tough, crea able film can be pressed easily at 325°C. EXAMPLE 2This example illustrates the preparation of copolyester using 50 mole percent of terephthalic aci The procedure described in Example 1 was us to prepare a copolymer from 50 mole percent 4-carboxy benzenepropionic acid, 50 mole percent terephthalic acid, and bisphenol A diacetate. The tough, light am polymer had an inherent viscosity of 0.70 and a glass transition temperature of 168°C. EXAMPLE 3Using the procedure described in Example 1, polyester was prepared from 77-6 g (0.4 mole) 4-carbo benzenepropionic acid and 120.8 g (0.4 mole) 4,4'-t.hi diphenol diacetate. The polyester had an inherent vi cosity of 0.74. A tough, creasable film can be press easily at 325°C. EXAMPLE 4Using the procedure described in Example 1, prepolymer was prepared from 19.4 g (0.1 mole) 4-car- boxybenzenepropionic acid and 22.2 g (0.1 mole) hydro quinone dipropionate. The prepolymer, which had solidified in the flask, was ground to pass a 20-mesh screen for subsequent solid-state polymerization. So state polymerization of the prepolymer was accomplish by heating the particles under reduced pressure (0.1 mm Hg) at 2δO°C. for four hours. The polyester had a melting point of 425°C. EXAMPLE 5 The procedure of Example 1 was used (except the vacuum was applied at 34θ°C. instead of 325°C.) to prepare a copolyester with 0.42 mole (70 mole per¬ cent) 4-carboxybenzenepropionic acid, 0.18 mole (30 mole percent) terephthalic acid, and 0.60 mole (100 mole percent) hydroquinone dipropionate. A high melt viscosity liquid crystalline insoluble copolyester with a melting point of 316 C. was obtained. EXAMPLE 6The procedure of Example 5 was used to prepare a copolyester with 0.20 mole 4-carboxybenzenepropionic acid, 0.20 mole terephthalic acid, 0.20 mole hydroqui¬ none diacetate, and 0.20 mole bisphenol A diacetate. The copolyester had an inherent viscosity of 0.88. EXAMPLE 7 A mixture of 14.4 g. (0.08 mole) p-acetoxy- benzoic acid,3.88 g. (0.02 mole) 4-carboxybenzenepro- pionic acid, and 4.44 g. (0.02 mole) hydroquinone dipropionate was placed in a 100-ml. flask equipped with a stirrer, a short distillation column, and an inlet for nitrogen. The flask was evacuated and purged three times with nitrogen before being lowered into a metal bath maintained at 110 C. The mixture was heated under a nitrogen atmosphere with stirring to a tem¬ perature of 260 C. at which point acetic acid began to distill rapidly from the flask. After the reaction mixture was heated with starring at this temperat.ure for about 1 hour, the temperature of the batch was increased to 300°C. for 30 minutes and then to 350 C. A vacuum of 0.5 mm of mercury was then applied over a period of 10 minutes. After stirring was continued under 0.5 mm of mercury at 35Q C. for about 10 minute a medium melt viscosity, opaque, fibrous, light tan polymer was obtained.A second polyester was prepared in a simila manner, except 4-carboxybenzeneoxyacetic acid was use in place of the 4-carboxybenzenepropionic acid in the first polyester and the final reaction temperature wa 340 C. to limit the considerable color formation.Ten mil films of both polyesters were press at temperatures ranging from 325 to 350 C. and were placed in a 150°C. forced air oven. Once a week the films were creased by hand. The number of weeks required for the film to break upon creasing was re¬ corded as heat stability. The following table sum- marizes the heat stability data for both polyesters.HeatStability ,Weeks toPolymer 1 20 ' >202 20 4The polyesters of this invention also have improved light stability compared to similar polyeste prepared with aromatic dicarboxylic acids other than 4-carboxybenzenepropionic acid. A pressed film of a polyester prepared from this acid and bisphenol A diacetate turned only slightly yellow when exposed fo 35 hrs. (40 fading units) in a fadeometer containing a xenon lamp. A film of a similar polyester prepared with terephthalic acid and bisphenol A diacetate turned deep yellow at the same time in the test.IJUOM . . WI | Claims:1. A high molecular weight polyester char¬ acterized by having been prepared from 4-carboxyben- zenepropionic acid and an unsubstituted aromatic diol. 2. A polyester according to Claim 1 wherein the acid portion of the polyester is modified with up to about 50 mole percent of an aliphatic, alicyclic or aromatic dicarboxylic acid.3. A polyester according to Claim 2 wherein the modifying acid is selected from terephthalic acid, isophthaliσ acid, isophthalic acid, 2,'6-naphthalenedi- carboxylic acid, cis or trans-l,4-cyclohexanedicar- box lic acid, 4,4'-oxydibenzoic acid, monochlorotere¬ phthalic acid, a dichloroterephthalic acid, methyl terephthalic acid, a dimethylterephthalic acid and 4,4'- diphenyldicaroxylic acid.4. A polyester according to Claim 1 wherein the unsubstituted aromatic diol is selected from hydro¬ quinone, 4,4'-isopropylidenediphenol, 4,4'-thiodiphenol, 4,4'-oxydiphenol, 4,4'-(2-norbornylidene)diphenol, 4,4'- (c clohexylmethylene)diphenol, 4,4'-dihydroxybipheny1, 1,4-naphthalenediol, 1,5-naphnaphthalenediol and 2,6- naphthalenediol.5. A polyester according to Claim 2 wherein the unsubstituted aromatic diols are selected from hydroquinone, 4,4f-isopropylidenediphe.nol, 4,4'-thio¬ diphenol, 4,4'-oxydiphenol, 4,4'-(2-norbornylidene)- diphenol, 4, '-(cyclohexyl ethylene)diphenol, 4,4'- dihydroxybiphenyl, 1,4-naphthalenediol, 1,5-naphth- alenediol and 2,6-naphthalenediol.6. A high molecular weight polyester h_aving the following divalent radicals :'BU E UOMPI (A) -8 - W V-CHsCHa-fr(B) -< • .-0- and-%(C) -o→. \ / V?-wherein the range of radical (C) is 10 to 90 mole per cent, based on the sum of radicals (A) and (C). | EASTMAN KODAK CO | JACKSON W; KUHFUSS H |
