description
stringlengths 2.98k
3.35M
| abstract
stringlengths 94
10.6k
| cpc
int64 0
8
|
|---|---|---|
FIELD OF THE INVENTION AND RELATED ART STATEMENT
This invention relates to heat-transfer medium compositions.
Heat-transfer media are used mostly at high temperature and are expected to be high-boiling and heat-resistant and, additionally, to remain liquid during shutdown of the equipment. Heat-transfer media based on aromatic hydrocarbons of excellent heat stability are known to possess the aforesaid characteristics. In particular, a large number of reports have been made on biphenyl-based heat-transfer media for their excellent performance. U.S. Pat. No. 1,882,809 describes a heat-transfer medium composed of biphenyl and diphenyl ether and this is commended for use as one of the most thermally stable organic heat-transfer media available at the present time. This particular heat-transfer medium is designed on the basis of the fact that its melting point has a minimum near a composition of 26.5% by weight of biphenyl and 73.5% by weight of diphenyl ether. The melting point in this case is approximately 13° C., which still appears somewhat high.
The melting point may be lowered by the use of low-melting substances. Such substances, however, are generally low-boiling or thermally unstable. In consequence, practically no organic heat-transfer media other than those mentioned above have been available until today for continuous service at temperatures as high as 400° C.
OBJECT AND SUMMARY OF THE INVENTION
The present inventors have conducted extensive studies to solve the aforesaid problems, found that an addition of diphenylene oxide to heat-transfer media based on biphenyl and diphenyl ether can lower their melting point without sacrificing their heat stability, and completed this invention.
Accordingly, it is an object of this invention to provide novel heat-transfer medium compositions with good heat resistance, high boiling point and low pour point.
This invention thus relates to heat-transfer medium compositions comprising biphenyl, diphenyl ether and diphenylene oxide with diphenylene oxide added in a proportion of 1 to 30% by weight.
Diphenylene oxide, of which another name is dibenzofuran, is a tricyclic aromatic compound with a melting point of 83° C. and a boiling point of 287° C. and occurs in relatively large quantities in coal tar. According to a study by the present inventors, the C--C, C--H and C--O linkages in diphenylene oxide are inferred to be as stable as those in biphenyl and diphenyl ether. Being high-melting and solid at ambient temperature, however, diphenylene oxide appeared unsuitable for heat-transfer use. Then came the finding that, when the compound was added to a mixture of biphenyl and diphenyl ether, the resulting composition had a substantially lower melting point and became liquid at ambient temperature.
The heat-transfer medium compositions of this invention based on biphenyl, diphenyl ether and diphenylene oxide comprise diphenylene oxide in a proportion of 1 to 30% by weight, preferably 2 to 22% by weight, more preferably 4 to 20% by weight and the sum of biphenyl and diphenyl ether in a proportion of 99 to 70% by weight, preferably 98 to 78% by weight, more preferably 96 to 80% by weight. With more than 30% by weight of diphenylene oxide, the composition solidifies above ambient temperature. With less than 1% by weight of diphenylene oxide, the effect of lowering the melting point becomes too small to be viable.
The ratio of biphenyl and diphenyl ether can be varied at will, but it ranges from 10 to 40 parts by weight of the former to 90 to 60 parts by weight of the latter, preferably from 15 to 30 parts by weight of the former to 85 to 70 parts by weight of the latter, more preferably from 20 to 28 parts by weight of the former to 80 to 72 parts by weight of the latter. It is advantageous to choose a ratio so that the melting point or the solidification of the final heat-transfer composition becomes 12.0° C. or less. Such a ratio can readily be chosen from the aforesaid range. The heat-transfer medium compositions of this invention need not be restricted to the above-mentioned three components and may additionally contain compounds of a suitable boiling point and heat stability, for example, phenanthrene and methylnaphthalene, in small quantities.
The heat-transfer medium compositions of this invention are fluid at ambient temperature, undergo virtually no decomposition at approximately 360° C. and can be used continuously over an extended period of time even at temperatures as high as 400° C. The compositions of this invention thus show the highest working temperature among organic heat-transfer media and they are useful for chemical reactors operated at high temperature and for solar heat power plants. Since the heat-transfer medium compositions of this invention boil in the vicinity of 250° C., they are used under pressure when the working temperature exceeds their boiling point.
The heat-transfer medium compositions of this invention show the highest level of heat resistance among organic heat-transfer media and are extremely useful for high-temperature equipment. In addition, they are easy to handle as their melting point or solidification point is equal to or below ambient temperature.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a graph showing the results of the heat stability tests run on the heat-transfer medium compositions.
FIG. 2 is a graph showing the relationship between temperature and vapor pressure on the heat-transfer medium compositions.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
This invention will be described in detail with reference to the accompanying examples and comparative examples.
EXAMPLE 1
Composition A containing 20.0% by weight of biphenyl and 80.0% by weight of diphenyl ether, Composition B containing 26.5% by weight of biphenyl and 73.5% by weight of diphenyl ether, Composition C containing 30.0% by weight of biphenyl and 70.0% by weight of diphenyl ether and Composition D containing 40.0% by weight of biphenyl and 60.0% by weight of diphenyl ether were prepared, diphenylene oxide was added to each composition in the proportion shown in Table 1, and the solidification point of each of the resulting heat-transfer medium compositions is shown in Table 1.
EXAMPLE 2
Heat-transfer medium composition 1 containing 85% by weight of Composition B and 15% by weight of diphenylene oxide, heat-transfer medium composition 2 containing 78% by weight of Composition C and 22% by weight of diphenylene oxide, heat-transfer medium composition 3 containing 78% by weight of ethylbiphenyl and 22% by weight of diphenylene oxide (solidification point -0.8° C.) and Composition B were submitted to a heat stability test by heating the specimens at 360° C. or 390° C. for 30 days in an atmosphere of nitrogen in an autoclave. The heat-transfer medium compositions other than 1 and 2 were tested for comparison. The passage of time and change in pressure are shown in FIG. 1 and the amount and composition of gases evolved and changes of physical properties in the heat stability test at 360° C. are shown in Table 2 and those in the test at 390° C. in Table 3. Gas-chromatographic analyses before and after the heat stability test detected no new peaks near the main components of heat-transfer medium compositions 1 and 2. Moreover, the vapor pressures of the heat-transfer medium compositions 1 and 2 and Composition B were measured. The results are shown in FIG. 2.
TABLE 1______________________________________ Solidification point ofComposition Proportion of heat-transfer mediumProportion diphenylene oxide compositionKind (wt. %) (wt. %) (°C.)______________________________________A 100 0 12.4A 90 10 8.6A 85 15 8.2A 80 20 8.4B 100 0 12.3B 95 5 10.4B 90 10 8.5B 85 15 7.3B 80 20 9.4B 79 21 9.4B 78 22 12.6B 77 23 14.2C 100 0 14.4C 90 10 14.0C 85 15 11.1C 80 20 9.9C 78 22 11.4C 77 23 14.2D 100 0 26.6D 95 5 25.6D 90 10 24.2D 85 15 22.8D 80 20 21.4D 75 25 20.5D 70 30 25.5______________________________________
TABLE 2______________________________________Heat stability test at 360° C. Heat-transfer medium composition 1 2 3______________________________________Proportion of components (wt %)biphenyl 22.5 23.4 --dipheny ether 62.5 54.6 --diphenylene oxide 15 22 22ethylbiphenyl -- -- 78Gases evolved (ml.) 69 73 859Composition (vol. %)H.sub.2 67.8 60.3 47.8CH.sub.4 18.2 26.0 25.2CO 5.8 5.7 2.4CO.sub.2 7.4 6.6 5.5C.sub.2 H.sub.4 ND*.sup.1 ND NDC.sub.2 H.sub.6 ND ND 18.0C.sub.3 H.sub.8 ND 0.7 0.9C.sub.4 H.sub.10 0.8 0.7 0.2Changes in properties (before test/after test)Specific gravity*.sup.2 1.074/1.073 1.077/1.078 1.035/1.033Viscosity 3.7/3.8 3.8/3.8 5.5/5.5(cp/25° C.)precipitation trace/trace trace/trace trace/traceresidual carbon <0.01/<0.01 <0.01/<0.01 <0.01/<0.02(wt %)Total amount of dis- 98.0/98.0 98.0/98.0 98.0/98.0tillate in distilla-tion test (vol %)______________________________________ *.sup.1 Not detected, *.sup.2 25/4° C.
TABLE 3______________________________________Heat stability test at 390° C. Heat-transfer medium composition Com- 1 2 position B______________________________________Gases evolved (ml.) 60 60 53Composition (vol. %)H.sub.2 83.2 83.2 76.0CH.sub.4 4.7 5.6 9.5CO 5.6 5.6 7.3CO.sub.2 3.7 2.8 3.1C.sub.2 H.sub.4 ND*.sup.1 ND NDC.sub.2 H.sub.6 1.9 1.9 3.1C.sub.3 H.sub.8 0.9 0.9 1.0C.sub.4 H.sub.10 ND ND NDChanges in properties (before test/after test)Specific gravity*.sup.1 1.074/1.072 1.077/1.077 1.061/1.060Viscosity 3.7/3.8 3.8/3.7 3.7/3.6(cp/25° C.)precipitation trace/trace trace/trace trace/traceresidual carbon <0.01/<0.01 <0.01/<0.04 <0.01/<0.01(wt %)Total amount of dis- 98.0/98.0 98.0/98.0 98.0/98.0tillate in distilla-tion test (vol %)______________________________________ *.sup.1 Not detected, *.sup.2 25/4° C.
|
The heat-transfer medium compositions of this invention contain biphenyl, diphenyl ether and diphenylene oxide with diphenylene oxide added in a proportion of 1 to 30% by weight and they are useful for high-temperature equipment such as chemical reactors and solar heat power plants for their long-term serviceability in the vicinity of 400° C. and their fluidity at ambient temperature.
| 2
|
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a non-provisional application which claims benefit under 35 USC §119(e) to U.S. Provisional Application Ser. No. 61/247,313 filed Sep. 30, 2009, entitled “Slim Hole Production System,” and to U.S. Provisional Application Ser. No. 61/247,386 filed Sep. 30, 2009, entitled “Producing Gas and Liquid from Below a Permanent Packer in a Hydrocarbon Well,” and also to U.S. Provisional Application Ser. No. 61/247,331 filed Sep. 30, 2009, entitled “Double String Pump for Hydrocarbon Wells,” all of which are incorporated herein in their entirety.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] None.
FIELD OF THE INVENTION
[0003] This invention relates to pumping liquids from hydrocarbon wells that are producing natural gas.
BACKGROUND OF THE INVENTION
[0004] The process of drilling hydrocarbon wells results in many wells with small diameter tubing or casing in the hydrocarbon bearing zone. Whether problems were encountered during drilling and more casing strings had to be installed than were originally anticipated. Since each string of casing is inherently smaller in diameter than the previously installed string to allow the successive casing string to be installed through the previous casing strings. For whatever the reason, many wellbores exist with casing in the hydrocarbon bearing zone with a diameter of less than three inches. When these wells are producing some amount of gas, the flow rate is sufficient to entrain and carry the liquids with the gas to the surface. Eventually, these slim holes mature to the point that the gas flow rate is not sufficient to carry the liquids to the surface. At the same time, there is still enough gas in the formation to continue to provide an economic incentive to keep the well open and producing.
[0005] Typically, some have installed coiled tubing that has a much smaller diameter than the small diameter casing to use the same gas productivity in the well to flow upwardly at a faster rate and keep the liquids entrained with the gas. This may work for a while, but the productivity of gas wells eventually diminishes to a point where it must be shut in.
[0006] In an ideal world, production tubing would be installed and a rod pump installed to positively pump the liquids from the bottom of the well and allow gas production continue for the longest potential time and greatest potential recovery. However, many slim holes are not large enough to accommodate production tubing in which a rod pump can operate.
SUMMARY OF THE INVENTION
[0007] The invention more particularly includes a system for producing liquids and solids from the bottom of a slim hole natural gas well where the system comprises a string of casing installed in a wellbore where a lower end of the casing string is near the bottom of the wellbore and a pump including a barrel and a plunger is inserted into the casing string such that the barrel is secured to the casing near the lower end of the casing string. A string of hollow rod is disposed within the casing string such that an annulus is formed around the hollow rod string within the casing and where the hollow rod string is connected to the plunger that is positioned within the barrel of the pump for movement up and down the barrel and liquids are produced to the surface from the plunger up through the hollow rod string.
[0008] In a preferred arrangement, check valves are placed at intervals in the hollow rod string equivalent to expected pumped volume per pump cycle to aid in transporting solids to surface. Solids and liquid will advance from one ball check to at least the next per pump cycle on low liquid volume wells.
[0009] In another aspect, the invention more particularly comprises a process for producing liquids and solids from the bottom of a cased slim hole natural gas well where the process includes installing a pump at the end of a string of hollow rod string where the pump includes a barrel and a hollow plunger and where the hollow plunger is connected to and in fluid communication with the hollow rod string. The plunger includes a traveling valve to admit liquids into the hollow interior of the plunger and the barrel is secured to the inside of the casing wherein an annulus is formed between the inside of the casing and the outside of the hollow rod string. The process further includes raising and lowering the plunger to draw liquids through the standing valve and through the traveling valve and eventually into the hollow rod string so that natural gas is produced through the annulus to the surface.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The invention, together with further advantages thereof, may best be understood by reference to the following description taken in conjunction with the accompanying drawings in which:
[0011] FIG. 1 is a cross section of a conventional wellbore with rod pump installed to produce liquid from the bottom of the wellbore;
[0012] FIG. 2 is a cross section of a slim hole wellbore with hollow rod pump of the present invention installed to produce the liquids and allow continuous production of the natural gas; and
[0013] FIG. 3 is an exploded perspective view of a hollow shear tool for providing preferred breakaway for the production system of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0014] Turning now to the preferred arrangement for the present invention, reference is made to the drawings to enable a more clear understanding of the invention. However, it is to be understood that the inventive features and concept may be manifested in other arrangements and that the scope of the invention is not limited to the embodiments described or illustrated. The scope of the invention is intended only to be limited by the scope of the claims that follow.
[0015] A hydrocarbon well having a internal diameter in the hydrocarbon bearing zone of less than about 3 inches is generally described as a slim hole well. Many such slim hole wells have accessed rich hydrocarbon deposits and produce natural gas and recoverable liquids. Typically, these slim hole wells produce sufficient gas to entrain and carry most liquids that were produced from the formation to the surface due to the high gas flow rate. Both the liquids and gas are collected and if the liquids comprise hydrocarbons, they are taken to market. Typically the liquid by-product is water which is disposed of. As a slim hole well produces natural gas over time, its flow rate gradually diminishes until liquids start accumulating at the bottom. High production rates may last many months or may last many years. However, gas rates inherently diminish as the reservoir is drained. As the gas rate diminishes, less of the liquid is carried with the gas flow to the surface such that a liquid volume at the bottom of the well is above the perforations that allow the gas into the wellbore. Although gas may continue to bubble through the liquid, the diminishing production rate typically gets quite choked down to a substantially lower rate.
[0016] In a conventionally sized well, operators typically install a rod pump. For example, as shown in FIG. 1 , a conventional wellbore, generally indicated by the arrow 10 , is shown formed or drilled into the ground G. According to conventional procedures, casing 12 has been inserted into the wellbore and sealed against the wall of the wellbore with cement 15 whereafter perforations 18 have been punched through the casing 12 and through the cement 15 and into a hydrocarbon-bearing formation in the ground G by explosive charges. Hydrocarbons in the hydrocarbon-bearing formation are then enabled to flow into the wellbore 10 through perforations 18 where natural gas and other gases would ascend up the wellbore through annulus 19 while liquids accumulate at the bottom of the wellbore 10 . The liquid level is drawn down by a production system including a pump, generally indicated by the arrow 20 , which is associated with a production tubing 50 . The pump 20 and production conduit 50 are run into wellbore 10 separately with the production conduit 50 being first inserted into the wellbore 10 . The production tubing 50 is sufficiently smaller than the casing 12 so that gas is easily able to flow up to the surface through annulus 19 . The production tubing 50 also has an open bottom end 51 preferably below the lowest of the perforations 18 and above the bottom of the wellbore 10 . Production tubing further includes a segment 52 , generally called a seating nipple, that includes an inside contour and dimension to receive barrel 30 and seal the barrel in place. Seating nipples typically have a shoulder stop or a reduction of the interior dimension also referred to as “ID”, and a highly machined surface or polished bore for packing seals on barrel 30 to engage into. Thus, the barrel 30 is installed after the production conduit 50 , but may be sealed in seating nipple 52 and therefore sealed and isolating the interior 55 of the production tubing 50 from the annulus 19 of casing 12 . The production tubing 50 is therefore divided into a small segment at the bottom, called a quiet zone 53 and a production path 55 above the seating nipple 52 .
[0017] The pump 20 includes a plunger 30 arranged to move up and down within the barrel 40 . The plunger 30 is attached to the bottom end of a sucker rod string 22 and is able to move up and down within the barrel 40 that is firmly connected or locked into the seating nipple 52 , but it should be understood that the periphery of the plunger 30 and the interior of the barrel 40 are each machined and sized so that any liquid flow around the plunger 30 is substantially restricted. The preferred path for liquids to travel through the barrel 40 is also through the interior of the plunger 30 . Below the barrel 40 is a strainer nipple 42 having a number of holes to allow liquids or gas that is in the quiet zone 53 to pass into the barrel through stranding valve 44 . Standing valve 44 is shown to be a ball and seat, but may be any suitable one-way valve technology. As the plunger 30 is lifted relative to the barrel 40 , liquids are drawn up through the strainer nipple 42 and through standing valve 44 to fill the space in the barrel 40 below the plunger 30 . The plunger 30 includes a travelling valve 34 that like the standing valve 44 , is shown as a ball and seat, but may be any suitable one-way valve technology. As the plunger 30 is lowered in the barrel 40 , standing valve 44 closes to keep liquid in the barrel but unseat the travelling valve so that the liquids in the barrel below the plunger 30 enter and flow into the plunger 30 . Liquids that were already in the plunger 30 before the plunger began its downward movement in the barrel exit the top of the plunger 30 through one or more vent holes 36 . Liquids that pass out of the vent holes 36 fill the production path 55 and are eventually delivered to the surface.
[0018] In a slim hole well, there simply is not room for a string of production tubing 50 to be installed that maintains annulus 19 for gas flow while accommodating a barrel and plunger inside the production tubing.
[0019] A solution for producing liquids at the bottom of slim hole wellbores is shown in FIG. 2 where like elements are presented with the same reference numbers used in FIG. 1 , but are identified with reference numbers that are three digit reference numbers with the first digit being “1” where the corresponding element in FIG. 1 has a two digit reference number. What should be seen as different about the invention as compared to the conventional arrangement is that the pump 120 is connected to hollow rod string 125 and arranged to pump the liquid up the axis of the hollow rod string. Secondly, there is no production tubing equivalent to production tubing 50 in FIG. 1 . The barrel includes a perforated nipple 142 with a pipe lock 160 attached to the bottom or distal end of the perforated nipple 142 . Pipe lock 160 includes dogs 162 that are deployed radially outwardly to lock into the casing 112 and hold the pipe lock 160 , perforated nipple 142 and barrel 140 in position near the bottom of the wellbore 110 . The perforated nipple 142 is attached to the barrel 140 by a hollow shear tool 126 that will be more fully described in reference to FIG. 3 , below. As natural gas continues to be produced from the formation through perforations 118 , the gas is allowed to rise up through annulus 119 outside of the hollow rod string 125 . Liquids that are produced descend from the perforations 118 and are drawn through holes in the perforated nipple 142 as the plunger 130 is lifted upwardly in the fixed barrel 140 . The liquid is drawn through standing valve 144 which is a one-way check valve of any suitable form to allow flow up into barrel 140 , but not down into the perforated nipple 142 . When plunger 130 descends in barrel 140 , standing valve 144 seats or closes and travelling valve 134 opens to allow the liquids in the working space 146 of the barrel 140 to enter into the plunger cavity 136 . Liquids in the plunger cavity 136 are pressed up through check valve 145 and into production path 155 inside the hollow rod string 125 .
[0020] Space in a slim hole is limited and liquid flow into the perforated nipple 142 may enter radially and may enter axially through core 163 of pipe lock 160 . The dogs 162 are spaced around the pipe lock 160 to generally center the barrel 140 and perforated nipple 142 and allow flow from below the pipe lock 160 to the perforated nipple 142 between the dogs. Typically three or four dogs 162 are used to hold the pipe lock 160 in position with respect to the casing 112 .
[0021] One aspect of the present invention is that it is preferred that any solids such as sand or other particles are produced with the liquid. The small diameter of the hollow rod string 125 along with check valves spaced apart up the length of the rod string 125 to the surface entrain the solids with the liquid by high flow rate and when the pump 120 ends a pump cycle, each of the check valves 125 keep such solids from descending all the way to the plunger 136 . In other words, each stroke of the plunger 130 may move the same volume of liquid, but the liquid moves far closer to the surface at a higher velocity so that the entrained solids are more likely to be carried farther up the production path 155 within the hollow rod string 125 during each pump operation cycle. Moreover, check valves such as shown at 145 are provided within the production path 155 so that when a pumping cycle is ended and the pump 20 is idled, the particles only settle down to the last check valve each particle may have passed. Ideally, by calculating the wellbore volume that liquid will be allowed to occupy and by spacing the check valves or ball checks within the string so that the volume between them does not exceed a pumping cycle volume then each operating cycle would cause the particles to pass through at least one check valve. Again, with the smaller diameter in the production path 155 , a pump rate can set at or above the lift velocity required for the well and re-entrainment of the solids into the liquid flow should be quicker and more certain.
[0022] In one further preferred aspect, a rod rotator may be installed at the top of the well near the location where the lifting mechanism attaches to the rod string 125 . The rod rotator rotates the hollow rod string 125 and spreads any wear from the up and down motion evenly around the outside of the sucker 125 to extend the life of the rod string 125 . Also, with the rod string 125 being hollow, it will likely and preferably have a larger diameter than equivalent non-hollow sucker rod of the same strength and will therefore have a larger radius distributing any load on the inside of the casing 112 in a manner that will reduce the cutting or damaging wear on the casing 112 .
[0023] It should further be understood that while the plunger 130 is shown with outside walls spaced from the inside surfaces of the barrel 140 , the adjacent surfaces of the outside of the plunger 130 and inside of barrel 140 are machined with close tolerances to prevent liquids from passing through the gap. As noted above, a series of check valves, such as check valve 145 are placed at intervals up the hollow rod string equivalent to expected pumped volume per pump cycle to aid in transporting solids to surface. Solids and liquids are arranged to advance from one check valve 145 to at least the next check valve 145 per pump cycle on low liquid volume wells.
[0024] Turning now to FIG. 3 , one particular aspect of the invention it to provide a well operator a way to most easily get back into the wellbore 110 in the event that the pump 120 needs to be withdrawn and the pipe lock 160 is corroded into the casing 112 . A hollow shear tool 162 provides a “weakest link” in the production system so that most of the string is recovered and that other tools may be used to recover only a small portion of the string nearest the most likely to be stuck element and that being the pipe lock 162 . The arrangement and operation of the hollow shear tool 162 will now be explained. The hollow shear tool 162 comprises three segments. Base segment 180 includes screw threads 180 a to attach to the perforated nipple 142 with ring segment 181 overlying the upper, smaller diameter portion 180 c of base segment 180 . The ring segment slides down smaller diameter portion 180 c until it contacts shoulder 180 b . Breakaway segment 182 also slides over smaller the diameter portion 180 c until holes 184 generally align with groove 188 in smaller diameter portion 180 c . Breakaway segment 182 , like base segment 180 includes screw threads that are arranged to attach to the hollow rod string plunger 140 . O-rings 186 a and 186 b are provided to seal the hollow interior passageway from the outside of hollow shear tool 162 . With a preselected number of screws screwed into holes 184 and into groove 188 , a predetermined breakaway strength can be provided so that when a tension between the barrel 140 and perforated nipple 142 exceeds the predetermined breakaway strength, the breakaway portion 182 will separate from the base portion. The predetermined breakaway strength may be easily tested using conventional machine shop stools such as a press and pressure gauge by removing ring segment 181 and inserting a number of screws 185 and applying compression force until the screws break. The screws 185 , in the arrangement of the hollow shear tool, should provide the same breakaway strength in compression and tension. The inventor expects that breakaway strengths of roughly 10,000 pounds or 15,000 pounds may be achieved and using stronger or weaker materials would expand the capacity range of such an arrangement. Clearly, the ease at which the breakaway strength may be successively measured should provide confidence in the actual breakaway strength. Screw holes that are not used are preferably blinded off to reduce the possibility of leaking.
[0025] Finally, the scope of protection for this invention is not limited by the description set out above, but is only limited by the claims which follow. That scope of the invention is intended to include all equivalents of the subject matter of the claims. Each and every claim is incorporated into the specification as an embodiment of the present invention. Thus, the claims are part of the description and are a further description and are in addition to the preferred embodiments of the present invention. The discussion of any reference is not an admission that it is prior art to the present invention, especially any reference that may have a publication date after the priority date of this application.
|
The invention relates to a slim hole production system for pumping liquids to the surface of a hydrocarbon well and especially a hydrocarbon well that is producing both natural gas and liquid liquids where the diameter of the hole in the production area is too small to get production tubing and a sucker rod into a productive arrangement. The slim hole pump includes a hollow tube that raises and lowers the plunger and carries the liquids to the surface and uses the annulus to produce the gas.
| 4
|
FIELD OF THE INVENTION
The present invention relates to a skimming system for removing a floating layer from a water surface, said system comprising at least one guide element that is movable relative to the floating layer, which guide element is provided with at least one floating layer removal unit.
The present invention also relates to a floating layer guide element for use in the skimming system.
The present invention furthermore relates to the use of the skimming system in removing a floating layer containing oil, chemicals, plants or algae from a water surface.
DISCUSSION OF THE BACKGROUND
Such skimming systems provided with guide elements are generally known, they are used in case of calamities, for example, for removing substances, usually chemical substances such as oil or oil-like contaminations, from the water surface on which said substances form a so-called floating layer.
A skimming system of the above type is known from EP-A-0 059 717. The skimming system that is known therefrom comprises at least one guide element that is movable relative to the floating layer. The guide element is connected by means of tow cables to the oil slick removal unit that is towed through the water by a vessel. While said unit is being towed through the water, oil is concentrated in a unit in the form of a fixed collecting box, from where the oil/water mixture is pumped into one or more storage units.
A drawback of the known system and the known method of removing oil from the water surface is that they are not always very effective in optimally removing various types of oil in practice.
SUMMARY OF THE INVENTION
The object of the present invention is to provide an improved skimming system by means of which the floating layer on the water surface can be removed in a more effective manner.
In order to accomplish that object, the skimming system according to the invention is characterised in that said at least one floating layer removal unit is provided with at least one collecting container that is detachably attached to the guide element.
The advantage of the skimming system according to the invention is that the collecting container can be exchanged and be substituted for another collecting container. This is furthermore advantageous in particular when the removal unit is provided with floating layer removal means that are generally attached to the collecting container, such as brushes (usually driven brushes), paddles, discs, pumps and/or overflow means. The fact is that it is possible in that case to obtain the degree of flexibility as regards the most optimum way of handling the removal of the oil slick that is very important in practice. It has become apparent that the effectiveness of the oil removal operation depends inter alia on factors such as: the nature and the composition of the floating layer, the viscosity, the layer thickness, the direction of the current, the velocity at which the floating layer moves, the degree to which the layer is mixed with water, the amount of air bubbles in the oil, the pumpability, and the local conditions, such as the waves, the temperature, the force and the direction of the wind, the environment etc. When the present invention is used, the desired floating layer removal means can be advantageously selected by exchanging the collecting container to which said means are already attached. Moreover, the aforesaid factors considered to be of paramount importance for the local situation can be optimally taken into account when making the aforesaid selection.
Exchanging the collecting container with removal means attached thereto for the purpose of carrying out an oil removing operation geared to the situation at hand is not only easy, but it is also cheaper and can be carried out in less time on site than detaching the old floating layer removal means and fitting the new one, which was previously necessary. A quick exchange in particular of the floating layer removal means in question is moreover important in order to be able to quickly repair any malfunctions on site.
Another embodiment of the skimming system according to the invention is characterised in that the skimming system comprises adjusting means by which the removal unit or the collecting container can be adjusted for height.
If the collecting container is vertically adjustable, the removal means attached thereto are automatically adjusted for height as well upon vertical adjustment thereof. Said vertical adjustment not only makes it easier to detach and exchange the collecting container, but in addition the floating layer removal means can be moved to a desired depth in or below the floating layer so as to realise an optimum removal of the floating layer, taking into account the aforesaid local factors. In all the situations in which brushes, paddles, discs and/or overflow means provided with an overflow wall are used, said vertical adjustment is advantageous in practice.
When such overflow means are used, it is possible to adjust the oil-water ratio by adjusting the height of the floating layer removal means. Because not all oil types exhibit the same degree of pumpability under certain circumstances, said pumpability can be influenced by admitting more water or less water into the collecting container together with the floating layer by adjusting the height, which water is subsequently pumped out.
Another embodiment of the skimming system according to the invention is characterised in that said at least one collecting container has an inlet that is provided at a location where water and floating layer are mixed to a minimum extent.
The inventor has also realised that an important reason for the discrepancy between the theoretically obtainable effectiveness of an oil slick removing operation and that which is actually realised in practice is the fact that turbulences and short waves occur at the location where the floating layer is being collected and pumped out, in particular at the interface between oil and water. These factors lead to oil and water being locally mixed in an uncontrolled ratio.
The turbulences in the collected oil that lead to the aforesaid undesirable mixing are often caused by the movement both of the vessel, which displaces comparatively much water, and of the guide elements, which are usually supported on pontoons and which have less draught than the vessel. The presence of an excess of air in the oil may also be caused by the fact that the collected oil is sucked in and forced out with too much force, however, which also has an adverse effect on the effectiveness. If the collecting point of the oil and the discharge point are located too close to the side wall of the vessel, this may lead to the aforesaid turbulence and short waves at the location of the collecting point under certain circumstances, for example sailing against the current, incoming wind or (overly) rapid skimming. For that reason the collecting point must be provided at the location on the guide element where the extent to which water and/or air are mixed with the floating layer is minimal. The idea is that the interface between oil and water and/or air will only be affected to a small extent and will still be reasonably flat when the location of the collecting point or intake point is suitably selected, so that oil can be removed in an effective manner. In addition, the dimension of the oil layer to be pumped out will be known more precisely in that case and it will be easier to gear the vertical adjustment of the system thereto, as a result of which the level efficiency will be enhanced even further.
Another embodiment of the skimming system according to the invention is characterised in that said at least one guide element forms a system of one or more interconnectable guide elements extending at specific angles relative to each other.
Such a system can be towed by a vessel via tow cables, but it may also be provided close to the vessel or, for example in case of a river, be fixed to the river banks by means of tow cables. The guide elements may be interconnected to obtain a V-formation or a reverse V-formation in such cases, depending on which formation produces the best results. Flexibility in the use of the skimming system according to the invention also applies as regards the selection of the location of the removal unit(s) with detachable collecting containers in said possibly harmonica-shaped formation.
Furthermore preferably, said at least one guide element is a rigid construction, and the interconnectable guide elements are hinged, so that the guide elements, will take up little space during transport, in particular on the deck of a vessel, in folded-up or collapsed condition or detached from each other.
The advantage of this is furthermore that a compact skimming system that can be rendered operational in a short time is obtained, which system is nevertheless capable of spanning a wide oil removal area. In addition, collecting containers may be disposed at several locations in the guide elements.
BRIEF DESCRIPTION OF THE DRAWINGS
The skimming system according to the present invention will now be explained in more detail with reference to the figures below, in which like parts are indicated by the same reference numerals, and wherein:
FIG. 1 is a schematic representation of the skimming system according to the invention, with the two skimming elements in unfolded condition;
FIG. 2 shows a possible embodiment of an unfolded guiding system for use in the skimming system that is shown in FIG. 1 ;
FIG. 3 shows the guide element of FIG. 2 in folded condition;
FIG. 4 shows a further elaborated representation of a removal unit for use in the skimming system that is shown in FIG. 1 ;
FIG. 5 is a perspective view of a collecting container for use in the removal unit of FIG. 4 ; and
FIGS. 6A , 6 B and 6 C show the skimming system according to the invention with opening angles of 120°, 90° and 60°, respectively, between the guide elements thereof.
DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 schematically shows a skimming system 1 , in this case comprising a vessel 2 and one or more series of floating layer guide elements 3 - 1 , 3 - 2 , which are coupled together and to the vessel 2 . It is also possible to tow said one or more of series of guide elements 3 beside or behind the vessel 2 by means of tow cables or, for example in case of contamination of a waterway, to fix a system of guide elements 3 to the banks by means of tow cables, in which case a propulsion vessel is not needed but advantageous use is made of the current in the water. In FIG. 1 , the vessel 2 moves the skimming system 1 provided with the guide elements through the water in the direction indicated by the arrow, and a contaminating substance that floats on the surface, e.g. oil, to be referred to below as “floating layer”, collects between the guide elements 3 - 1 and 3 - 2 . In a special embodiment, the shell of the vessel may form part of the floating layer guide elements 3 in that the vessel 2 moves forward at an angle in that case.