WO-1979001034-A1 | 1,979,001,034 | WO | A1 | EN | 19,791,129 | 1,979 | 20,090,507 | new | C08G63 | null | C08G63, D01F6 | C08G 63/60D | LIQUID CRYSTAL COPOLYESTERS CONTAINING PHENYLHYDROQUINONE | Liquid crystal copolyesters having excellent mechanical properties. The copolyesters are prepared from an aromatic dicarboxylic acid, phenylhydroquinone and a p-acyloxybenzoic acid. | LIQUID CRYSTAL COPOLYESTERS CONTAINING PHENYLHYDROQUINONETechnical FieldThis invention relates to liquid crystal co¬ polyesters prepared from an aromatic dicarboxylic acid, a phenylhydroquinone and a p-acyloxybenzoic acid.When liquid crystal polyesters are calendared or subjected to other ther oforming operations the poly¬ esters are heated above their softening point . If the softening point of the polyester is high and close to the melting point of the polyester, the calendering or thermoforming operation can cause a substantial reduc¬ tion in the physical properties of the polyester. For many liquid crystal polyesters the softening point is only 10-30 C. below the melting point of the polyester and when these polyesters are heated above their soften¬ ing point a loss of the high strength and high stiffness characteristics of the polyesters occurs.It is highly desirable that liquid crystal polyesters have softening points substantially lower than their melting points so that the loss of desirable physical properties can be avoided during calendaring or thermoforming. Background ArtBelgian Patent 860,959 discloses polyesters prepared from terephthalic acid, 2-phenylhydroquinone . and up to 10 mole % , based on all repeating units of p-hydroxybenzoic acid.(PHB). This PHB content is equivalent to 22 mole % t based on the total moles of erepnt-naiic acid. These polyesters have softening points that aarree oonnllyy 1100°CC.. oorr lleessss b.elow their melting points. Disclosure of InventionThis invention provides copolyesters that have surprisingly low softening points and in some instances the softening points are 100 C. and more below the melting points.The copolyesters of this invention are pre¬ pared from a dicarboxylic acid, which can be tereph- thalic acid or 2,6-naphthalenedicarboxylic acid or mix¬ tures thereof, phenylhydroquinone or a substituted phenylhydroquinone, and a p-acyloxybenzoic acid. This copolyester can be specifically defined as a copoly- ester having a fiber-forming molecular weight and havin the following radicals:wherein Rj is -• •'. ■%-■ ••-- oorr I T. vIIII vT T or mixtures thereof ,R2 is hydrogen, chlorine , bromine or a monovalent alkyl radical having one to four carbon atoms , n is 1 , 2 or3, and the range of is from 25 to 80 mole percent, based on the total moles of radical' (A) and radical (,C) combined.Preferably,R2 is hydrogen and the range of radical (C) is from 30 to 6 mole percent and more pre¬ ferably the dicarboxylic acid is terephthalic acid. Radical (A) is the radical remaining after removal of the hydroxyl groups from the dicarboxylic acid, radical (B) is the radical remaining after removaOM 1. WI of the terminal hydrogen atoms from phenylhydroquinone or a substituted phenylhydroquinone, and radical (C) is the radical remaining after removal of the terminal hydroxyl group and acyl group from a p-acyloxybenzoic acid.The copolyesters of this invention can be pre¬ pared by an acidolysis procedure wherein terephthalic acid or 2,β-naphthalenedicarboxylic acid or combinations of terephthalic acid and 2,6-naphthalenedicarboxylic acid, a diacyl ester of phenylhydroquinone and a p-acyl¬ oxybenzoic acid are contacted at a temperature of 2β0 - 300°C. until most of the monocarboxylic acid has evolved. The temperature is then increased to 350-390 C. and the pressure is decreased to form a high molecular weight polymer. If the polymer solidifies prior to achieving a fiber-forming molecular weight, its molecular weight may be increased to a fiber-forming value by heating particles of the polymer in. an inert atmosphere or under reduced pressure at a temperature just below the sof- tening point of the polymer.The inherent viscosity of the copolyesters of this invention are at least 0.53 and preferably at least 1.0, measured at 25 C. using 0.1 gram of polymer per 100 ml. of a solvent composed by weight of 25 percent phenol, 35 percent tetrachloroethane, .and 40 percent p-chlorophenol. The molecular weights of the copolyes¬ ters of the invention are high enough to be in the fiber-forming range. The minimum fiber-forming molecu¬ lar weight of the polymer is about 5,000. In most cases the copolyester of the invention has a molecular weight above 8,000 and can have a molecular weight as high as 20,000. In some instances the molecular weight can range up to 2 3000 or even higher. As a specific example, a mixture of 8.3 g (0.05 mole) terephthalic acid, 13-5 g (0.05 mole) of the diacetate ester of phenylhydroquinone and 9.0 g (0.05 mole) p-acetoxybenzoic acid was placed in a 100-ml. flask equipped with a stirrer, a short distil¬ lation column, and an inlet for nitrogen. The flask was evacuated and purged three times with nitrogen before being lowered into a metal bath maintained at 110°C. The mixture was heated under a nitrogen atmos- phere with stirring to a temperature of 260 C. at which point acetic acid began to distill rapidly from the flask. After the reaction mixture was heated with stir ring at this temperature for one-half hour, the temper¬ ature of the bath was increased to 300 C. for 30 minute and then to 36θ°C. A vacuum of 0.5 mm of mercury was then applied over a period of 10 minutes. After stirri was continued under 0.5 mm of mercury at 360 C. for about 10 minute's, a high melt viscosity, opaque, fibrou light tan polymer was obtained. The polymer had a mole cular weight -above 10,000 and an inherent viscosity of 2.9. The polymer can be melt-spun into a fiber.The above polymer was dried in an oven at 100°C. overnight and injection molded to give 2-1/2 x 3/8 x l/16-inch tensile bars and 5 x 1/2 x 1/8-inch flexure bars for testing. ASTM procedures were used for measuring the tensile strength and elongation (ASTM D1708), flexural modulus (ASTM D790), Izod impact strength (ASTM D256 Method A) , and heat deflection tem¬ perature (ASTM D648). Bars injection molded at 38θ°C. were smooth, clear and light amber.Molded flexure bars of this composition were thermoformed at 210°C. using a thermoforming die and a press. The bar was preheated at 210°C. for 30 seconds and easily formed within 20 seconds... O Other copolyesters within the scope of the invention containing 2,6-naphthalenedicarboxylic acid instead of all or part of the terephthalic acid can be prepared by a similar procedure but using slightly different reaction temperatures because of differences in melting, points.Crystalline melting points and softening points of copolyesters prepared from 2-phenyl-l,4-pheny- lene diacetate, terephthalic acid and p-acetoxybenzoic acid are listed below. The softening points (Ts) were determined with a Du Pont 9^1 Thermomechanical Analy¬ zer, using a 10-g weight on a tipped probe (0.025-in. diameter) and a scan rate of 10 C/min. The melting points (T ) were determined with a differential scan- ning calorimeter. TABLE 1 p-Acetoxybenzoic Acid, Mole 7. Ts, °C. Tm, °C.0 331 3415 325 33510 311 317 . 20 283 29930 227 30950 202 32560 185 37370 188 379 80 335 379Softening points and crystalline melting points of copolyesters prepared from 2-phenyl-l,4-pheny- lene diacetate, 2,6-naphthalenedicarboxylic acid, and p-acetoxybenzoic acid are as follows:TABLE 2 p-Acetoxybenzoic Acid, Mole % Ts , °C. Tm, a .0 379 3 3i8 39930 307 3 3<4 iβ650 232 NNoonn<e ϊ DDeeitected80 246 NNoonn«e ϊ DDeeltected A wide variety of diesters of phenylhydro¬ quinone can be used to prepare the copolyesters of this invention. Examples of diesters include the dia¬ cetate, dipropionate, dibutyrate and dibenzoate. The diacetate and dipropionate are preferred.The p-acyloxybenzoic acid that provides radi¬ cal (C) in the copolyester of this invention correspond to the structure wherein R is phenyl or a monovalent alkyl radical of 1 to 8, preferably 1 to 4, carbon atoms. Examples of p- acyloxybenzoic acids include p-acetoxybenzoic acid, p- propionyloxybenzoic acid, p-butyryloxybenzoic acid, and p-phenoxybenzoic acid. Preferably, R is a monovalent alkyl radical having one carbon atom, in which case the p-acyloxybenzoic acid is p-acetoxybenzoic acid.The p-acyloxybenzoic acids can be prepared by conventional processes, such as reaction between p- hydroxybenzoic acid and a carboxylic anhydride, such as acetic anhydride. Other processes for preparation of the p-acyloxybenzoic aromatic carboxylic acids are well known in the art. The copolyesters of this invention can con¬ tain other divalent radicals in minor amounts. For example, minor amounts of other isomers of naphtha- lenedicarboxylic acid can be used. The copolyesters of this invention can contain nucleating agents, fillers, pigments, glass fibers, asbestos fibers, antioxidants, stabilizers, plasticizers, lubricants, fire-retardants, and other additives.OM fa WI | We Claim:1. The copolyesters having the following divalent radicals:wherein R, is •o or mixtures thereof,R ls hydrogen, chlorine, bromine or a monovalent alkyl radical having one to four carbon atoms, n is 1, 2 or3j characterized by the range of -o— S» ~\/•- l£- beingfrom 25 to 80 mole percent, based on the total moles of radical (.A) and radical (C) combined.2. The copolyesters of Claim 1 wherein therange of -o—» /•_c_ is from 30 to 65 mole percent3. The copolyesters of Claim 1 wherein R, is4. The copolyesters of Claim 1 wherein R is hydrogen. 5. A shaped article made from the copoly¬ ester of Claim 1. | EASTMAN KODAK CO | GEBEAU G; JACKSON W; KUHFUSS H |
WO-1979001035-A1 | 1,979,001,035 | WO | A1 | EN | 19,791,129 | 1,979 | 20,090,507 | new | H04N9 | G02B27, G03B35 | H04N13 | H04N 13/00S4G7 | SYSTEM FOR THREE-DIMENSIONAL VIEWING OF STEREOSCOPIC PROJECTIONS | A system for three-dimensional viewing of stereoscopic projections, comprising a group of devices, Fig. 1 (2, 3, 4) that permits alternating projection of the right and left images of pairs of stereoscopic films or diapositives, or alternating display of the odd-numbered line fields corresponding to the left images and the even-numbered line fields of the right images of the stereoscopic programs received from television transmitters, so that, on the projection screens or television sets, one image is shown at a time, that is, one left-handed one, one right-handed one, and so on, in a certain frequency of images or fields per second, permitting the viewer or televiewer using eyeglasses with alternating shutters, Fig. 4 (3-8) synchronized with the projection devices or television sets to see with the left eye only the left images or odd-numbered line fields, and with the right eye the right images or even-numbered line fields, of stereoscopic pairs, at the same frequency of images or fields per second projected or transmitted resulting in the impression of three-dimensional images, although the images are projected or displayed on an essentially two-dimensional surface. | DESCRIPTION SYSTEM FOR THREE-DIMENSIONAL VIEWING OF STEREOSCOPIC PROJECTIONS .The methods currently in use simultane- ously project through polarizing filters the images of stereo¬ scopic slide pairs, which are also viewed simultaneously through eyeglasses with polarizing filters which permit each separate eye to observe only the image intended for it.This invention refers to five devices interconnected in such a manner as to permit three-dimensio¬ nal viewing of film or diapositive stereoscopic pairs suitab¬ ly projected, as well as of stereoscopic pair images of films, diaposi ti ves , video-tapes and live program takes, on tele¬ vision receivers also suitably transmitted and received. This system for three-dimensional viewing of stereoscopic projec¬ tions, though not doing away with the use of special eye¬ glasses, to the contrary of those currently in use does not employ polarizing filters, which therefore makes it possible for spectators not only to observe the images clearly and in perfect color on any screen but also to use the sa es kind of eyeglasses for the movies, television and slide project¬ ion, in the event the respective program is three-dimensio¬ nal .The five devices referred to above are: Alternative Synchronizing Shutter; Alternating Field Circuit; Vertical Synchronism Pick-up Circuit, Alternate Shutter Eyeglasses and Alternate Field Plates.Figure 1 is a simplified drawing of a stereoscopic diapositive or film projector, showing the two-ξ^TS-EOM objectives (1) and the Synchronizing Alternating Synchronize (2) which, like those commonly used in filming or film proje tion units, are free to rotate around their shaft (3) to a suitable position and open up alternatively one objective or 5 the other at a particular frequency so that the two images are never projected at the same time.The electric impulses for operating th Alternating Shutter Eyeglasses in synchronism with the pro¬ jector shutter, may be obtained from a luminous source in10. the projector which, through the shutter itself (2) excites one or two LDR's at the frequency of the images projected. The later, in turn, control a low powered transmission unit with one or two channels, operating in the 27 MHz band which, as a remote control device, operates in the eyeglass receive15 that is synchronized to the same frequency.Figure 2 contains a schemati csi pl if i ed view of the studio of a television station, adapted for broadcasting of three-dimensional programs. Connected to the cutting table (1) are the stereoscopic film or slide pro20 jectors (2), the stereoscopic video-tape units (3) and the TV cameras for stereoscopic takes (4). The program selected or, rather, the signals from the selected pair of units, go to the Field Alternating Circuit (5). The latter, like an electronic switch, selects the odd numbered lines of the25 fields in the left-hand machine and the fields with even numbered lines in