The opening angle between said one or more guide elements 3 - 1 , 3 - 2 is preferably about 120°, or smaller, but it depends on the skimming velocity and the width of the floating layer. In case of a smaller skimming angle, a higher skimming velocity can be obtained, and conversely. In case of the aforesaid skimming angle, a velocity of 2 miles/hour is achievable if fixed-structure guide elements are used. Such guide elements usually have a strong lattice construction, so that a stable and rigid structure is obtained, which enables an effective guidance of the moving floating layer along the walls of the guide elements 3 . One or more float bodies are provided in the guide element 3 in a manner that is known per se, so that the guide element is self-floating.
The oil passes between the guide elements 3 towards a removal unit 4 as shown in FIG. 4 , which is configured as a so-called “skimmer housing”. Disposed in the removal unit 4 is a collecting container 5 that is vertically adjustable to a desired depth, into which the floating layer consisting of oil and water flows when an overflow system is used. Further floating layer removal means 6 (only shown schematically), such as moving brushes, paddles, discs, by means of which the concentrated floating layer is moved into the collecting container 5 , may be attached to the collecting container 5 . When discs or brushes are used, the oil is collected and removed in pure form, i.e. without any additional free water, in that the oil adheres thereto as a result of its hydrophobic action, which oil is subsequently scraped off and lands in the collecting container, from which it is then pumped out.
The drawings of FIGS. 4 and 5 schematically show an overflow system with an overflow wall 7 . Via the overflow wall 7 , which may be adjusted for height together with the collecting container 5 , the floating layer flows into the container 5 in the layer thickness as set and in the desired oil-water ratio. According to another possibility, only the overflow wall 7 is provided with means (not shown) for adjusting only the wall 7 (in that case) for height. The schematically indicated means M for guiding and vertically adjusting the collecting container 5 are manually driven in some cases, but usually they are driven hydraulically or possibly pneumatically, and they may be operated by remote control. Suitable pressure and/or current velocity sensors connected to the adjusting means M may be provided near the overflow wall 7 and/or in the collecting container 5 for influencing the influx of the floating layer momentarily by adjusting the height of the collecting container 5 accordingly.
FIG. 5 shows the separate—detached—collecting container 5 , which may be provided with a lifting eye, via which the container 5 can in principle be adjusted for height by means of a hoisting device. The container 5 as shown herein is provided with a hinged grid R, which, in the raised position thereof, collects debris floating on or in the layer of oil. In FIG. 5 the grid R is shown in lowered condition, when it is lowered a little further, however, the collected debris will be carried along by the current under the container 5 and thus be removed from the inlet into the container.
The skimming system 1 is provided with one or more pumps that are connected to the collecting container 5 . The pumps 8 may be present on one or more of the guide elements 3 , but they may also be present on the collecting container 5 , on the shore and/or on the vessel 2 . Examples of suitable pumps 8 are: vacuum pumps, force pumps, suction pumps and/or so-called ejectors. In practice, hydraulic plunger pumps or force pumps are frequently used for pumping highly viscous substances. When highly viscous oil is to be pumped, it will be advantageous to pump it with comparatively more water, so that the capacity of the companies is used more efficiently. The actual vertical adjustment of the overflow system may be adapted to this desired ratio. Said pumping takes place into or out of the storage tanks T 1 , T 2 that are present on the vessel 2 .
The inlet of the collecting container 5 , where the removal means 6 are present, is provided at a position on the guide element 3 where no excessive mixing of water and/or air with oil takes place. Generally, said position is located a considerable distance inter alia from the side walls and the propeller of the vessel 2 , so that the turbulence, the current, waves or wave reflections produced near or by the vessel 2 and/or the skimming frames 3 do not have an adverse or destabilising effect on the desired final ratio in particular of oil and water to be pumped.
In the embodiment of the skimming system 1 that is shown in FIG. 1 , the collecting container 5 is positioned approximately halfway along the V-shaped (in this embodiment) system of the guide elements 3 - 1 , 3 - 2 , in the apex of the V-shape, where the concentration point of the floating layer is located. The guide element 3 may be hinged in several points. The apex of the V-shape may point—as a reverse V—in a direction opposed to the direction of the current as indicated by an arrow, and the system may have a harmonica shape or a W-shape. Furthermore, the removal unit 4 may in principle be positioned at any desired location or locations. When a reverse V-formation is used, the oil is driven apart by the moving elements 3 and the concentration points of the floating layer are located at the ends of the two legs of the V. In that case the removal unit 4 , usually together with the collecting container 5 , will be present in said points.
In case of a malfunction of one of the guide elements 3 , the defective or damaged guide element can readily be exchanged for another by means of a hoisting tool. The guide elements 3 , which may be interconnectable for forming larger systems, if desired, and which may be collapsible, take up a little space on board the vessel 2 , they can be stored individually or in collapsed or folded-together condition, whilst large skimming widths can be realised.
One or more tow cables may be provided between the skimmer housing 4 and/or one end of one of the arms 3 for the purpose of keeping the skimming system 1 stable during movement from the water containing the various types of oil and make it easier to maneuver the skimming system 1 .
In addition to the foregoing it is noted that it is advantageous, in particular when strong winds prevail, to only provide one or more guide elements 3 - 1 , 3 - 2 on the lee side instead of on both sides. After all, there is less turbulence in the water/oil surface on the lee side, especially at the interface between water and oil.
If the guide element 3 is provided with one or more float bodies, as already explained in the foregoing, the element 3 will be self-floating. FIG. 1 shows that the tow cables hold the skimming system 1 in place, in this case against the wall of the vessel 2 . The system 1 moves free from the vessel 1 in that case, as a result of which the relative movements of the vessel 2 and the skimming system 1 take place independently of each other, at least in vertical direction. This enables the skimming system 1 to move along with the local swell in the floating layer, and as a result a higher degree of precision regarding the layer thickness of the floating layer that is being removed can be achieved in combination with the vertically adjustable wall 7 and/or the container 5 . This has a positive effect on the oil/water ratio of the mixture that is being pumped out and it is advantageous with a view to filling the storage tanks T 1 and T 2 in an efficient manner.
Advantageously, a rubber protection bumper is provided at the location where the end U of a guide element 3 - 1 makes contact with the wall of the vessel 1 that moves independently of the element 3 - 1 . By making the protection bumper hollow and passing a pulling wire or chain therethrough, for example, the rubber protection bumper can be pulled firmly around the (usually curved) end of the element and be held in position thereon by exerting a pulling force on said wire or chain.
FIGS. 6A , 6 B and 6 C show opening angles of 120°, 90° and ° C., respectively, between the guide elements 3 - 1 and 3 - 2 of the skimming system 1 . The figures show how a tow cable 9 - 1 , which is fastened to the front side of the vessel 1 , branches off into two (in this case) tow cable parts 9 - 2 and 9 - 2 at the location of a branch point P, which tow cable parts are fastened to the one guide element 3 - 1 that may be present, at the location of the hinge point S thereof, and to the end of the other guide element 3 - 2 . If no element 3 - 1 is present, the tow cable part 9 - 2 may be fastened to the removal unit 4 . Securing the skimming system 1 by tow cables in this manner and towing it behind or along the vessel 1 appears to enable easier maneuvering when compared to the system of FIG. 1 . Furthermore it is easier to hold the skimming system in position against the vessel. This obtains in particular when the system is moved through the water at an angle as already explained before, because this requires less navigational skill on the part of the person at the rudder of the vessel 1 . It is advantageous if the tow cable parts include an angle of about 90° with each other at the location of the branch point P. The length of the various tow cables and tow cable parts is preferably adjustable, so that an optimum skimming result can be obtained by flexibly anticipating the constantly changing conditions and factors on site with due professional skill.
Providing it does not add to the self-weight of the skimming system 1 , a drive shaft may be provided at the hinge point S, if desired, at an angle of 90° thereto, making it possible to realise a certain degree of independence of movement between the guide elements 3 - 1 and 3 - 2 .
|
A skimming system for removing a floating layer from a water surface. The skimming system includes at least one guide element that is movable relative to the floating layer, which guide element includes at least one unit that catches the floating layer. The at least one removal unit includes at least one collecting container that is detachably attached to the guide element. The collecting container is furthermore vertically adjustable, so that it is not only easy to detach and exchange the collecting container but that it is moreover possible to position the floating layer removal means at a desired depth in or below the floating layer. In this way an optimum removal of the floating layer can be realized. The inlet of the collecting container is present at a location where the extent to which water is mixed with the floating layer is minimal.
| 4
|
RELATED APPLICATION(S)
[0001] This application is the United States national phase entry under 35 U.S.C. §371 of
[0002] International Patent Application No. PCT/EP2015/063140, filed Jun. 12, 2015, which is related to and claims the benefit of priority of German Patent Application No. DE 10 2014 108 705.4, filed Jun. 20, 2014. The contents of International Patent Application No. PCT/EP2015/063140 and German Patent Application No. DE 10 2014 108 705.4 are incorporated by reference herein in their entireties.
FIELD
[0003] The present invention relates to a bone screw system, especially a pedicle screw system, comprising a bone screw or a pedicle screw, resp., a receiving sleeve and a clamp screw adapted to be screwed into the latter, wherein the receiving sleeve includes a sleeve wall which forms a seat for a longitudinal support for the surgical connection of adjacent bone screws or, resp., pedicle screws and is provided with an internal thread, wherein the clamp screw is provided with an external thread and is adapted to be screwed into the internal thread of the receiving sleeve.
BACKGROUND
[0004] Bone screws and pedicle screws are known from the state of the art. They serve, for example, for the dorsal stabilization of the spinal column by means of transpedicular screwing. Pedicles screws are placed in the pedicles of adjacent vertebrae, whereupon an angularly stable connection is made between the pedicle screws which are axially superimposed and an axially extending longitudinal support or land. The pedicle screws and the longitudinal supports form a vertebral stabilizing system.
[0005] Usually a pedicle screw includes a screw shank extending in the axial direction and including an external thread to which a receiving sleeve, the so called tulip, is connected on the side of the screw head. Said tulip is substantially U-shaped having opposed wall portions and a gap formed therebetween and extending in the radial direction for the longitudinal support or land. An internal thread extending in the axial direction is introduced into the tulip. The longitudinal support is inserted in the gap of the tulip in the radial direction and is fixed by means of a locking element or a clamp screw, typically in the form of a stud screw or threaded nut, which is also referred to as set screw and is screwed into the internal thread.
[0006] When a set screw is attached to a pedicle screw, especially in the case of an open operation there is a risk of jamming due to tilted attachment of the set screw. This situation occurs in particular when the thread of the set screw and the internal thread of the tulip are twisted about approx. 180° when the set screw is attached, i.e. a threaded flank abuts a threaded flank, as illustrated in the enclosed FIG. 1 .
[0007] In the case of known pedicle screws, even when the set screw is correctly attached, slight tilting or jamming of the set screw relative to the axis of the pedicle screw and, resp., the tulip thereof may entail a “rough” attachment, which increases the risk of jamming. To make matters worse, in practical use the set screw is usually pressed onto the tulip with a certain force. Said axial pre-force may detrimentally result already in the set screw getting jammed with respect to the tulip, as the planar upper side of the tulip usually does not correspond to the thread geometry of the set screw.
[0008] Jamming may lead to the thread chamfer, especially the one of the set screw, being damaged. In the worst case, a so called “cross-threading” may occur, meaning that the set screw is tilted with respect to the longitudinal axis of the screw shank and the external thread thereof so far that the thread start of the set screw, viz. the lead-in thread turn or turns, engage(s) in the wrong thread turn of the internal thread of the tulip, which may lead to damage of the thread up to uselessness of the set screw and/or of the pedicle screw. A clicking when attaching the set screw which is caused by jamming will unsettle the user. The latter is not sure whether the thread has been damaged.
[0009] In order to reduce the afore-described problems, particular thread designs such as e.g. rectangular threads or undercut threads are known and are described to “reduce cross-threading”. However, correct attachment of the set screw appears to be the crucial action for avoiding damage of threads. For this purpose, pedicle screw systems are known in which a rotatable guide cap is mounted on the set screw and enables the set screw to be additionally guided in the tulip head thread. It is moreover known to chamfer the thread lead-in of the set screw, in other words to reduce the thickness thereof. In this way, engagement of the thread lead-in of the set screw into the thread lead-in of the tulip head is facilitated. Apart from that, there are systems offering a guide for the set screw so as to prevent the same from tilting with respect to the screw axis. This guide subsequently will be broken away. During percutaneous operation the coupled sleeve may prevent the set screw from tilting in numerous cases. During open operation a set screw starter instrument including a guiding sleeve aligning relative to the body may limit such problematic tilting.
[0010] The afore-described pedicle screw systems known from the state of the art are disadvantageously cost-intensive and complex. As a rule, they are not adapted to facilitate and reliably ensure correct attachment of a set screw to a pedicle screw. A screw driver including a guiding sleeve may prevent tilting to a restricted extent only, as said guiding sleeve requires a certain play for coupling. In addition, said sleeve restricts the surgeon's vision onto the bone or pedicle screw. An optimization of the chamfer improves finding the thread, but jamming may occur despite this measure. Jamming of a “chamfered” set screw is critical, as the latter may be damaged very easily due to the smaller wall thickness.
SUMMARY
[0011] Based on the afore-described state of the art, the object underlying the invention is to provide a bone screw system, especially a pedicle screw system, which facilitates and renders the correct attachment of a set screw to a bone or pedicle screw safer without any additional elements such as guiding sleeves etc. being required or the vision of the operating surgeon being reduced.
[0012] According to the present invention, this object is achieved by a bone screw system or, resp., pedicle screw system, wherein a thread turn of the internal thread on the lead-in side includes a widened lead-in region.
[0013] The present description is made with reference to a bone screw system and a bone screw, respectively. However, the invention relates especially to a pedicle screw system and a pedicle screw, respectively. The term bone screw is therefore meant to designate a pedicle screw and vice versa.
[0014] In accordance with the invention, the lead-in region is widened as compared to the residual and usual run of the thread turn. The internal thread of the receiving sleeve as well as the external thread of the clamp screw may be single-start or multi-start threads. In the case of multi-start threads it is of particular advantage when each thread turn includes a widened lead-in region and is widened on the lead-in side.
[0015] It is advantageously achieved by the widened lead-in region that the cross-sectional window available for engagement in a lead-in thread land of the clamp screw is increased vis-à-vis screw systems known from the state of the art. Even if the clamp screw is attached to the receiving sleeve in a tilted manner, i.e. in the case of attachment with non-aligned axes, there will be no “seizing” of the external thread and the internal thread. Rather, the external thread of the clamp screw may enter into the internal thread without any damaging contact with a threaded flank of the latter. Depending on the size of widening, the clamp screw may tilt without damage vis-à-vis the receiving sleeve with the alignment of the axes of the clamping screw and the receiving sleeve deviating more or less strongly. It is a particular advantage of the invention that with an increasing screwing depth into the internal thread the clamp screw gets aligned relative to the receiving sleeve. Such alignment is advantageously carried out automatically until the axes of the clamp screw and the receiving sleeve are aligned and the clamp screw is located straightly and correctly within the internal thread. Therefore it is no longer required for an operating surgeon to turn special attention to non-tilted attachment of the set screw, which considerably alleviates work and entails benefits in terms of time-saving.
[0016] The widened thread entry or thread turn start so-to-speak forms sort of a ramp in order to guide or lift a clamp screw or set screw initially obliquely attached or tilted during attachment, when it is further screwed into the actual thread turn, and to align the clamp screw or set screw again coaxially with respect to the internal thread of the receiving sleeve.
[0017] Preferably, the lead-in region is widened in the axial direction. Such widening especially efficiently prevents jamming or tilting of the clamp screw with respect to the axis of the receiving sleeve. Alternatively or additionally, the widening of the lead-in region may be formed in the radial direction, which brings about an especially simple positioning of the clamp screw in the radial direction relative to the receiving sleeve. This is of advantage especially for operations offering a strongly reduced vision.
[0018] In an embodiment the lead-in region includes a flank. Said flank may be inclined in the peripheral direction vis-à-vis the flank in the further run of the residual thread turn, i.e. outside the lead-in region. It may have a smaller inclination than the residual thread turn, but it may also rise especially into the internal thread. Preferably it is the flank of the lead-in region facing the threaded base. The inclination of the flank in the case of the flank facing the threaded base is preferably flatter and in the case of the flank facing the thread entry is preferably steeper than the inclination of the flank in the further run of the residual thread turn. It may correspond especially to 0.5 to 0.9 times, more preferably to 0.6 to 0.8 times and especially preferred to 0.7 times the inclination of the flank in the residual run of the thread turn. In the case of the flank facing the thread entry the respective inverse values are applicable. These inclinations enable the clamp screw to be easily aligned during screwing into the internal thread and at the same time prevent the threaded flanks from being excessively weakened and the internal and external threads from being seized. It is within the scope of the invention when both flanks of the lead-in region, i.e. the flank facing the threaded base and the flank facing the threaded lead-in, are configured in the aforementioned shape with deviating inclination. In this way, the lead-in window may be very large.
[0019] In particular, the cross-section of the thread turn, especially the cross-section in the radial direction, may correspond at the thread lead-in to 1.7 to 1.2 times, preferably to 1.6 to 1.3 times and especially preferred to 1.5 to 1.4 times the cross-section of the thread turn outside the lead-in region. Furthermore, the thickness in the axial direction of a threaded land provided between the lead-in region and an adjacent thread turn may be reduced as compared to the thickness of a threaded land between adjacent thread turns by less than 50%, preferably by less than 35% and especially preferred by less than 20%.
[0020] According to the invention, the lead-in region may extend into the internal thread differently far in the circumferential direction. It is preferred when the lead-in region extends in the circumferential direction over a radial portion between approx. 20° and approx. 135°, preferably between approx. 40° and approx. 115°, more preferred between approx. 60° and approx. 90°. In this way, the clamp screw finally is not aligned before it is screwed sufficiently far into the internal thread for required support inside the same so that repeated jamming or release of the clamp screw can be safely prevented. Moreover, the load capacity of the thread is weakened, as is inevitable by forming the lead-in region, only over a small part of the thread so that with particular advantage the load capacity of the thread remains almost unchanged.
[0021] In an embodiment of the invention the internal thread of the receiving sleeve and/or the external thread of the clamp screw is/are an undercut thread, especially an undercut buttress thread. The thread turn may as well have a T-shaped or L-shaped cross-section. This may especially cause the clamp screw to be clamped or secured inside the internal thread.
[0022] The screw system according to the invention may be a mono-axial or poly-axial system. This is to say that the receiving sleeve may be formed integrally with the bone screw or that the receiving sleeve may be adapted to be positioned as a separate element, especially arranged at an angular position relative to the bone screw on the latter. In the case of a mono-axial bone screw, the receiving sleeve is tightly connected to the shank thereof, for example manufactured in one piece, welded or soldered. In the case of a poly-axial bone screw, said screw may have an external thread portion manufactured as a separate shank component and having a spherical or (semi)-spherical screw head. The receiving sleeve may be arranged on the same to be adapted to be angularly positioned. The receiving sleeve may engage behind the screw head in the transitional area to the bone screw shank. In this way the receiving sleeve may be pivoted and/or rotated relative to the shank after screwing the bone screw into a bone so as to obtain a desired position and alignment substantially independently of the alignment of the shank. The undercut prevents the receiving sleeve from being removed from the shank head. Subsequently, the receiving sleeve can be fixed in position on the screw head of the bone screw by means of the clamp screw with the longitudinal support/land being interposed or by means of an additional screw element.
[0023] The object stated in the beginning is moreover achieved by a method of manufacturing a bone screw system according to the invention, especially a bone screw system according to any one of the enclosed claims, wherein the widening in the lead-in region is formed by milling, especially by milling the widening into the already formed thread turn, preferably by means of a T-groove cutter.
BRIEF DESCRIPTION OF THE DRAWING FIGURES
[0024] Further features and advantages of the present invention will be evident from the following exemplary and non-limiting description of the invention by way of a pedicle screw system as an example of a bone screw system by way of Figures. These Figures are merely schematic and merely serve for the comprehension of the invention, wherein:
[0025] FIG. 1 shows a cutout of a pedicle screw system showing the head area as an example of a bone screw system in a lateral view;
[0026] FIG. 2 shows a perspective representation of an internal thread of a pedicle screw head known from the state of the art;
[0027] FIG. 3 shows a perspective view of an internal thread of a pedicle screw head according to the invention; and
[0028] FIG. 4 shows a further embodiment of the internal thread according to the invention in a perspective view.
DETAILED DESCRIPTION
[0029] FIG. 1 illustrates the head area of a pedicle screw system 1 in a lateral view. The pedicle screw system 1 includes a pedicle screw 2 , a receiving sleeve 3 and a clamp screw 4 . The receiving sleeve 3 basically may be formed integrally with the pedicle screw 2 as a so called tulip or as a separate component. The latter may be arranged to be movable on the pedicle screw 2 so that a poly-axial pedicle screw system is formed in which the receiving sleeve 3 is adapted to be angularly positioned relative to the pedicle screw 2 . The following description will be given with reference to a receiving sleeve 3 formed integrally with the pedicle screw 2 ; it is also applicable to a poly-axial pedicle screw system, however.
[0030] The pedicle screw 2 is provided on the side opposed to the receiving sleeve 3 with an external thread not shown in the Figures by which it is adapted to be screwed into a pedicle canal of a vertebra (as an example of a bone). For this purpose, on the side of the receiving sleeve 3 the pedicle screw 2 is provided with a screwdriver engagement not shown in the Figures. The receiving sleeve 3 is substantially U-shaped including a hole 6 introduced in the same in the axial direction and including an internal thread 5 . In other words, the receiving sleeve 3 may be formed by removing material from a hollow cylinder on radially opposed sides in the axial direction and providing the hole of the hollow cylinder with the internal thread 5 . Two radially opposed sleeve wall portions 7 , 8 whose inner surfaces facing each other delimit the hole 6 and are provided with the internal thread 5 are retained from the hollow cylinder.
[0031] The clamp screw 4 in the form of a stud screw common for this purpose is provided with an external thread 9 and a front-face tool holder, for example a hexagonal recess, which is not shown in the Figures.
[0032] FIG. 2 shows the internal thread 5 of a pedicle screw system 1 as known from the state of the art. The internal thread 5 is configured to be a single-start thread. It has one single thread turn including a first thread portion 10 in the first sleeve wall portion 7 , a second thread turn portion 11 in the opposite sleeve wall portion 8 , a third thread turn portion 12 in the first sleeve wall portion 7 , a fourth thread turn portion 13 again provided in the opposite sleeve wall portion 8 etc. The thread turn portions 10 , 12 in the first sleeve wall portion 7 comprise a lead-in side 14 and a lead-out side 15 . The thread turn portions 11 , 13 in the second sleeve wall portion 8 equally comprise a lead-in side and a lead-out side. FIG. 1 illustrates the clamp screw 4 at the beginning of screwing into the receiving sleeve 3 . It is clearly visible that for correctly screwing its external thread 9 into the internal thread 5 the clamp screw 4 has to be aligned relative to the receiving sleeve 3 such that the axis 16 of the clamp screw 4 is congruent with the axis 17 of the internal thread 5 . FIG. 1 shows such positioning. It is obvious that especially in the case of polygonal pedicle screws and/or with a reduced vision and/or with poor accessibility such positioning may be very problematic.
[0033] FIGS. 3 and 4 illustrate a lead-in region 18 of the internal thread 5 of the receiving sleeve 3 configured according to the invention in two different embodiments. In the embodiment of FIG. 3 the lead-in region 18 extends over the entire peripheral length of the first thread turn portion 10 . When comparing the first thread turn portion 10 to the third thread turn portion 12 configured in a conventional way, it becomes obvious that the cross-section of the thread turn portion 10 is widened in the axial direction as compared to a first thread turn portion 10 configured in a conventional manner (cf. e.g. FIG. 1 ). In the shown embodiment only the first thread turn portion 10 is widened in this way, while the other thread turn portions 11 , 12 , 13 etc. conventionally have a constant cross-section. It is achieved in an advantageous manner by the widened lead-in region 18 that the cross-sectional window available for engagement with the lead-in thread land 19 of the clamp screw 4 is enlarged as compared to the state of the art. Even in the case of a tilted attachment of the clamp screw 4 to the receiving sleeve 3 , i.e. in the case of attachment with non-aligned axes 16 , 17 , no “seizing” of the external thread 9 and the internal thread 5 , and especially of the lead-in thread land 19 and the flank 21 of the first thread turn portion 10 can occur. Rather, the lead-in thread land 19 may enter without any damaging contact with the thread flank of the first thread turn portion 10 into the latter from the lead-in side 14 , namely depending on the size of the widening with more or less strongly deviating alignment of the axes 16 , 17 . With an increasing screwing depth into the internal thread 5 , the clamp screw 4 is aligned relative to the internal thread 5 until the axes 16 , 17 are finally aligned and the clamp screw can be straightly and correctly screwed into the internal thread 5 .
[0034] FIG. 4 illustrates a slightly deviating embodiment of the widened lead-in region 18 . In this embodiment, the lead-in region 18 extends less far into the first thread turn portion 10 in the peripheral direction. Moreover, the widening in the axial direction is smaller than in the embodiment of FIG. 3 . This entails little weakening of the axial thickness of the thread land 20 on the lead-in side 14 between the first thread turn portion 10 and the third thread turn portion 12 . Another difference consists in the fact that the thread turn of the internal thread 5 is configured to have an L-shaped cross-section.
|
A bone screw includes a receiving sleeve having a sleeve wall which forms a seat for a longitudinal support for the surgical connection of adjacent bone screws. The bone screw includes an internal thread. A thread turn of the internal thread has a widened lead-in region on the thread lead-in side.
| 0
|
CROSS-REFERENCE TO RELATED APPLICATION
This application is related to Ser. No. 07/944,619 filed Sep. 14, 1992, for Hydrogen Fluoride Alkylation Apparatus and Vapor Recovery Method to G. P. Partridge, Jr.; K. R. Comey, III; J. Mudra IV and L. K. Gilmer now U.S. Pat. No. 5,277,881.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention is an environmental safety apparatus in combination with means for using hydrogen fluoride. The invention is also a safety method of collecting an airborne release of hydrogen fluoride.
2. Description of the Related Art
The catalytic alkylation of an isoparaffin with an olefin to produce a branched paraffin is a commercially important process for producing high octane gasoline. In general, the process comprises the reaction of an isoparaffin such as isobutane with an olefin such as propylene, 1-butene, 2-butene or mixtures thereof in the presence of a liquid acid alkylation catalyst in a reaction zone. Reaction is followed by separation of the product and unreacted hydrocarbons from the liquid alkylation catalyst in a settling zone and purification of the alkylate product. If the isoparaffin is isobutane and the olefin is a butene, the alkylate product is isooctane. Alkylate product is used to enhance the octane number of automotive gasoline and aviation gasoline.
Anhydrous hydrogen fluoride is a particularly effective catalyst for the alkylation process. Though effective, the volatility and destructive effect of hydrogen fluoride on animal tissue has curtailed expanded use of this catalyst in the petroleum refining industry due to a concern over accidental releases.
There is a need in the petroleum refining industry for an apparatus and method which will contain an accidental release of hydrogen fluoride from a major process vessel.
SUMMARY OF THE INVENTION
The invention is an environmental safety apparatus for collecting an airborne release of hydrogen fluoride from a hydrogen fluoride utilizing means.
The environmental safety apparatus comprises a containment baffle defining a volume sufficient to substantially enclose the utilizing means. At least one hydrogen fluoride detecting means is mounted within the containment baffle. Flood means has a capacity to substantially flood the containment vessel with an aqueous liquid. Means is provided responsive to detecting means to activate the flood means. Means is provided to receive the aqueous liquid from the containment baffle.
The invention is used in combination with hydrogen fluoride utilizing means such as an alkylation process vessel, containment vessel or transportation vessel to capture an accidental airborne release of hydrogen fluoride. As a result, escape of the release is prevented and damage to the environment is prevented.
BRIEF DESCRIPTION OF THE DRAWING
The Drawing is a schematic flow diagram illustrating a preferred embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
The alkylation reaction is carried out between an isoparaffin and a monoolefin in the presence of alkylation catalyst. The preferred isoparaffin is isobutane. Isopentane is also used. Common monoolefins include propylene, isobutylene, 1-butene, 2-butene, pentylenes and mixtures thereof. The preferred monoolefin is a C 4 olefin, typically a mixture of 1-butene, 2-butene and isobutene. A typical C 4 olefin mixture is one fraction from a fluid catalytic cracking process comprising about 25 vol % 1-butene, 45 vol % 2-butene and 30 vol % isobutylene. Diolefins or higher functionality olefins are to be avoided in the reaction. Higher functionality olefins alkylate at each double bond, forming polymers which are not useful for gasoline blending.
The alkylation catalyst is hydrogen fluoride, referred to in the art as hydrofluoric acid or simply by its molecular symbol HF. Generally, anhydrous hydrogen fluoride is supplied to the process. In use, a typical analysis shows 1 wt % to 2 wt % water and 5 wt % to 15 wt % acid soluble oil.
The reaction may be carried out at pressures varying from atmospheric to as high as 1000 psia (68 atm) or higher, preferably about 125 to 220 psia (8.5 to 15 atm) and at residence times of 20 seconds to 5 minutes. The pressure is selected in cooperation with the temperature to maintain the hydrocarbon reactants in liquid phase and generally ranges from −40° F. (−40° C.) to about 150° F. (66° C.). In the preferred reaction of isobutane with a C 4 monoolefin the reaction temperature is between about 60° F. (15° C.) and about 100° F. (38° C.) and most preferably about 90° F. (32° C.).
In the alkylation reaction a substantial molar excess of isoparaffin to olefin is employed to provide an isoparaffin/olefin feed ratio in excess of about 1/1, generally 4/1 to 70/1 and preferably 5/1 to about 20/1.
Reference is made to the Drawing. The isoparaffin feed in line 24 and the olefin feed in line 25 are combined and introduced into reactor vessel 30 via lines 26 , 27 and 28 . Fresh, anhydrous hydrogen fluoride in tank 10 is passed via line 17 into reactor vessel 30 which is either horizontally or vertically elongated and cylindrical in shape. The volume of anhydrous, liquid hydrogen fluoride exceeds the volume of the isoparaffin and monoolefin mixture. The liquid hydrogen fluoride constitutes a continuous phase in reactor vessel 30 and the hydrocarbon feedstocks constitute a discontinuous phase. Coolant, such as cooling water is passed via line 21 through heat exchanger tubes (not shown) exposed to the reaction mixture in reactor vessel 30 , thereby moderating reaction temperature to the selected range. Coolant is discharged via line 22 .
Reaction effluent, comprising alkylate product, unreacted isoparaffin and liquid catalyst are withdrawn from reactor vessel 30 via line 34 and discharged into catalyst settler vessel 50 which is vertically elongated and cylindrical in shape. The catalyst settler vessel 50 allows for separation of the reaction effluent from the alkylation reactor into an upper liquid hydrocarbon phase and a lower liquid catalyst phase containing hydrogen fluoride catalyst, acid soluble oil, and water. The catalyst settler vessel 50 may contain separation trays and vertical downcomers (not shown) positioned within the vessel to enhance separation.
The alkylate product phase is withdrawn via line 57 and processed by fractional distillation (not shown) to recover unreacted isoparaffin and alkylate product.
The liquid catalyst phase is withdrawn via line 60 and passed to spent acid tank 70 . A portion of this acid may be recycled (not shown) from spent acid tank 70 to reactor vessel 30 .
Surrounding and enclosing each of the major process vessels is a containment baffle. The containment baffle allows for a vapor space between the vessel and the baffle. Fresh acid tank 10 is enclosed by containment baffle 12 , providing vapor space 11 and fluid communication with the air via slots 12 s. Reactor vessel 30 is enclosed by containment baffle 32 , providing vapor space 31 and fluid communication with the air via slots 32 s. Acid catalyst settler 50 is enclosed by containment baffle 52 , providing vapor space 51 and fluid communication with the air via slots 52 s. Spent acid tank 70 is enclosed by containment baffle 72 , providing vapor space 71 and fluid communication with the air via slots 72 s.
Each of the vessels is cylindrical in shape as is each containment baffle. Preferably each containment baffle has a cylindrical radius 0.25 inches (0.635 cm) to 36 inches (91.44 cm) greater than the cylindrical radius of the vessel. Should a major process vessel leak, the vapor space provides volume for hydrogen fluoride to collect while limiting escape to the atmosphere via the slots. Hydrogen fluoride vapor at an initial escape velocity of 50 ft./sec. to 1500 ft./sec. has been found to condense on the baffle at atmospheric temperature and pressure, forming a vapor-condensate mixture.