the right-hand machine to be transmitted alternatively, so that the pictures are composed of stereo- scopi c fields .Figure 3 depicts an ordinary television 0 unit (1) to which has been adapted a Vertical Synchronism Pick-up Circuit (2) purpose of which is to pick up the verti cal synchronism signal of the television so as to control a one or two-channel low power transmitter operating in the 27 MHz band. The latter, like a remote control unit, acts on 35 the Alternative Shutter Eyeglasses unit, figure 4, which are tuned to the same frequency, to supply the electric impulses to the electric magnets of the Alternating Field Plates, Figure 5.Figure 4 shows the Alternating Shutter Eyeglasses. The latter will be seen to consist of an ordi¬ nary frame (1) and, instead of the lenses, or together with the latter, an opaque plate (2) with two rectangular slots (3) at the viewing point of the eyes; on this plate, and at each shorter side of the slots, are set the holders for the bearings (4) of the ends of the shafts (5) of the two shutters (6). These shutters are in the form of small rectangular tubes, with the ends of the shafts set in the centers of the shorter sides (5); also attached to the shutters are two small straight permanent magnets (7), parallel to the smaller faces, whose neutral ends coincide with the align¬ ment of the axes of rotation and alignment of the lines of force in the gaps of the electric magnets (8), and are at¬ tached to the plate (2) alongside the slots (3). The North- South directions of these small magnets (7) form angles which are slightly larger or smaller than 90- to the lines of force of the gaps of the electric magnets, dependent on whether the shutters (6) are open or closed. Attached to the plate (2) and in suitable position are the dampers (9) which restrict the rotary movement of the shutters (6) in both directions. A lid (10) shaped like the plate (2) and with the slots (11) in the same corresponding positions, covers the group of components. The windings of each electric magnet are connected in series or in parallel so as to form at each electro-magnet (8) one North and one South Pole, when traversed by a direct current.The terminals of the groups of windings of the electric magnets are connected with the receiver of the synchron zing signals. The latter, whether assembled separate from the eyeglasses or in the empty spaces of the latter, supply the electric impulses to open and close the shutters alternately, in synchronism with the devices transmitting the synchronizing signals of the stereoscopic film or slide projectors and stereoscopic television units.Figure 5 shows the device termed the Field Alternative Plate set, to be mounted at the front >of the television unit (1), close to the luminescent screen (2). It consists of two plates (3) of about the same size as the screen of the cinescopes; each one has a number of equidistant horizontal slots (4) equal to the number of field lines received. Mounted one in front* of the other and by means of lugs (5), they fit into the guides (6) of a supporting device (7). This support (7) is a rectangular molding which, as already noted, has guides (6) at the shorter sides in which the lugs slide; the upper - portion holds the springs (8) which, by means of traction, keep the two plates (3) supported on the upper dampers (9);the lower portion is fitted with bottom dampers (9) and the electro¬ magnets (10) close to the lower edges of the two plates(3). To these edges, close to the poles of the electro-magnets, the anchors (11) of the latter are attached. The system operates as follows: in the event stereoscopic diapositives or films are projected, each stereoscopic pair is projected in such a manner that the right and-left diapositives are projected alternately by means of the Synchronizing Alternating Shutter, (2) shown in figure 1 , at a certain frequency of images per second. The spectator, using the Alternating Shutter Eye-glasses, figure 4, and receiving, through his own set, the synchronism signa of the projection transmitter, sees, also alternately, the right image with the right eye only and the left image with the left eye only, in view of the action of the shutters on the glasses, which open and close at the appropiate times, thus producing a perfect three-dimensional effect.In case of television, the system is applied in simillar manner: the two cameras, (4) of figure 2 which pick up the scene, are arranged so as to supply stereo copic images, i.e., two images pick up from different angles in line with the technique adopted in stereoscopy. Stereoscopic images may also be obtained with stereoscopic fil es and dia¬ positives, (2) in figure 2, and stereoscopic video-tapes, (3) in figure 2. Only the fields of even lines in each pictures, of the right-hand image, and the fields of odd numbered lines of each frame of the left image are transmitted alternatively through the Field Alternating Circuit, (5) in figure 2, at the particular field per second frequency adopted, so that each frame is composed of a pair of stereoscopic fields, i .e., a field of odd lines from one machine and a field of even lines from the other. The televiewer, using the Alternating Shutter Eyeglasses, figure 4, who receives via his receiving set the synchronising signals of the transmitter of the Vertical Synchronism Pick-up Circuit, (2) of Figure 3, sees, also alternately, the odd-numbered line fields only with the left eye and the even-numbered fields only with the right eye as a result of the action of the eyeglass shutters which open and close at the appropriate moments causing the concept of three-dimensions of the image to be. a perfect one. Of course, for this effect to be obtained, the luminescence of one field on the cinescope screen must not persist until the commencement -of the ensuing field. It is therefore necessary to alter the proportion or composition of the fluorescent material used to make existing cinescopes, or if the same ones are to be used, then use must be made of the Alternating Field Plates, figure 5. These, when fitted to the front of the television set, function as follows: When in a state of repose, the two plates, (3) of figure 5, remain supported by the dampers, (9) of figure 5, at the top, so that the slots of one do not coincide with those of the other, i.e., the television screen, (2) of figure 5, remains fully covered. When in operation, the impulses obtained through the Vertical Synchronism Pick-up Circuit, (2) in figure 3, are alternately passed to one or other electro-magnet, (10) of figure 5, dependent on whether