The containment baffles dissipate the momentum of the escaping hydrogen fluoride vapor and reduce the velocity of the vapor-condensate mixture to that of the ambient air or less, generally 0 to 15 miles/hr. (22 ft./sec.), typically 0 miles/hr (0 ft./sec.) to 5 miles/hr. (7.3 ft./sec.).
This slow moving mixture under the containment baffle is sufficiently concentrated that it is detectable by detecting means. Commercially available hydrogen fluoride composition detectors are sufficiently sensitive to react to concentrations of 1 part per billion parts by weight to 1 part per million by weight in 15 seconds to 1 minute. This threshold is below the concentration of 20 parts per million by weight considered an immediate danger to life and health by the National Institute of Occupational Safety and Health. As little as 50 parts per million parts by weight is considered lethal. Secondary hydrogen fluoride detecting means includes hydrocarbon detectors and temperature and pressure sensors. A massive release would be indicated by the presence of hydrocarbon or a sudden or large temperature or pressure change under an impingement baffle. For example, a temperature change of 10° F. (5.5° C.) or more or a pressure change of 1 psi or more would indicate a vapor release.
Primary, composition detectors and secondary detectors are shown as detector 110 associated with tank 10 , detector 130 associated with reactor vessel 30 , detector 150 associated with catalyst settler vessel 50 and detector 170 associated with spent acid tank 70 . It is understood that the drawing is schematic and an array of detectors may be distributed within each containment baffle. Such an array would incorporate both primary, composition detectors and secondary detectors including hydrocarbon detectors, thermocouples and pressure sensors.
Each detector produces a signal when activated by the presence of hydrogen fluoride. Detector 110 produces signal 111 which is transmitted to valve actuator 113 . Valve actuator 113 actuates quick open valve 115 providing a flood of aqueous liquid from water supply 114 into containment baffle 12 via flood line 116 . The aqueous liquid is water. Incorporated in the liquid water may be alkali agents, buffers and surfactants to improve effectiveness in dissolving and neutralizing hydrogen fluoride. The water is passed via fog nozzle 117 which is representative of a plurality of fog nozzles positioned around containment baffle 12 . Fog nozzles are available which produce water mists having an average droplet size of 300 micron to 2000 micron and greater. This droplet size provides a large amount of surface area for the capture of hydrogen fluoride vapor.
The hydrogen fluoride dilute aqueous liquid is passed via drain line 15 to vented sump 90 where it is collected. Vapor recoveries up to 90% have been demonstrated experimentally with water/hydrogen fluoride vapor ratios of 6/1 to 40/1 by weight.
Likewise detector 130 , signal 131 , actuator 133 , water supply 134 , quick open valve 135 , flood line 136 and external spray head 138 are shown. Likewise detector 150 , signal 151 , actuator 153 , water supply 154 , quick open valve 155 , flood line 156 a, flood line 156 b, fog nozzle 157 and external spray head 158 are shown. Likewise detector 170 , signal 171 , actuator 173 , water supply 174 , quick open valve 175 , flood line 176 a, a flood line 176 b, fog nozzle 177 and external spray head 178 are shown. The drawing is schematic and each vessel may contain a plurality of fog nozzles and external spray heads.
Hydrogen fluoride dilute aqueous liquid is passed via drain lines 35 , 55 and 75 to vented sump 90 where it is collected. Sump 90 may be used in combination with ground containment means such as earthen, concrete and asphaltic dikes.
U.S. Pat. No. 5,073,674 to Olah incorporated herein by reference discloses catalytic alkylation using liquid onium polyhydrogen fluoride complexes. These compositions show less volatility at alkylation conditions than anhydrous hydrogen fluoride. These complexes in combination are therefore more susceptible to recovery by water flood and are the Best Mode for carrying out the invention contemplated by inventors.
While particular embodiments of the invention have been described, it will be understood, of course, that the invention is not limited thereto since many modifications may be made, and it is, therefore, contemplated to cover by the appended claims any such modification as fall within the true spirit and scope of the invention. For example, hydrogen fluoride utilizing means is understood to include vessels for carrying out hydrogen fluoride manufacture, fluorocarbon manufacture, fluorination, and the aromatic alkylation process.
|
A safety apparatus has been found for recovering an airborne hydrogen fluoride release in a hydrocarbon alkylation process. The safety apparatus comprising containment baffles and hydrogen fluoride detectors. Hydrogen fluoride detectors activate water flood means which discharge into the containment baffles. The water flood containing essentially all of the hydrogen fluoride release is recovered for disposal. Recoveries of 90 wt % have been demonstrated.
| 2
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a ladder working limit based ladder stopping device for vehicle equipped with a vertically and horizontally swingable and extensible ladder (or a fire engine truck).
2. Description of the Prior Art
In an aerial ladder truck of the type described, the vertical swing and extension of the ladder are carried out by oil pressure. Thus, a ladder vertical angle indicator and a ladder extension indicator are separately attached to the truck. The operator of the ladder carries out the operation of the ladder while watching said two indicators in such a manner that when he finds that the ladder approaches a dangerous condition, he stops the operation and then handles the ladder so as to avoid the danger. In order to determine whether the ladder is in a dangerous condition or not, he reads the indicated values on said two indicators and checks them with a conversion table or the like to find the bending moment acting around the pivoted point on the ladder. With such procedure, however, there is a disadvantage that it is impossible to take a quick and proper measure. Another disadvantage is that whether the ladder has got out of the danger or not cannot be immediately ascertained.
SUMMARY OF THE INVENTION
The present invention has been accomplished to eliminate the above-mentioned disadvantages of the prior art aerial ladder truck and comprises a vertical angle indicator, an extension indicator and a bending moment load indicator which are collected in a single indicating section so that the conditions of the ladder can be grasped at a glance, the arrangement being such that when the ladder approaches a dangerous condition, the operation of the ladder is automatically stopped and the automatic stopping device is then manually operated toward the safety side to remove the danger, whereupon it can be easily ascertained that the ladder has really got out of the danger.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic side view of the principal portions of an aerial ladder truck according to the present invention;
FIG. 2 is a front view, in longitudinal section, of a gauge case;
FIG. 3 is a plan view of the gauge case;
FIG. 4 is a side view of an indicating mechanism inside the gauge case;
FIG. 5 is a front view of said indicating mechanism;
FIG. 6 is a schematic view of an automatic stopping device;
FIG. 7 is an electric circuit diagram for said device; and
FIG. 8 is a schematic view of the base portion of a ladder showing an example of a marker lamp fixing position.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In FIG. 1, the character 1 designates an aerial ladder truck; 2, a turntable mounted on the rear portion of the truck; 3, a ladder support pillar erected on the turntable; 4, a ladder support frame pivotally mounted on the ladder support frame; and the character 6 designates a ladder supported on the ladder support frame.
The ladder 6 is adapted to be vertically swung by a hydraulic cylinder 7 interposed between the ladder support pillar 3 and the ladder support frame 4. Further, the ladder 6 is extended and contracted by a rope winding drum 8 coaxially mounted on the pivot 5. Thus, the rope (not shown) passes around the ladder in zigzags in such a manner that when the rope is wound around the drum 8, the ladder is extended and that when the rope is unwound, the ladder is contracted. The drum 8 is connected to a hydraulic motor. The rotation or horizontal swing of the ladder is effected by rotating the turntable 2. The turntable is driven by a hydraulic motor. These two hydraulic motors and the hydraulic cylinder 7 for vertical swing of the ladder are connected to a single hydraulic pump through separated pipes each having a manually operated valve placed in an intermediate portion thereof.
The hydraulic pump is mounted on the aerial ladder truck and driven by the truck engine or by a separate engine. The hydraulic pump is provided with means whereby the r.p.m. and the rate of discharge are controlled.
The manually operated valves are collectively installed on a control tower 9 on the turntable 2 and each valve has an operating lever.
The construction described above is substantantially the same as a conventional aerial ladder truck.
The amount of extension and the vertical angle of the ladder are indicated on the control tower 9 by an arrangement to be presently described.
A gauge case 10 as shown in FIG. 2 is mounted on the control tower 9. An arcuate plate 11 is attached to the upper surface of the gauge case. As shown in FIG. 3, the plate is marked with a load scale 12 and with a vertical angle scale 13 and an extension scale 14 on either side of said scale 12. An angle pointer 15 associated with the vertical angle scale 13 and an extension pointer 16 associated with the extension scale 14 project through elongated openings 17 and 18, respectively, in the plate 11.
The angle scale 13 and extension scale 14 on the plate 11 are interconnected by limit load lines 19. The limit loads are determined by allowing for a safety factor to some extent. In determining such limit load, the limit of extension of the ladder is calculated when the angle is fixed. This will be explained by referring to FIG. 3. Thus, when the angle is 30°, the allowable extension is 8 m, beyond which danger exists. Similarly, for an angle of 50°, the extension limit is 10 m; for 60°, it is 13 m; and for 70°, it is 16 m. The limit loads for an aerial ladder truck are entirely different from those for a crane and determined on the basis of bending moment loads. Thus, as the ladder is extended, the bending moment increases. Further, the smaller the vertical angle, the greater the bending moment. Therefore, it follows that if the vertical angle decreases, this is dangerous unless the amount of extension of the ladder is decreased.
The angle pointer 15 and extension pointer 16 are rigidly secured to sleeves 21 and 22, respectively, loosely fitted over a fixed shaft 20, as shown in FIG. 4. The sleeves 21 and 22 have chain wheels 23 and 24 secured to their outer ends and an angle cam plate 25 and extension plate 26 secured to their inner ends, respectively. The angle cam plate 25 is formed with a cam groove 27, as shown in FIG. 5. A pin 29 on a movable arm 28 extends through said cam groove 27. The movable arm 28 is loosely fitted over a shaft 30 which is parallel to the fixed shaft 20. The movable arm is disposed intermediate between said angle cam plate 25 and said extension plate 26 and has said pin 29 on one surface thereof and a contact 31 on the other. The pin 29 is inserted in the cam groove 27 in the angle cam plate 25, as described above. The contact 31 is adapted to contact an electrically conductive plate 32 provided on the inner surface of the extension plate 26. The contact 31 and electrically conductive plate 32, as schematically shown in FIG. 5, have connected thereto the terminals of an electric circuit 35 including a power source 33 and a lamp 34. The contact 31 and electrically conductive plate 32 constitutes a switch for said electric circuit 35.
In FIG. 2, it is so arranged that as the two pointers 15 and 16 move from right to left, the indicated values increase. If, therefore, the indicated value by the angle pointer 15 is large and the indicated value by the extension pointer 16 is small, the electrically conductive plate 32 and the contact 32 are separated from each other, so that the lamp 34 is not turned on. The lighting of the lamp 34 indicates the working limit of the ladder 6. Therefore, the lamp may be replaced by other warning device such as buzzer.
The two pointers 15 and 16 are moved along the elongated openings 17 and 18 by the rotation of the chain wheels 23 and 24 to indicate the vertical angle and amount of extension of the ladder. Thus, the vertical angle is converted into the rotation of a chain wheel 36 fixed on the ladder support frame 4, said rotation being transmitted to the chain wheel 23 through a chain 37, while the amount of extension of the ladder is converted into the rotation of the ladder extension and contraction rope winding drum 8 journaled in the support frame 4 of the ladder 6, said rotation being transmitted to the chain wheel 24, (see FIG. 1). When the chain wheel 23 is rotated, the angle cam plate 25 integral therewith is moved. As a result, the movable arm 28 is rotated clockwise or counterclockwise by the action of the cam groove 27. In the condition shown in FIG. 2, if the extension pointer 16 approaches the angle pointer 15, the contact 31 contacts the electrically conductive plate 32. This means that the two pointers 15 and 16 indicate one of the limit load lines 19 drawn obliquely on the load scale 12. As a result, the circuit 35 of the lamp 34 is closed to turn on the lamp 34. If the lamp is replaced by a buzzer, the buzzer is rung to tell that the working limit of the ladder is reached. In addition, the angle cam plate 25, extension plate 26 and movable arm 28 are made of an insulating material. As shown in FIG. 6, a solenoid valve 38 is placed in series in the electric circuit 35 which has been described above with reference to FIG. 5. In FIG. 6, the character 39 designates an oil tank; 40, an oil pump; 38, a manual valve for extension and contraction of the ladder; and the character 42 designates an operating lever for said valve. The oil tank 39 and oil pump 40 are mounted on the aerial ladder truck (not shown). The manual valve 41 and operating lever 42 are provided in the control tower 9. Working oil is fed into the manual valve 41 from the oil pump 40. Such oil is fed into a hydraulic motor (not shown) for the ladder extension and contraction rope winding drum 8 shown in FIG. 1. The solenoid valve 38 is placed in an oil pipe 44 branching off from an oil pipe 43 through which working oil from the oil pump is conveyed to the manual valve 41. The branch oil pipe 44 is connected to a hydraulic cylinder 45 for returning the operating lever 42 to its neutral position. The hydraulic cylinder 45 has a piston rod 46 opposed to the operating lever 42. The operating lever has two more positions, namely, an extension position and a contraction position on both sides of the neutral position. When the solenoid valve 38 is energized, the hydraulic cylinder 45 receives working oil from the oil pump 40 through the oil pipe 44 so that the piston rod 44 is projected. When the solenoid valve 38 is not energized, the supply of oil from the oil pump 40 is interrupted and the cylinder oil chamber communicates with the oil tank 39 to allow the free movement of the piston. The relation between the hydraulic cylinder 45 and the operating lever 42 is such that when the operating lever is on the extension side, the solenoid valve 38 is energized to project the piston rod 46, thereby pushing the operating lever 42 to its neutral position. In other cases, for example, when the operating lever is in its neutral position or in its contraction position, the projection of the piston rod 46 has no influence on the operating lever 42. In addition, when the solenoid valve 38 is energized with the piston rod 46 projected by the working oil from the pump 40, it becomes impossible to move the operating lever to the extension position. In this condition, the operating lever is still free to be moved to its contrction position. That is, it is when the working limit of the ladder 6 is reached that the solenoid valve 38 is energized. At such time, the extending operation of the ladder is automatically stopped. Thus, the contracting operation of the ladder is made possible.
The same arrangement as that shown in FIG. 6 is employed in the operating valve for the hydraulic cylinder for vertical swing of the ladder, though such construction is not shown. In the case of vertical swing, however, it has a raising position and a lowering position on both sides of its neutral position. It is so arranged that the operation toward the lowering side is made impossible by the piston rod of the cylinder and that when the working limit of the ladder 6 is reached during lowering operation, the lowering operation is automatically stopped. In this case also, a solenoid valve for automatically stopping raising and lowering operation is used.
The solenoid valve for automatically stopping raising and lowering operation and solenoid valve for automatically stopping extension and contraction are connected in an electric circuit such as shown in FIG. 7. In FIG. 7, the character 10 designates a gauge case; 33, a power source; 34, a warning device; 47, a manual switch for removing working limit condition; 38, a solenoid valve for automatically stopping extension and contraction; 48, a solenoid valve for automatically stopping raising and lowering operation; and the character 49 designates a marker lamp. The marker lamp 49 will remain turned on so far as the switch mechanism in the gauge case 10 is not opened, even if the manual switch 47 is opened.
The manual switch 47 is installed on the control tower 9 and normally closed. During the operation of the ladder, if the switch mechanism in the gauge case 10 is closed, the working limit is reached. That is, an electric current flows through the warning device 34, solenoid valves 38 and 48 and marker lamp 49. When this condition is established, the operating lever of the ladder 6 is automatically returned to its neutral position. Therefore, the operation of the ladder 6 is stopped at the working limit. Moreover, the operation toward the danger-increasing side is made impossible. However, the operation toward the safety side is possible.
Further, when the ladder is operated away from the working limit toward the safety side, this can be ascertained since the marker lamp 49 is turned off. The marker lamp may be installed on the control tower 9 or on the base portion of the ladder 6 as shown in FIG. 8. The operation of the ladder is carried out at the position of the control tower 9. Since the operator often operates the ladder 6 while watching the ladder, it appears that the best position for mounting of the marker lamp 49 is at the base portion of the ladder as shown in FIG. 8.
Whiles there have been described herein what are at present considered preferred embodiments of the several features of the invention, it will be obvious to those skilled in the art that modifications and changes may be made without departing from the essence of the invention.
It is therefore to be understood that the exemplary embodiments thereof are illustrative and not restrictive of the invention, the scope of which is defined in the appended claims and that all modifications that come within the meaning and range of equivalency of the claims are intended to be included therein.
|
There is provided a ladder working limit based ladder stopping device for a vehicle equipped with a vertically and horizontally swingable and extensible ladder (or a fire engine truck), wherein a working limit of the ladder is preset on the basis of an extended length of the ladder corresponding to a particular vertical angle assumed by the ladder, so that when the combined situation of the vertical angle and extended length of the ladder reaches said preset condition, the operating mechanism for the ladder is automatically returned to its neutral position while actuating a warning device and turning on a marker lamp, the operating mechanism being then operated toward the safety side, whereupon the marker lamp is turned off to indicate that the ladder is now safe.
| 4
|
REFERENCE TO CO-PENDING APPLICATIONS FOR PATENT
[0001] The present application is related to the following co-assigned U.S. Patent Applications, which are expressly incorporated by reference herein:
[0002] U.S. application Ser. No. ______, entitled “SOCIAL COLLABORATIVE SCORING FOR MESSAGE PRIORITIZATION BASED UPON AN APPLICATION INTERACTION RELATIONSHIP BETWEEN SENDER AND RECIPIENT” (docket no. RSW920070284US1 (348U1)), filed on Jan. __, 2008.
[0003] U.S. application Ser. No. ______, entitled “SOCIAL COLLABORATIVE SCORING FOR MESSAGE PRIORITIZATION BASED UPON A TEMPORAL FACTOR BETWEEN SENDER AND RECIPIENT” (docket no. RSW920070442US 1 (348U2)), filed on Jan. __, 2008.
[0004] U.S. application Ser. No. _____, entitled “SOCIAL COLLABORATIVE SCORING FOR MESSAGE PRIORITIZATION BASED UPON AN ORGANIZATIONAL RELATIONSHIP BETWEEN SENDER AND RECIPIENT” (docket no. RSW920070444US1 (348U4)), filed on Jan. __, 2008.
BACKGROUND OF THE INVENTION
[0005] 1. Field of the Invention
[0006] The present invention relates to the field of computer messaging and more particular to message prioritization in a message folder.
[0007] 2. Description of the Related Art
[0008] Messaging is the lifeblood of the Internet. The ability for different users geographically dispersed about the globe to exchange messages instantaneously and to universally read those messages irrespective of the type of computer involved has enabled the explosive growth of computing worldwide. Messaging generally includes not only traditional, asynchronous forms of communication including e-mail, discussion forums, blogging, wikis, shared calendaring and tasking, but also synchronous forms of communication including instant messaging, group chats, and the like. Irrespective of the mode of messaging, however, that remote individuals can instantaneously communicate provides the pulse of modern computing.
[0009] The ease in which end users can compose and transmit messages to others in an instantaneous fashion is not without consequence, however. Whereas traditional forms of communication—namely the telephone, facsimile and postal service—required some effort on the part of communicants, composing and transmitting a message like an e-mail or instant message requires little effort. Accordingly, the volume of messages traversing the global Internet each minute far exceeds by orders of magnitude those messages transmitted using traditional methods. As a result, entirely new management tools are required to manage the sheer mass of messages end users receive and process each day.
[0010] For casual users of messaging, message management can be limited to sorting a view of an inbox for inbound messages. Yet, for advanced users—particularly corporate users—the constraint of the physical size of the view inhibits the ability to see all messages so as to permit manual management of messages through sorting. The problem of message management can be compounded when the number of messages to be managed sums to the hundreds and thousands. In the latter instance, an end user may require days to process each message resulting in a lapse of communication comparable to that of pre-Internet, traditional messaging—the very problem sought to be overcome by Internet based messaging.
[0011] To address the problem of message management for a large volume of messages, tools have been developed to prioritize messages either manually or automatically. Once messages have been prioritized, the messages can be sorted in a view to the messages so that the messages of highest priority can appear within eyeshot of an end user. Consequently, the end user can process those messages of greatest importance first, leaving those messages of lesser importance for later processing. Most tools permit the classification of messages by numerical priority, and advanced tools perform prioritization according to the identity of the sender of the message, the time of receipt of the message or keywords in the subject line of the message.
[0012] Recently, message management systems have combined different prioritization criteria for automatically sorting and/or filtering messages wherein each of the criteria can be manually weighted by the end user to express a preferred balancing of application of the criteria to inbound messages. Exemplary criteria include whether or not the sender is recognized as an entry in the address book of the recipient, the priority of the message as established by the sender, the extent of participation of the recipient in a thread associated with the message (known as thread participation), and whether the message recipient was designated as the direct recipient, or as the recipient of a carbon copy or blind carbon copy (known as message directness). While the foregoing criteria can be important to many users, in the organizational and social context, the criteria cannot properly prioritize a message according to the relative importance of the message in a social collaborative structure of messengers.
BRIEF SUMMARY OF THE INVENTION
[0013] Embodiments of the present invention address deficiencies of the art in respect to message prioritization and provide a novel and non-obvious method, system and computer program product for social collaborative prioritization of messages in a messaging system. In an embodiment of the invention, a method for social collaborative prioritization of messages can be provided for a messaging system. The method can include receiving a message from a sender as directed to a recipient, determining a value for a different social collaborative criterion based upon a social networking relationship between the sender and the recipient, transforming the value into a priority for the message, and associating the priority with the message in the messaging system.
[0014] In one aspect of the embodiment, the method also can include further determining a value for a different social collaborative criterion and weighting each of the values into a single value for transformation into the priority. In another aspect of the embodiment, the method further can include disabling a determination of one of the social collaborative criterion. In yet another aspect of the embodiment, receiving a message from a sender as directed to a recipient can include receiving a message such as an e-mail, an instant message, a discussion forum posting and a wiki posting, and determining values for different social collaborative criterion based upon a relationship between the sender and the recipient can include determining values for different social collaborative criterion based upon any combination of an organizational relationship, a temporal relationship, and an application interaction relationship.
[0015] In another embodiment of the invention, a messaging data processing system can be provided. The system can include a messaging server configured for coupling to multiple different messaging clients over a computer communications network. The system also can include social collaboration prioritization logic. The logic can include program code enabled to determine a value for a different social collaborative criterion for a received message based upon a relationship between a sender and a recipient of the message, to transform the value into a priority for the message, and to associate the priority with the message.
[0016] Additional aspects of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The aspects of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0017] The accompanying drawings, which are incorporated in and constitute part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention. The embodiments illustrated herein are presently preferred, it being understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown, wherein:
[0018] FIG. 1 is a pictorial illustration of a process for social collaborative prioritization of messages;
[0019] FIG. 2 is a schematic illustration of a messaging system configured for social collaborative prioritization of messages; and,
[0020] FIG. 3 is a flow chart illustrating a process for social collaborative prioritization of messages in a messaging system.
DETAILED DESCRIPTION OF THE INVENTION
[0021] Embodiments of the present invention provide a method, system and computer program product for social collaborative prioritization of messages in a messaging system. In accordance with an embodiment of the present invention, social collaborative criteria can be weighted and applied to inbound messages in order to either sort or filter the messages in a message view in a messaging system. The social collaborative criteria can include the organizational relationship between a sender of the message and a recipient of the message, an application interaction relationship expressing a number of different applications used by the sender of the message to message the recipient of the message, a temporal relationship indicating whether or not an associated thread of interaction between the sender and the recipient remains active, and a social networking relationship measuring proximal connectivity between the sender and the recipient.
[0022] In further illustration, FIG. 1 is a pictorial illustration of a process for social collaborative prioritization of messages. As shown in FIG. 1 , social collaborative criteria 120 for a message 110 can be subjected to weighting 130 to produce a priority 140 for the message 110 . The social collaborative criteria 120 can include an organizational relationship 120 A. The organization relationship 120 A can include a position in an organizational hierarchy for the sender of the message 110 either as an absolute value, or as a relative value compared to a position in the organizational hierarchy of the recipient of the message 110 . Optionally, where multiple recipients of the message 110 have been designated, a combination score for the organization relationship 120 A can be computed, for instance a summed value, a diminished value by the number of recipients or an average value.
[0023] The social collaborative criteria 120 also can include a temporal relationship 120 B. The temporal relationship 120 B can be defined by the duration in which an associated message thread between the sender of the message 110 and the recipient of the message 110 has been active. The longer the message thread has enjoyed continuous activity, the higher the score for the temporal relationship 120 B. Once the thread has gone inactive, specifically when no responsive messages have been posted to the thread in a threshold period of time, the score for the temporal relationship 120 B will be diminished.
[0024] The social collaborative criteria 120 yet further can include a social networking relationship 120 C. The social networking relationship 120 C can be defined by the close connectivity between the sender of the message 110 and the recipient of the message 110 in a social network. In this regard, the fewer relationships the link the sender of the message 110 and the recipient of the message 110 , the higher the score assigned to the social networking relationship 120 C indicating a closer relationship between the sender of the message 110 and the recipient of the message 110 .
[0025] Finally, the social collaborative criteria 120 can include an application interaction relationship 120 N. The application interaction relationship 120 N can be defined by a number of different messaging applications utilized by the sender of the message 110 in attempting to contact the recipient of the message 110 within a threshold defined period of time. The more applications used by the sender of the message 110 indicate a higher sense of urgency of the message 110 resulting in a higher score for the application interaction relationship 120 N.
[0026] Notably, the weights 130 can vary from user to user. The weights 130 can be assigned manually and individually for each of the social collaborative criteria 120 , or the weights 130 can be assigned as a set. Different sets of the weights 130 can be arranged for different roles in an organization so that the set of weights 130 for a manager may differ from the set of weights 130 for a clerk. Yet further, individual ones of the social collaborative criteria 120 can be enabled or disabled either manually by the end user, or automatically based upon environmental criteria such as time of day. Again, the enablement and disablement of the social collaborative criteria 120 can be included as an automated set and can vary based upon the different roles in an organization for a recipient of the message 110 .
[0027] The process illustrated in FIG. 1 can be performed within a messaging data processing system. In illustration, FIG. 2 schematically depicts a messaging system configured for social collaborative prioritization of messages. The system can include a host server 210 configured for communicative coupling over computer communications network 220 to different computing devices 230 , each hosting a corresponding messaging client 240 . The host server 210 can support the operation of a messaging server 250 , for example an e-mail server, instant messaging server, discussion forum server, wiki server, collaborative server, and the like.
[0028] Notably, social collaborative prioritization logic 300 can be coupled to the host server 210 , to the messaging clients 240 , or both. The social collaborative prioritization logic 300 can include program code enabled to compute a weighted priority for messages flowing from the messaging server 250 to the messaging clients 240 based upon social collaboration criteria, including an organizational relationship of the sender, a temporal relationship between the sender and the recipient, a social networking relationship between the sender and the recipient, and an application interaction relationship between the sender and the recipient of the message. Weights 260 can be applied to each of the collaborative criteria automatically or manually and selectively and the applied ones of the weights 260 can vary based upon the placement of the recipient in an organizational hierarchy or environmental factors. Finally, different ones of the collaborative criteria can be selectively enabled and disabled either manually by the recipient, or automatically based upon the placement of the recipient in the organizational hierarchy or environmental factors.
[0029] In yet further illustration of the operation of the social collaborative prioritization logic 300 , FIG. 3 is a flow chart illustrating a process for social collaborative prioritization of messages in a messaging system. Beginning in block 310 , a message can be received from a sender as directed to a recipient. In block 320 , a value for each of the social collaborative criteria can be determined for the message. Thereafter, in block 330 , each of the values can be weighted and combined to form a priority and in block 340 , the priority for the message can be applied to the message. In this way, messages in a view can be sorted or filtered by priority as the priority relates to the social relationship between the sender and the recipient.
[0030] Embodiments of the invention can take the form of an entirely hardware embodiment, an entirely software embodiment or an embodiment containing both hardware and software elements. In a preferred embodiment, the invention is implemented in software, which includes but is not limited to firmware, resident software, microcode, and the like. Furthermore, the invention can take the form of a computer program product accessible from a computer-usable or computer-readable medium providing program code for use by or in connection with a computer or any instruction execution system.
[0031] For the purposes of this description, a computer-usable or computer readable medium can be any apparatus that can contain, store, communicate, propagate, or transport the program for use by or in connection with the instruction execution system, apparatus, or device. The medium can be an electronic, magnetic, optical, electromagnetic, infrared, or semiconductor system (or apparatus or device) or a propagation medium. Examples of a computer-readable medium include a semiconductor or solid state memory, magnetic tape, a removable computer diskette, a random access memory (RAM), a read-only memory (ROM), a rigid magnetic disk and an optical disk. Current examples of optical disks include compact disk-read only memory (CD-ROM), compact disk-read/write (CD-R/W) and DVD.
[0032] A data processing system suitable for storing and/or executing program code will include at least one processor coupled directly or indirectly to memory elements through a system bus. The memory elements can include local memory employed during actual execution of the program code, bulk storage, and cache memories which provide temporary storage of at least some program code in order to reduce the number of times code must be retrieved from bulk storage during execution. Input/output or I/O devices (including but not limited to keyboards, displays, pointing devices, etc.) can be coupled to the system either directly or through intervening I/O controllers. Network adapters may also be coupled to the system to enable the data processing system to become coupled to other data processing systems or remote printers or storage devices through intervening private or public networks. Modems, cable modem and Ethernet cards are just a few of the currently available types of network adapters.
|
Embodiments of the present invention address deficiencies of the art in respect to message prioritization and provide a novel and non-obvious method, system and computer program product for social collaborative prioritization of messages in a messaging system. In an embodiment of the invention, a method for social collaborative prioritization of messages can be provided for a messaging system. The method can include receiving a message from a sender as directed to a recipient, determining a value for a different social collaborative criterion based upon a social networking relationship between the sender and the recipient, transforming the value into a priority for the message, and associating the priority with the message in the messaging system.
| 7
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention concerns oil well drilling, in general, and more specifically relates to a tool for use in deep well testing operations.
2. Description of the Prior Art
Heretofore, in making tests of a multiple-zone completed well, it has been necessary to run a test tool down the hole at least once for each formation. Also, the test procedures involved cement squeezing and wireline setting of bridge plugs. Consequently, and particularly in connection with deep hole drilling, the saving in rig time is very substantial if only a single trip into the hole with the test tool could be accomplished.
Consequently, it is an object of this invention to provide a well tool that is able to test and seal off a series of down hole formation zones utilizing hydraulically set bridge plugs and with only a single trip into the hole.
SUMMARY OF THE INVENTION
Briefly, the invention concerns a composite multiple zone test tool for deep well operations. It comprises in combination a full bore test tool adapted for running into a well on a tubing string. It also comprises a plurality of full opening bridge plugs integrally attached to said test tool.
Again briefly, the invention concerns a composite multiple zone test tool for deep well operations, which comprises in combination a full bore test tool adapted for running into a well on a tubing string, and three full opening bridge plugs integrally attached in series below said test tool when in a well. The lowermost of the said bridge plugs is settable with a differential pressure of about 1500 pounds per square inch, and the middle one of said bridge plug is settable with a differential pressure of about 2500 pounds per square inch. Also, the upper most of said bridge plugs is settable with a differential pressure of about 3500 pounds per square inch. The tool also comprises first shear means for detaching the lowermost of said bridge plugs in said series with about a 20,000 pound force, and second shear means for detaching the middle one of said bridge plugs in said series with about a 35,000 pound force. It also comprises third shear means for detaching the uppermost of said bridge plugs in said series with about a 50,000 pound force. Each of the said bridge plugs has a landing groove for receiving a sealing plug selectively therein. The said uppermost bridge plug has the shortest landing groove, and the said middle bridge plug has an intermediate length landing groove. Also, the said lowermost bridge plug has the longest landing groove. Each of the said bridge plugs incorporates a fishing neck for use in retrieving the plugs after testing has been completed.
Once more briefly, the invention concerns the combination of a multiple zone test tool for testing a plurality of vertically spaced formations with a single trip into a borehole. The combination comprises a full bore retrievable portion having a packer for carrying out a formation test, and a plurality of bridge plugs serially attached beneath said retrievable portion when said tool is in the borehole. The said bridge plugs each have means for selectively landing a sealing plug for sealing off said borehole there beneath, following the said formation test. Also, it comprises shear means for the releasing of the said bridge plugs in sequence beginning with the lowermost one.
BRIEF DESCRIPTION OF THE DRAWING
The foregoing and other objects and benefits of the invention will be more fully set forth below in connection with the best mode contemplated by the inventor of carrying out the invention, and in connection with which there is an illustration provided in the drawing, wherein:
The FIGURE of drawing is a schematic crosssectional showing of a tool according to the invention, as located in a borehole.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The drawing FIGURE is a schematic illustration of a tool according to the invention. It is illustrated as being located down hole in a borehole 11, that is shown with a casing 12 in place therein. It will be understood that the borehole 11 penetrates different formations such as a formation 15 that is schematically indicated. After the borehole has been completed, promising formations will be given tests to determine whether or not such formations will produce desired products.