the field received is even - or odd - numbered and dependent on whether the signal transmitted to the eyeglasses is right - or left-handed, so that one of the plates, (3) in figure 5, the one at the back, for ins¬ tance, is moved downwards to a distance corresponding to that separating two consecutive even or odd line, leaving exposed to view only the odd line field. When the follow¬ ing impulse excites the other electro-magnet, (10) of figure 5, the front plate moves down the same distance as that corresponding to the distance between *two consecutive even or odd lines, at the same time that the rear plate rises to the resting position under the action of the springs, (8) in figure 5. Hence only the even line field remains uncovered. A new impulse moves the rear plate down at the same time that the forward plate rises to the rest position under the effect of the respective springs and the odd line field becomes uncovered. This sequence is repeated time after time in synchronism with the fields received and with the eyeglass shutters, so that the odd line field is always exposed when the sweeping starts in this field, and when the left eyeglass shutter opens, or', on the other hand, when the even line field is exposed, with the commencement of the sweep in this field, with opening of the right eyeglass shutters-. | CLAIMS1. System for three-dimensional view¬ ing of stereoscopic projections , characterized by the fact that, through an Alternative Synchronizing Shutter, alternating projection is effected of the images of stereoscopic pairs, at the same time that transmission is effected by electro¬ magnetic means of synchronism signals for the alternating shutters of eyeglasses that permit viewers to see the image of the left diapositive of the stereoscopic pair with the left eye only and the image of the right diapositive of the same pair with the right eye only.' 2. System for three-dimensional view¬ ing of stereoscopic projections , characterized by transmitting, via a television station, only the odd-numbered line fields of the frames obtained by one of two cameras, arranged for stereoscopic takes, or of one of the two machines for project¬ ing films, diapositives or video-tapes, provided the latter are equipped respectively with one of the stereoscopic tapes, diapositive of the stereoscopic pair or stereoscopic video- tape, alternatively with the even-numbered line fields of the frames obtained by the other camera or the other machines • for projecting films, diapositives or video-tapes, provided the latter are equipped respectively with another stereoscopic tape or another diapositive of stereoscopic pair or another stereoscopic video-tape, so as to view by the televiewer arrangement in a television set, by the left eye of the spectator, only the odd-numbered line fields of the frames taken by the machines of the transmitter which effect the left take or are fitted with diapositives or recordings of the left of stereoscopic pairs, with the right eye of the spectator viewing only the even-numbered line fields of the frames obtained by the machines of the transmitter which effect the right take or are fitted with the devices or right recordings of the said stereoscopic pairs, through alternat¬ ing shutters on the eyeglasses synchronized with the vertica synchronism signals of the television set, the latter being obtained and transmitted by an electronic circuit fitted to the television set itself.3. System for three-dimensional view ing' of stereoscopic projections , characterized by an eyeglas frame which instead of lenses or together with them possesse two mutually synchronized shutters arranged so that when one closes the other opens, alternatively, so that at no time ar both open at the same time, they being controlled by electro magnets excited by electric impulses derived from a receiver which in turn receives them from the devices transmitting the synchronized signals from projectors or stereoscopic films or stereoscopic diapositives or stereoscopic televisio un ts .4. System for three-dimensional view ing of stereoscopic projections , characterized by having two plates for size and shape approximately equal to the screens of the cinescopes, each having a number of horizontal mutually equidistant slots equal to the number of lines of the field received by the television set. Mounted one in front of the other, and by means of lugs, they fit into guides arranged on the shorter sides of a rectangular support in th form of a molding or frame. The said support is also fitted in the upper portion with springs whose tractive effect maintains the two plates supported on dampers also attached to the upper portion. The lower portion is fitted with dampers and electro-magnets close to the lower edges of the two pl-ates; and on these edges, close to the poles of the electro-magnets, the anchors for the latter are fitted.O | MENSCH W | MENSCH W |
WO-1979001040-A1 | 1,979,001,040 | WO | A1 | XX | 19,791,129 | 1,979 | 20,090,507 | new | C08G63 | null | C08G63, C08G69 | C08G 63/19 | LIQUID CRYSTAL COPOLYESTERS | Liquid crystal copolyesters having melting points low enough to allow the copolyesters to be melt-processed in conventional equipment. The copolyesters are prepared from terephthalic acid, 2,6-naphthalenedicarboxylic acid, a diacyl ester of hydroquinone and a diacyl ester of resorcinol and contain the following divalent radicals: | IQUID CRYSTAL COPOLYESTERSTechnical FieldThis invention relates to liquid crystal co- polyesters having the high mechanical properties of liquid crystal copolyesters and melting points low enough to allow the copolyesters to be melt-processed into useful articles using commercially available equipment. Background of the InventionLiquid crystal cop'olyesters that are all-aro¬ matic have excellent mechanical properties. Examples of these, polyesters are the copolyesters prepared from terephthalic acid, 2,6-naphthalenedicarboxylic acid, hydroquinone and resorcinol. U.S. Patents 3,lβ0,β02 and 3,778,410 describe processes that can be used to' prepare these copolyesters. It has been difficult to use these copolyesters because the melting points of the polymers have been so high that the polymers cannot be melted and formed into useful articles in conventional process¬ ing equipment. Disclosure of InventionWe have found that certain all-aromatic co¬ polyesters prepared from terephthalic acid, 2,6- naphthalene dicarboxylic acid, hydroquinone and resor¬ cinol have melting points that are low enough to permit' the copolyesters to be processed into useful articles, such as fibers and molded