A tool 16 according to this invention is schematically illustrated in cross section and located in the borehole 11. It is attached to the lower end of a string of tubing 19 upon which it is run into the borehole from the surface.
At the upper end of the tool 16, there is a full bore test tool 20. Such a test tool may be like one that is commercially available. It is designated by Halliburton as its Retrievable Test-Treat-Squeeze Packer.
Attached beneath the test tool 20 there are three bridge plugs 23, 24 and 25, in series. These are attached with shear rings 28, 29 and 30 respectively. As will be explained more fully below, the tensile force required to detach each of these bridge plugs is different. The least force is required at the bottom one, so that the bridge plugs may be detached in sequence one at a time.
Each of the three bridge plugs 23-25 is made up of two parts, one part being a packer section 33, 34 and 35 respectively. The other part of each bridge plug is a landing nipple section 38, 39 and 40 respectively. It will be observed that the landing nipple sections 38, 39 and 40 have different length grooves 45, 46 and 47 respectively, which are progressively longer as each bridge plug is added down the tool. By having this structure, a particular sealing plug (not shown) may be dropped down the tubing into the tool when desired, and by beginning with the longest of such sealing plugs (to match the longest landing nipple section 40), that sealing plug will continue down to be seated in that particular landing nipple.
As was the case with the test tool 20, each of the bridge plugs 23-25 may be made up of conventional elements. These elements (bridge plugs) might take the form of a combined hydraulic-set packer and a selective landing nipple. Such tools are both available commercially. For example, Otis Engineering Corporation of Dallas, Texas (a Halliburton Company) supplies a hydraulicset packer designated by the trademark Perma-Trieve. Also, Otis supplies a selective landing nipple that would be appropriate.
It will be observed that there is an open bore 49 which extends the entire length of the tool 16. This permits the desired use of the tool, which will now be described. It may be noted here that the details of the various elements of the entire tool are only indicated schematically since, it will be clear to any one skilled in the art that these elements may be combined as necessary, in order to form a composite multiple zone test tool according to the invention.
OPERATION
The complete tool 16 will be made up with the various parts joined together, as indicated by the description above, showing the tool in a schematic illustration thereof. The upper end of the tool 16 is attached to the tubing string 19 for running everything down into the borehole. The entire tool 16 will be run down hole to a point somewhat above the lowermost formation to be tested. Then the packer of the test tool 20 will be set.
Next, the casing may be perforated at the desired formation. This will be followed by the carrying out of a swab or flow test. Thereafter the packer of the test tool 20 will be released, and a reverse circulation will be carried out to move the formation fluid out through the tubing 19.
The foregoing completes the testing of the first, i.e. the lowest formation down hole. Next, a sealing plug (not shown) that matches the lowermost landing nipple groove 47, will be dropped down the tubing 19 and landed in the groove. It will be noted that it will not be landed in the grooves 45 or 46 in the sections above, since they have shorter grooves.
When the sealing plug has been landed, pressure will be applied in the tubing 19 up to about 1500 pounds per square inch which will set the lower bridge packer section 35. Of course, after the sealing plug has first landed it is good practice to attempt to circulate fluid in both directions first, in order to determine that the plug is properly landed.
After the sealing plug has been landed, as indicated above, by applying the tubing pressure of about 1500 pounds per square inch, the lowermost bridge plug 25 will be set. The lower bridge plug 25 will then be detached by pulling up on the tubing 19 (with tool 16 attached) using a differential force of about 20,000 pounds, which will shear the lower shear ring 30. Then the bridge plug 25 seals off the borehole from that point down, and the tool 16 may be raised to the next formation location that is to be tested.
It will be understood that the same procedure may be carried out again in order to make another formation test, followed by setting the second bridge plug to seal the borehole from that point down. It will be appreciated that for this second test the pressure to set the packer section 34 will be about 2500 pounds per square inch, and the differential force for detaching that bridge plug portion 24 of the tool 16 will be about 35,000 pounds, to shear the next shear ring 29.
The next upper formation may be tested in a similar manner, and pressure for setting the bridge plug will be another step higher as also will be the differential force required to detached the shear ring. Thus, in the indicated structure, the setting pressure for the packer section 33 will be about 3500 pounds per square inch, and the differential force for detaching the shear ring 28 will be about 50,000 pounds pull.
Of course, another formation may be tested with the tool 20 before it is withdrawn from the borehole. Thus, it will be observed that by employing three bridge plug sections 23-25 on the tool 16, tests may be carried out for four different formations without having more than the one trip for the complete tool 16 down into the hole. This will result in substantial saving in rig time as well as avoiding the need for cement squeezing and wireline setting of bridge plugs.
It may be noted that by including a fishing neck 52 on each of the bridge plug sections of the tool, the plugs may be removed after the testing of all formations has been carried out. The removal would be carried out by jaring on the fishing neck in each instance, to release the upper slips and allow the plug to be removed.
While a particular embodiment of the invention has been described above in considerable detail, in accordance with the applicable statutes, this is not to be taken as in any way limiting the invention but merely as being descriptive thereof.
|
An oil well type of tool for testing a plurality of formations in a single trip into the hole. It has a full bore test tool which has a retrievable packer for making conventional tests. In addition there are a plurality of bridge plugs releasably connected in series below the test tool for plugging the hole above each formation after it is tested, without any additional trips into the hole.
| 4
|
BACKGROUND OF THE INVENTION
[0001] The present invention relates to reaching devices and in particular to reaching devices with telescoping handles.
[0002] Individuals often have a need to retrieve nearby items, but are unable to easily or safely reach for the items. In some instances, the individual is driving an automobile and needs to pick up an item which has fallen, for example, on the passenger-side floor of the car. Such items include ipod® personal audio devices, sunglasses, compact disks, and especially cell phones. Often, a driver leaves their cell phone unsecured in the car. While rounding a turn, the cell phone may side from it's resting place and onto the car's floor often landing on the passenger side floor and beyond the driver's reach.
[0003] Because drivers often have an unexpected need for their cell phone, they may attempt to retrieve the fallen phone. Attempting to reach for the phone while still driving may result in an accident. The driver may pull to the side of the road and reach for the phone, but may not be able to reach the phone while still wearing a seatbelt, and thus have to release the seat belt. In some instances, the driver may still be unable to reach the phone after releasing the seat belt, or may be unable to reach the phone without straining their back. In these instances the driver may have to exit the car and walk to the passenger door to be able to reach the phone, which may involve some risk on a busy highway.
[0004] There are many other instances where objects are beyond easy reach. Examples include an individual with a back injury or an elderly individual, when an item falls behind large objects.
[0005] Reaching devices are known for retrieving items beyond easy reach. One example is the “Gopher Pick Up & Reach Tool” made by Ontel Products in Fairfield, N.J., and the “40ez EZ Reach” made by AM Leonard in Piqua, Ohio. While both of these products provide a reaching capability, they are too long to easily carry in an automobile or in a pocket.
[0006] A reaching device with telescoping handles is disclosed in U.S. Pat. No. 5,152,569 for “Litter Picking Tool.” The device of the '569 patent includes telescoping handles attached to a jaw mechanism. The handles are connected at an end opposite the jaws and the jaws include a toothed mechanism for opening the jaws then the handles are squeezed together. Unfortunately, the toothed mechanism adds significant complexity to the reaching tool thus adding to cost and reducing reliability.
BRIEF SUMMARY OF THE INVENTION
[0007] The present invention addresses the above and other needs by providing a compact reaching device which includes jaws and telescoping handles. The jaws are joined by a hinge pin and are biased towards a closed position. Legs extend opposite the jaws and squeezing the legs together opens the jaws. Telescoping handles are attached to each leg and may be extended opposite the jaws to allow reaching.
[0008] In accordance with one aspect of the invention, there is provided a reaching device including an alligator clip or the like and telescoping handles attached to the alligator clip. The alligator clip includes first and second members, pivot pin, and a spring. The members have jaws, legs opposite the jaws, and pivots between the jaws and the legs, and the leg have receiving loops. The pivot pin passes through the pivots to pivotally join the members and the spring cooperates with the members to bias the jaws towards a close position. The arms have telescoping sections, and the smallest telescoping sections of each of the telescoping sections passes through the receiving loop of each leg, reaching near to the pivot pin, and are attached to the legs of each alligator clip, and the arms are extendable approximately opposite the jaws. The attached sections are preferably brazed to the legs, and preferably retain their original shape, for example, are not deformed by crimping.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
[0009] The above and other aspects, features and advantages of the present invention will be more apparent from the following more particular description thereof, presented in conjunction with the following drawings wherein:
[0010] FIG. 1A is a side view of a reaching device according to the present invention with telescoping handle fully extended and jaws in a closed position.
[0011] FIG. 1B is a side view of the reaching device telescoping handle fully extended and with the jaws in an open position.
[0012] FIG. 1C is a side view of the reaching device telescoping handle partially extended and with the jaws in an open position.
[0013] FIG. 1D is a side view of the reaching device telescoping handle closed and with the jaws in an open position.
[0014] FIG. 2 is a detailed partial side view of the reaching device with cover removed from one leg and jaw.
[0015] FIG. 3A is a side view of one leg and one jaw of the reaching device.
[0016] FIG. 3B is a top view of one leg and one jaw of the reaching device.
[0017] FIG. 3C is a bottom view of one leg and one jaw of the reaching device.
[0018] FIG. 3D is a front view of one leg and one jaw of the reaching device.
[0019] FIG. 4 is a cross-sectional view of the reaching device taken along line 44 of FIG. 3D .
[0020] Corresponding reference characters indicate corresponding components throughout the several views of the drawings.
DETAILED DESCRIPTION OF THE INVENTION
[0021] The following description is of the best mode presently contemplated for carrying out the invention. This description is not to be taken in a limiting sense, but is made merely for the purpose of describing one or more preferred embodiments of the invention. The scope of the invention should be determined with reference to the claims.
[0022] A side view of a reaching device 10 according to the present invention with telescoping handle 14 fully extended and jaws 12 in a closed position is shown in FIG. 1A , a side view of the reaching device 10 with the telescoping handles 14 fully extended and with the jaws 12 in an open position is shown in FIG. 1B , a side view of the reaching device 10 with the telescoping handles 14 partially extended and with the jaws 12 in an open position is shown in FIG. 1C , and a side view of the reaching device 10 with the telescoping handles 14 retracted and with the jaws 12 in an open position is shown in FIG. 1D . The jaws 12 pivot about a pivot pin 16 to open and close the jaws 12 . The reaching device 10 includes a spring 26 (see FIGS. 3C and 4 ) which biases the jaws toward the closed position, and preferably biased the jaw 12 to a closed position. The handles 14 include telescoping sections which allow the handles 14 to be closed to a compact size for easy storing and carrying. A plunger type keychain 15 may be attached to the reaching device 10 at attachment points 13 on the ends of either handle 14 .
[0023] The reaching device 10 may be a compact easily carried device, or a larger device for use in, for example, a shop or garage. With the telescoping handles 14 in the retracted position (see FIG. 1D ) a compact embodiment of the reaching device is preferably sufficiently small to carry in an automobile glove compartment, a clothing pocket, to similar small area. Preferably, the overall length of the compact embodiment of the reaching device 10 , with the handles 14 retracted, is less than approximately seven inches, and more preferably between approximately six and approximately seven inches.
[0024] A detailed partial side view of the reaching device 10 with a leg cover 18 residing on one leg, a jaw cover 20 residing on one jaw, and a handle cover 21 residing on an end of the handle 14 opposite the jaws 12 , is shown in FIG. 2 . Preferably, the reaching device 10 includes jaw covers 20 on both jaws 12 a , leg covers 18 on both legs 12 b , and handle covers 21 on both handles 14 . Preferably, when the telescoping handles 14 are fully retracted (see FIG. 1D ), the handle cover 21 meets or nearly meets the leg cover 18 . An end section 14 a of the telescoping handle 14 is attached to each leg 12 b . The end section may be a large diameter end of the telescoping handle 14 , but is preferably a small diameter end (i.e., the inner telescoping section) of the telescoping handle 14 .
[0025] A side view of one end section 14 a of the telescoping handle 14 , one leg 12 b , and one jaw 12 a of the reaching device 10 is shown in FIG. 3A , a top view of the end section 14 a of the telescoping handle 14 , the leg 12 b , and the jaw 12 a of the reaching device 10 is shown in FIG. 3B , a bottom view of the end section 14 a of the telescoping handle 14 , the leg 12 b , and the jaw 12 a of the reaching device 10 is shown in FIG. 3C , and a front view of the end section 14 a of the telescoping handle 14 , the leg 12 b , and the jaw 12 a of the reaching device 10 is shown in FIG. 3D . The leg 12 b includes a receiving loop 22 and the ends section 14 a passes through the loop 22 and into the leg 12 b . Preferably, the end section 14 a extends proximal to the pivot pin 16 . The end section 14 a is preferably brazed to the leg 12 b by brazing 24 , and more preferably by brazing 24 extending along most of the length of the end section 14 a residing in the leg 12 b . A spring 26 resides over the pivot pin 16 and biased the jaws 12 a toward a closed position, and preferably biases the jaws to a closed position.
[0026] The telescoping handle 14 is generally constructed from thin wall tubing. The torque applied to the end section 14 a near the entry of the end section 14 a into the leg 12 b may be large, and approaches the limit of the end section 14 a . Thin wall tubing loses much of its strength if it is deformed, for example, flattened. As a result, it is important to retain the original shape of the end section 14 a , and to not crimp and deform the end section 14 a when constructing the reaching device 10 .
[0027] A cross-sectional view of the reaching device 10 taken along line 44 of FIG. 3D is shown in FIG. 4 . The end section 14 a is seen to enter the leg 12 b , pass through the loop 22 , and extend proximal to the pivot pin 16 .
[0028] The reaching tool may be used by holding the handles 14 in one hand, positioning the jaws 12 on opposite sides of an object to be retrieved, preferably aligned at a narrow portion of the object, and releasing one of the handles to allow the jaws to snap closed on the object. The reaching tool thus allows reaching for an object using a single hand.
[0029] While the invention herein disclosed has been described by means of specific embodiments and applications thereof, numerous modifications and variations could be made thereto by those skilled in the art without departing from the scope of the invention set forth in the claims.
|
A compact reaching device includes jaws and telescoping handles. The jaws are joined by a hinge pin and are biased towards a closed position. Legs extend opposite the jaws and squeezing the legs together opens the jaws. Telescoping handles are attached to each leg and may be extended opposite the jaws to allow reaching.
| 4
|
FIELD OF THE INVENTION
The present invention relates to engines, and more particularly engines that are supplied with reformed fuel, and methods for operating such engines.
BACKGROUND
Engine systems that effectively use reformed fuel remain an area of interest. Some existing systems have various shortcomings, drawbacks, and disadvantages relative to certain applications. Accordingly, there remains a need for further contributions in this area of technology.
SUMMARY
One embodiment of the present invention is a unique method for operating an engine. Another embodiment is a unique engine system. Other embodiments include apparatuses, systems, devices, hardware, methods, and combinations for engines and engine systems. Further embodiments, forms, features, aspects, benefits, and advantages of the present application will become apparent from the description and figures provided herewith.
BRIEF DESCRIPTION OF THE DRAWINGS
The description herein makes reference to the accompanying drawings wherein like reference numerals refer to like parts throughout the several views, and wherein:
FIG. 1 schematically illustrates some aspects of a non-limiting example of an engine system in accordance with an embodiment of the present invention.
DETAILED DESCRIPTION
For purposes of promoting an understanding of the principles of the invention, reference will now be made to the embodiments illustrated in the drawings, and specific language will be used to describe the same. It will nonetheless be understood that no limitation of the scope of the invention is intended by the illustration and description of certain embodiments of the invention. In addition, any alterations and/or modifications of the illustrated and/or described embodiment(s) are contemplated as being within the scope of the present invention. Further, any other applications of the principles of the invention, as illustrated and/or described herein, as would normally occur to one skilled in the art to which the invention pertains, are contemplated as being within the scope of the present invention.