articles, in conventional equipment. The copolyesters of this invention are prepared from terephthalic acid, 2,6-naphthalenedicarboxylic acid, a diacyl ester of hydroquinone and a diacyl ester of resorcinol and can be defined as copolyesters having molecular weights suitable for forming fibers and containing the following divalent radicals: In our copolyestErs the range of terephthali acid is from 20 to 0 mole percent, based on the total moles of terephthalic acid and 2,6-naphthalenedicar- boxylie acid combined. Since the range of terephthali acid is based on the sum of the moles of terephthalic acid and 2,6-naphthalenedicarboxylic acid, at 20 mole percent terephthalic acid the copolyesters have 80 mol percent 2,6-naphthalenedicarboxylic acid and at 50 mol percent terephthalic acid the copolyesters have 50 mol percent 2,6-naphthalenedicarboxylic acid.In preferred copolyesters the range of tere¬ phthalic acid is from 30 to 45 mole percent, based on the total moles of terephthalic acid and 2,6-naphtha- lenedicarboxylic acid combined.Also In our copolyesters the amount of resor cinol is from 20 to 6 mole perent, based on the total moles of hydroquinone and resorcinol combined. Thus, at 25 mole percent resorcinol, the copolyesters have 75 mole percent hydroquinone, and at 65 mole percent resorcinol the copolyesters have 35 mole percent hydro quinone.In preferred copolyesters- the range of resor cinol is from 30 to 50 mole percent, based on the tota moles of resorcinol and hydroquinone. The precise manner In which the melting points of the copolyesters of the invention are unexpectedly lower than the melting points of similar copolyesters is illustrated in the Figure. In the Figure the amount of terephthalic acid, based on the total moles of terephthalic acid and 2,6- naphthalenedicarboxylic acid, has been plotted on the abscissa. The temperature in degrees Centigrade has been plotted on the ordinate. Melting points have been plotted for copolyesters of the invention, containing a quantity of terephthalic acid in the range of 20 to 50 mole percent, based on the total moles of tereph¬ thalic acid and 2,6-naphthalenedicarboxylic acid. Suitable curves have been drawn through the data points for copolyesters containing the same amount of resor¬ cinol. For example, the lowermost curve drawn through the closed circular data points represents the melting points of copolyesters containing 40 mole percent resor¬ cinol, based on the total moles of hydroquinone and resorcinol combined.The data for the copolyesters of the inven¬ tion were obtained by preparing each of the copolyesters using a process known in the art and then determining the melting points of each copolyester. The -copolyesters of the invention were pre¬ pared by an acidolysis procedure whereby terephthalic acid, 2,6-naphthalenedicarboxylic acid, a diacyl ester of hydroquinone and a diacyl ester of resorcinol were reacted under an increasing temperature ranging up to 3-*J0-3δ0°C. and a decreasing pressure to form a high molecular weight polymer. As a specific example, the following procedure was used to prepare a copolyester from 40 mole percent terephthalic acid and 60 mole per¬ cent 2,6-naphthalenedicarboxylic acid, based on the moles of terephthalic acid and 2,6-naphthalenedicarboxy- lic acid combined, and 60 mole percent hydroquinone andOMPI 40 mole percent resorcinol, based on the moles of hydro quinone and resorcinol combined.A mixture of 33•2 g. (0.20 mole) terephthalic acid, 64.8 g. (0.30 mole) 2,6-naphthalenedlcarboxylic acid, 38.8 g. (0.20 mole) resorcinol diacetate, and 66. g. (0.30 mole) hydroquinone dipropionate was placed in a 500-ml. flask equipped with a stirrer, short distilla tion column and an inlet for nitrogen. The flask was evacuated and purged three times with nitrogen and drie at 100-110°C. for 30 minutes at <0.3 mm. pressure befor being immersed in a bath at 275°C. After the mixture was stirred for 30 minutes at 280 C, the temperature was raised to 300°C. for 30 minutes and then to 325°C. for 30 minutes. Finally the temperature was raised to 355°C. for 25 minutes and a vacuum of 0.5 mm. was ap¬ plied. The polymerization was complete within 20 to 30 minutes. The tough, fibrous, opaque polymer obtaine had a softening point of 332°C. and a melting point of 34l°C. Fibers with tenacities >3 g./denier can be melt spun at 36θ°C. Heat-treated fibers had tenacities of 10 g./denier -and higher.The other copolyesters containing different amounts of 2,6-naphthalenedicarboxylic acid, tereph¬ thalic acid, hydroquinone and resorcinol were prepared by a similar procedure but using slightly different reaction temperatures because of differences in melt¬ ing points.Solid-phase polymerization also may be used to increase the molecular weight of the copolyesters of the Invention by heating polymer particles in an inert atmosphere or under reduced pressure at a tem¬ perature below that at which the particles will become tacky and tend to fuse together. Since this thermal treatment may give polymers with increased crystall- inity and melting points, compared to melt phase-BUROM W1P polymerization, melt phase polymerization is generally preferred. Solid-phase polymerization is preferred, however, if the melting point is above 38O C.The melting points of the copolyesters of the invention were determined with a differential scan¬ ning calorimeter.The accompanying Figure shows that the melting points of the copolyesters of the invention containing 20 to 50 mole percent terephthalic acid and 20 to 65 mole percent resorcinol are unexpectedly lower than the melting points of copolyesters containing less than 20 or more than 50 mole percent terephthalic acid. For example, consider the copolyester which contains a con¬ stant value of 40 mole percent resorcinol and is repre- sented by the lower curve connecting the closed circular data points. When the amount of terephthalic acid is below 20 mole percent, the melting point is above 400 C. As the amount of terephthalic acid is increased, the melting point falls and reaches a minimum value of 330 C. at 30 mole percent terephthalic acid. As the amount of terephthalic acid is increased, the melting point increases and is 385 C. at 50 mole percent tere¬ phthalic acid.Although the details of the reduction in melting point have been discussed only for the copoly¬ esters containing 40 mole percent resorcinol, the same lowering of the melting point applies to the other co¬ polyesters of this invention. For example, the melting point of the copolyesters containing 20 and 60 mole per- cent resorcinol is also substantially lowered when from 20 to 50 mole percent terephthalic acid is used. Al¬ though melting point data is not plotted for copolyes¬ ters containing less than 20 mole percent terephthalic acid, it is clear from the shape of the curve melting points are above 400°C. A wide variety of diacyl esters of hydroqu one and resorcinol can be used to prepare the copoly esters of this invention. Examples of diesters Incl the diacetate, dipropionate, dibutyrate and dibenzoa The diacetate and dipropionate are preferred.The copolyesters of this invention can con tain minor amounts of other naphthalenedicarboxylic acid isomers in addition to the 2,6-isomer. Also, m amounts of dicarboxylic acids other than terephthali acid and diols other than hydroquinone can be used. The copolyesters of this invention can also contain nucleating agents, fillers, pigments, glass fibers, asbestos fibers, antioxidants, stabilizers, plastici -zers, lubricants, fire-retardants, and other additiv The inherent viscosity of the copolyesters of this invention cannot be determined because the c polyesters of this Invention are insoluble in typica solvents used for determining inherent viscosity. A though the inherent viscosity of the copolyesters of invention has not been measured, the molecular weigh of the copolyesters of the invention are high enough to be in the fiber-forming range. The minimum fiber forming molecular weight of the copolyesters is abou 5,000. In most cases copolyesters of the invention have molecular weights above 8,000 and can have mole cular weights as high as 20,000 and- in some instance the molecular weights can range up to 25,000 or even higher. | We Claim :1. Copolyesters having a fiber-forming mole¬ cular weight and containing the following divalent radicals: the copolyesters being characterized by the amount ofbeing from 20 to 50 mole percent, b ar*-nt ofle percent,b and2. The copolyester of Claim 1 wherein therange of the amount of is from 30 to 45 mole percent and the range of the amount of -8-is from 30 to 50 mole percent. | EASTMAN KODAK CO | JACKSON W; MORRIS J |
WO-1979001046-A1 | 1,979,001,046 | WO | A1 | EN | 19,791,129 | 1,979 | 20,090,507 | new | A43B5 | B65D63 | A43B5 | A43B 5/04D2B | PROTECTION FOR BOOTS OR THE LIKE | A protector device (1) adapted for removable attachment to a ski boot (32) whereby a skier can walk on hard abrasive surfaces without damaging the bottom surface of the boot. The protector device (1) is in the form of a resilient member which is adapted to be received about opposite outer peripheral edges of the sole and along the bottom of the boot. | DescriptionProtection For Boots Or The Like Background Of The InventionThe present invention relates to boot protection devices, and more particularly to a sole protector arranged to be removably mounted onto a ski boot, thereby protecting the sole of the boot from damage caused by walking on hard abrasive surfaces, such as parking lots or the like.Description Of The Prior ArtFor the past several years virtually all alpine ski boots have included an outer shell made from relatively hard, thin plastic material which is designed to reduce the weight of the ski boot to a minimum. If these ski boots are worn when walking on abrasive surfaces, such as roadways, parking lots, or the like, the soles of the ski boots become scarred, rounded on the edges, and eventually worn through the outer shell to the footbed of the boot. This wear problem is com¬ pounded by friction resulting between the rough ski boot sole and the ski, thereby impeding the proper functioning of the binding while increasing the changes of injury by improperly functioning equipment. It is apparent that there is a need in the prior art to have a suitable means to pro¬ tect the bottom of ski boots from being scarred or other¬ wise damaged while walking on hard abrasive surfaces. Al¬ though there have been prior art attempts to solve this pro¬ blem, all of the prior protective devices have been too bulky to conventiently store when not in use, and they have been too heavy and too difficult to install on the sole of the boot.It has now been found that by practice of the present invention there is provided a convenient protective- device for the sole of a boot which overcomes numerous disadvan¬ tages of prior art devices, while providing a simple, commercially practical, highly convenient solution for pro- -2- tecting the sole of a rigid boot, such as a ski boot, from damage by abrasive surfaces.Summary Of The Invention Generally stated, the present invention provides a protector device for the sole of a boot-. The protector device is removably attached to the sole surface of the boo and includes a resilient strap which is adapted to be mounted over the outer peripheral edge of the sole. Pre- ferably, the resilient strap includes a ridge portion dis¬ posed under the forefoot and heel sections of the sole. Th resilient strap may be configurated with sufficient thick¬ ness along the body portion thereof providing that the thic ness of the strap is sufficient to prevent the boot sole from contacting rough surfaces and narrow enough to enable the strap to be mounted over the outer peripheral edge of the sole, such as by twisting the resilient strap to form intermediate loops. A substantial portion of the resilient strap is thus maintained beneath the sole of the ski boot when the strap is in use.It is an object of this invention to effectively pro¬ tect the soles of boots from damage caused when the soles contact rough, abrasive surfaces.It is another object of this invention to provide a ski protector device, especially for the soles of ski boots, which is commercially practical and which is adjustable to fit many boot sizes, in a simple convenient manner.It is another object of the invention to provide a protector device that has very little weight and is easy to use.Another object of the invention is to provide a pro¬ tector device that can be easily stored while not in use.It is another object of the invention to provide a protector device that is inexpensive to manufacture. These and other objects and advantages of the present invention will become apparent with reference to the accompa ing drawings wherein similar elements are identified by lik numerals throughout the several views.Brief Description Of the DrawingsFigure 1 is- a perspective view of the protector device of the present invention;Figure 2 is a cross-sectional view of the device of Figure 1, taken along sectional lines 2-2 thereof;Figure 3 is a cross-sectional view taken along line 3-3 of Figure 1; Figure 4 is a side elevational view showing the protector device of the present invention mounted onto a ski boot;Figure 5 is a bottom view of the ski boot of Figure 4, showing the protector device mounted onto a ski boot; Figure 6 is a side elevational view showing the pro¬ tector device mounted onto a ski boot when fastened to a ski; andFigure 7 is a perspective view of an embodiment of the protector device of the present invention.Description of Preferred EmbodimentsIn the drawings, Figure 1 illustrates protector device 10 formed as an elongated multi-shaped loop or member having first loop end 12 and second loop end 14 with longitudinal surfaces 16 and IS integrally connecting the loop ends. Longitudinal surface 16 includes a pair of segments 19 and 21 having textured surfaces 20 and 22, respectively thereon, whereas the longitudinal surface 18 includes a further pair of segments 23 and 25 having tex- tured surfaces 24 and 26, respectively, thereon. It will be recognized that loop end portions 12 and 14 are of a uniform, rectangular, strap-shaped configuration. It will likewise be recognized that the intermediate portions of the longitudinal surfaces 16 and 18 are of a rod-shaped configuration, whereas the outer portions comprising the segments of the longitudinal surfaces 16 and 18 are of a rectangular configuration and of greater thickness. The intermediate portions and the loop end portions comprise connecting portions.Figure 2 illustrates, in cross-section, one of the segments and its textured surface in greater detail. InFigure 2, the thicker longitudinal surface 20 is illustra with rib member 28 in relationship to loop end portion 12Figure 3 illustrates, in cross-sectional view taken along line 3-3 of Figure 1, the intermediate rod-shaped configuration of longitudinal surface 16 in relationship to the thicker textured surface 20 of segment 19. The rib member 28 provides an anti-skid surface.Figure 4 illustrates a ski boot 32 generally depict of the type formed of rigid plastic material with ski binding toe member 34 and ski binding heel member 36. Th protector device 10 of Figure 1 may be attached by simply twisting the intermediate portions of longitudinal sur¬ faces 16 and 18 while attaching the first loop end por¬ tion 12 to ski binding toe member 34 and the second loop end portion 14 to ski binding heel member 36. Figure 5 illustrates in greater detail the protecto device 10 attached about the sole portion of a boot 32. In Figure 5, the twisting engagement of the protector device 10 is more clearly illustrated by twist 38. One twist is sufficient to form a generally illustrated figure eight configuration for attachment to the sole por tion of the ski boot.Figure 6 illustrates the protector device 10 posi¬ tioned on ski boot 32 when the boot is fastened to a ski 44 by means of ski binding toe member 40 and ski binding heel member 42.Figure 7 illustrates a further embodiment of pro¬ tector device 50 of the present invention where the thick portions or segments of the loop 52, 54, 56 and 58 are tapered gradually to longitudinal surfaces 60 and 62 and likewise tapered gradually to loop end portions 64 and 66. The protector device of the present invention may b formed by molding, extrusion and subsequent adhesion, or related techniques well known in the art. The material forming the protector device of the present invention is desirably 'an elastic material, such as plastic, rubber, or the like. It has been found that for convenience of wear, rubber formulated compositions are preferred for preparing the present protector device.When the resilient protector device is not in use, it may be completely removed from the ski boot and stored in a coat pocket, or it may be left on the ski boot simply by releasing the strap at either the toe end or heel end to eliminate the twist therein and the entire strap is slipped over the boot sole and positioned immediately above the sole where it is held In place and out of the way. In this posi¬ tion, the protector device protects the sides of the boots from being damaged by the metal edges of the skis.The present protector device may be conveniently pre¬ pared in one size and because of the elasticity thereof it may be secured to a variety of ski boot sizes. However, to accommodate all boot sizes, several different length pro- tectpr devices are necessary. The surface of the segments of the protector device is textured to provide traction or anti¬ skid protection while walking on slippery surfaces which are frequently encountered on roadways.The invention and its attendant advantages will be understood from the foregoing description and it will be apparent that various changes may be made in the form, con¬ struction and arrangement of the parts of the invention with¬ out departing from the spirit and scope thereof or sacrificing its material advantages, the arrangement hereinbefore described being merely by way of illustration and not to be restricted to the specific form shown except as defined in the accompanying claims. | ClaimsA protector device for protecting at least the bottom sole portion of a boot comprising in combination: a member formed of a resilient, stretchable materia capable of being twisted to form a pair of loops adapte to be mounted over an outer peripheral edge of the sole of a boot within the regions of the heel and toe, respectively, said member including a plurality of segments of a dimension greater than the dimension of the connecting portions of said member and spaced apart therealong whereby when said member is twisted to form said loops and said member is mounted on said boot at least a pair of segments are disposed under the fore¬ foot and heel areas of said sole.The protector device as recited in claim 1 wherein the segments have a textured, anti-skid surface.3. The protector device as recited in claim 1 wherein at least the connecting portions mounted over said outer peripheral edge are of a rectangular strap-like con¬ figuration.4. The protector device as recited in claim 1 wherein the segments are of a rectangular configuration.5. The protector device as recited in claim 4 wherein said segments have a textured, anti-skid surface.6. The protector device as recited m claim 1 wherein the connecting portions adapted to be twisted to form said loops are substantially round in cross-section.7. The protector device as recited in claim 1 wherein the segments at least at the ends toward the loop end are tapered. 8. The protector device as recited in claim 1 wherein the segments at least at the ends toward the twist are tapered. | KNUDSEN P | KNUDSEN P |
Subsets and Splits