Referring to FIG. 1 , some aspects of a non-limiting example of an engine system 10 in accordance with an embodiment of the present invention are schematically illustrated. Engine system 10 is configured for reduced NO x emissions by employing a reformer to generate hydrogen (H 2 ) as part of a hydrogen assisted lean operation scheme. Engine system 10 includes an engine 12 and a fuel delivery system 14 . In one form, engine 12 is an internal combustion engine, e.g., a spark-ignition piston engine. In other embodiments, engine 12 may take other forms, e.g., a gas turbine engine, or another type of reciprocating engine. Engine 12 includes, among other things, an air intake 16 and a combustion chamber 18 . In various embodiments, air intake system 16 may be pressurized by a compressor (not shown), e.g., a turbocharger, a supercharger and/or any other type of compressor. In one form, combustion chamber 18 is a pre-combustion chamber positioned upstream of and in fluid communication with one or more main combustion chambers, e.g., piston combustion chambers or, e.g., a precombustion zone in or coupled to gas turbine engine combustion chambers. In other embodiments, combustion chamber 18 may be or include one or more main combustion chambers, e.g., a main piston engine combustion chamber or a main gas turbine engine combustion chamber.
In one form, fuel delivery system 14 is an auxiliary fuel delivery system that delivers to engine 12 only a portion of the fuel consumed by engine 12 during engine 12 operations, whereas the balance of fuel is supplied by a main fuel system (not shown). In other embodiments, fuel delivery system 14 may supply most or all of the fuel consumed by engine 12 during engine 12 operations. In one form, fuel delivery system 14 includes a compressor 20 operative to receive an oxidant from an oxidant source 22 ; a fuel flow control valve 24 operative to receive and regulate a flow of fuel from a fuel source 26 , a merging chamber 32 and a reformer 34 . In one form, oxidant source 22 is air pressurized by an engine 12 compressor (not shown), e.g., a compressor used to pressurize engine air intake 16 . Compressor 20 is configured to increase the pressure of the oxidant to above the pressure at the engine air intake. In other embodiments, oxidant source 22 may be, for example and without limitation, ambient air or oxygen-enriched air or nitrogen enriched air. In one form, fuel source 26 is a source of pressurized fuel, for example and without limitation, compressed natural gas (CNG). In other embodiments, other fuels may be employed, e.g., other hydrocarbon fuels, pressurized or not. Where fuel source 26 is not pressurized, a pump or compressor may be included to pressurize the fuel received from fuel source 26 . Fuel flow control valve 24 is configured to control the amount of fuel supplied to fuel delivery system 14 , or more particularly, to reformer 34 . In embodiments, where fuel source 26 is not pressurized, fuel flow control valve 24 may include a pump or compressor or may be a pump or compressor.
Merging chamber 32 is in fluid communication with the output of compressor 20 and fuel flow control valve 24 , and is configured to receive and combine the fuel and oxidant and discharge a feed mixture containing both the fuel and the oxidant. The oxygen to carbon molar ratio (substantially the same as the volume ratio under anticipated operating conditions) supplied to reformer 34 may vary with the needs of the application, and may be, for example and without limitation, in the range of 0.5 to 2. The corresponding oxygen content of the oxidant may be, for example and without limitation, 5% to 50% by molar ratio (e.g., volume ratio). Reformer 34 is configured to receive the feed mixture and to reform the feed mixture into a reformed fuel having flammables, including primarily hydrogen (H 2 ) and carbon monoxide (CO), and methane slip, e.g., 0.25%-3%, and trace amounts of higher hydrocarbon slip, such as ethane. The total flammables content of the reformed fuel, associated with the corresponding ranges immediately above, may be, for example and without limitation, in the range from near 0% to approximately 80%. In various embodiments, other gases in various proportions may be included in the reformed fuel in varying amounts, e.g., depending on the oxidant/fuel ratio of the feed stream supplied to reformer 34 , including, for example and without limitation, nitrogen (N 2 ), carbon dioxide (CO 2 ), also small amounts of steam. The form of merging chamber 32 may vary with the needs of the application. For example, in one form, merging chamber 32 is a simple plumbing connection joining the oxidant stream with the fuel stream. In various embodiments, any arrangement that is structured to combine an oxidant stream with a fuel stream, with or without mixing, may be employed. In some embodiments, a mixing chamber, e.g., having swirler vanes to mix the streams, may be employed, e.g., as part of merging chamber 32 or disposed downstream of merging chamber 32 .
Reformer 34 is in fluid communication with merging chamber 32 , and is operative to receive the fuel and oxidant from merging chamber 32 . In one form, reformer 34 is a catalytic reactor having a catalyst 36 . Catalyst 36 may be any catalyst suitable for reforming a gaseous hydrocarbon fuel with an oxidant. Some suitable catalysts include, for example and without limitation, an active material including group VIII noble metals, such as Pd, Pt, Rh, Ir, Os and Ru. A carrier may be employed in conjunction with the catalyst, e.g., a high surface area carrier, including, for example and without limitation, stabilized alumina, zirconia and/or silica-alumina. A catalyst support may also be employed, for example and without limitation, pellets in a fixed bed arrangement, or a coated monolith or honey comb support, e.g., formed of a metallic or refractory. One suitable refractory is cordierite. In a particular form, reformer 34 is a catalytic partial oxidation (CPOX) reformer configured to reform the fuel with the oxidant using catalyst 36 . In other embodiments, other types of reformers may be employed. Combustion chamber 18 is in fluid communication with reformer 34 . Disposed downstream of reformer 34 is a temperature sensor 38 . Temperature sensor 38 is configured to sense the temperature of the reformed fuel after it exits reformer 34 . A sense line 40 electrically couples temperature sensor 38 to fuel flow control valve 24 . In other embodiments, sense line 40 may be an optical or wireless link. Fuel flow control valve 24 is configured to control the amount of fuel supplied to reformer 34 based on the temperature of the gases, e.g., the reformed fuel, exiting the reformer 34 .
In various embodiments, fuel delivery system 14 includes one or more additional components, which may include one or more of a cooler 42 , a junction 44 , a check valve 46 , a junction 48 , a check valve 50 , a valve 52 , a valve 54 , a startup heating system 67 and one or more heaters 80 . Cooler 42 is configured to reduce the temperature of the reformed fuel output by reformer 34 . In one form, cooler 42 is a heat exchanger that is cooled by engine 12 coolant. In other embodiments, cooler 42 may be an air cooled heat exchanger, or may be one or more of other types of cooling systems. In embodiments so equipped, combustion chamber 18 is in fluid communication with cooler 42 , and is configured to receive the cooled reformed fuel from cooler 42 .
Engine air intake 16 is in fluid communication with valve 52 , which is in fluid communication with reformer 34 and cooler 42 via junction 44 . In one form, valve 52 is a back-pressure regulating valve. In other embodiments, valve 52 may be one or more of any type of valve. Junction 44 is operative to allow the venting of some or all of the reformed fuel discharged by reformer 34 from combustion chamber 18 and direct the vented amount of the reformed fuel to another location via valve 52 , such as to engine air intake 16 , to an engine exhaust (not shown), to atmosphere, or to another venting location, including a device or application.
Valve 54 is in fluid communication with fuel supply 26 and junction 48 . Junction 48 is in fluid communication with combustion chamber 18 via check valve 50 . Valve 54 is configured to selectively provide unreformed fuel to combustion chamber 18 . Check valve 46 is configured to prevent the backflow of unreformed fuel toward junction 44 , hence preventing the backflow of unreformed fuel toward reformer 34 and valve 52 . Check valve 50 is configured to prevent backflow from combustion chamber 18 into fuel delivery system 14 .
Startup heating system 67 is in fluid communication with merge chamber 32 , and is configured to heat the feed mixture received from merge chamber 32 to a sufficient temperature to achieve catalytic auto-ignition of the fuel and oxidant upon its exposure to catalyst 36 in reformer 34 in order to start up reformer 34 . Startup heating system 67 includes a start control valve 69 having a valve element 70 and a valve element 72 ; and a feed mixture heater 74 . In one form, valve elements 70 and 72 are part of a combined valving element or system. The inlets of valve elements 70 and 72 are downstream of and fluidly coupled to merging chamber 32 . The outlet of valve element 70 is fluidly coupled to reformer 34 for providing the feed mixture to catalyst 36 of reformer 34 . The outlet of valve element 72 is fluidly coupled to the inlet of feed mixture heater 74 . In one form, start control valve 69 is a three-way valve that operates valve elements 70 and 72 to direct flow entering valve 69 into catalytic reactor 34 directly from merge chamber 32 and/or via feed mixture heater 74 . It is alternatively considered that other valve arrangements may be employed, such as a pair of individual start control valves in place of start control valve 69 with valve elements 70 and 72 .
Feed mixture heater 74 includes a heating body 76 and a flow coil 78 disposed adjacent to heating body 76 . The outlet of feed mixture heater 74 is fluidly coupled to reformer 34 for providing heated feed mixture to catalyst 36 . In the normal operating mode, valve elements 70 and 72 direct all of the feed mixture directly to reformer 34 . In the startup mode, feed mixture is directed through feed mixture heater 74 via flow coil 78 , which is then heated by heating body 76 . In one form, all of the feed mixture is directed through feed mixture heater 74 , although in other embodiments, lesser amounts may be heated, and some of the feed mixture may be passed directly to reformer 34 from merge chamber 32 .
Feed mixture heater 74 is configured to “light” the catalyst 36 of catalytic reactor 34 (initiate the catalytic reaction of fuel and oxidant) by heating the feed mixture, which is supplied to catalytic reactor 34 from feed mixture heater 74 . In one form, the feed mixture is heated by feed mixture heater 74 to a preheat temperature above the catalytic auto-ignition temperature of the feed mixture (the catalytic auto-ignition temperature is the temperature at which reactions are initiated over the catalyst, e.g., catalyst 36 ). Once catalyst 36 is lit, the exothermic reactions taking place at catalyst 36 maintain the temperature of catalytic reactor 34 at a controlled level, based on the amount of fuel and oxidant supplied to catalyst 36 . Also, once catalyst 36 is lit it may no longer be necessary to heat the feed mixture, in which case valve elements 70 and 72 are positioned to direct all of the feed mixture directly to the catalytic reactor 34 , bypassing feed mixture heater 74 . In some embodiments, feed mixture heater 74 may be maintained in the “on” position when engine 12 is not operating, but is required to start quickly.
Heaters 80 are disposed adjacent to catalytic reactor 34 and configured to heat catalyst 36 . In one form, heaters 80 are also configured to maintain catalyst 36 at a preheat temperature that is at or above the catalytic auto-ignition temperature for the feed mixture supplied to reactor 34 . This preheat temperature may be maintained during times when engine 12 is not operating, but is required to start quickly. Some embodiments may employ either or both of startup heating system 67 and heater(s) 80 . In other embodiments, it is alternatively considered that another heater 82 may be used in place of or in addition to startup heating system and heater(s) 80 , e.g., a heater 82 positioned adjacent to catalytic reactor 34 on the upstream side. Such an arrangement may be employed to supply heat more directly to catalyst 36 in order to initiate catalytic reaction of the feed mixture in an upstream portion of catalytic reactor 34 .
In one form, heaters 74 , 80 and 82 are electrical heaters, although it is alternatively considered that in other embodiments, indirect or direct combustion heaters may be employed in addition to or in place of electrical heaters. Also, although the present embodiment employs both feed mixture heater 74 and heaters 80 to rapidly light the feed mixture on the catalyst, it is alternatively considered that in other embodiments, only one such heater may be employed, or a greater number of heaters may be employed.
During operation, the oxidant, e.g., air, is pressurized by compressor 20 and discharged therefrom toward merge chamber 32 . Fuel is delivered to merge point from fuel supply 26 via valve 24 , which controls the rate of flow of the fuel. The oxidant and fuel combine at merge chamber 32 , and are directed to reformer 34 . During a start cycle of engine system 10 , heating body 76 is activated, and valve elements 70 and 72 are activated by a control system (not shown) to direct fuel and oxidant through feed mixture heater 74 . In various embodiments, some or all of the fuel and oxidant feed stream may be directed through feed mixture heater 74 . Heating body 76 adds heat to the feed stream to raise its temperature to the catalytic auto-ignition temperature, i.e., a temperature sufficient for catalytic auto-ignition of the feed stream upon contact with catalyst 36 . The catalytic auto-ignition temperature may vary with the type of catalyst used and the life of the catalyst. For example, with some catalysts, such as at least some of those mentioned herein, the catalytic auto-ignition temperature may be 300° C. at the start of the catalyst's life, but may be 450° C. near the end of the catalyst's life. In various embodiments, one or more of heaters 80 and 82 may be employed to heat the catalyst and/or feed stream to a temperature sufficient for catalytic auto-ignition of the feed stream.
The fuel and oxidant are reformed in reformer 34 using catalyst 36 . Temperature sensor 38 senses the temperature of the reformed fuel exiting reformer 36 . The temperature data from temperature sensor 38 is transmitted to flow control valve 24 via sense line 40 . Valve 24 controls the flow of fuel, and hence the oxidant/fuel mixture based on the sensed temperature, thus maintaining catalyst 36 at a desired temperature. The reformed fuel exiting reformer 34 is then cooled by cooler 42 and discharged into combustion chamber 18 via junctions 44 and 48 and check valves 46 and 50 .
In some circumstances, such as a cold start of engine system 10 , it may be desirable to start engine 12 by supplying unreformed fuel to combustion chamber 18 , and then transition from unreformed fuel to reformed fuel as reformer 34 reaches the ability to reform the fuel. For example, in some situations, fuel is supplied to combustion chamber from fuel supply 26 via flow control valve 54 . Reformer 34 may be started before, during or after engine 12 is started, using one or more of startup heating system 67 , and heater(s) 80 and 82 , e.g., depending upon the embodiment and the needs of the particular application, and the needs of the particular start cycle, e.g., cold start vs. hot restart. Valves 24 , 52 and 54 form a valve system that is configured to transition between 100% unreformed fuel and 0% reformed fuel being supplied to combustion chamber 18 and 0% unreformed fuel and 100% reformed fuel being supplied to the combustion chamber 18 . When reformer 34 is started, e.g., is capable of catalytic auto-ignition of the feed mixture, valves 24 , 52 and 54 , controlled by a control system (not shown), transition from supplying 100% of the fuel being delivered to combustion chamber 18 in the form of unreformed fuel with 0% reformed fuel, to supplying 100% reformed fuel and 0% unreformed fuel to combustion chamber 18 . In one form, the transition is a gradual continuous process. In other embodiments, the transition may be a sudden transition or otherwise stepwise transition. In either case, during the transition, in some embodiments, excess reformed fuel may be vented, e.g., to engine air intake 16 , bypassing combustion chamber 18 , e.g., until the complete transition to 100% reformed fuel being supplied to the combustion chamber is made. In other embodiments, valves 24 , 52 and 54 may modulate the flow of reformed and unreformed fuel without producing an excess of reformed fuel during the start cycle. During the start cycle, the output of compressor 20 may be varied in order to control the rate of flow of oxidant before, during and after the transition to supplying combustion chamber 18 with reformed fuel. The output of compressor 20 may also be varied during normal engine 12 operations in response to demand for reformed fuel.
In one form, during normal operations of engine 12 , e.g., after engine 12 has been started and has achieved steady state operation, combustion chamber 18 is supplied with 100% reformed fuel. In other embodiments, a mixture of reformed fuel and unreformed fuel may be supplied to combustion chamber 18 .
In various embodiments, fuel delivery system 14 controls the output of reformed fuel by varying the output of compressor 20 and by varying the amount of fuel delivered by valve 24 via a control system (not shown). In some embodiments, a valve (not shown) downstream of compressor 20 may be employed to be able to respond more quickly to a demand for higher or lower flow. In some embodiments, the valve may vent excess flow at lower engine 12 operating points, e.g., to intake 16 , to atmosphere, or to engine 12 exhaust. In such embodiments, upon a demand for more output from fuel delivery system 14 , the valve may be closed in order to reduce or eliminate venting. Upon a demand for decreased output from fuel delivery system 14 , the valve would increase the amount of vented oxidant.
In some embodiments, it may be desirable for engine 12 to change operating points quickly, e.g., to switch from low power to high power or from high power to low power fairly quickly. In the event the particular engine 12 configuration is able to change operating points more quickly than the particular fuel delivery system 14 maximum response rate, some embodiments of fuel delivery system 14 may be configured to produce an excess of reformed fuel at a particular operating point or range of operating points in order to provide operating margin. In such embodiments and situations, the excess reformed fuel may be vented, e.g., to air intake 16 via valve 52 , bypassing combustion chamber 18 . In such embodiments, valve 52 , which is in fluid communication between reformer 34 and air intake 16 , is configured to control the amount of flow of the reformed fuel to combustion chamber 18 by bypassing a portion of the reformed fuel to air intake 16 , thereby diverting that portion of reformed fuel flow from combustion chamber 18 .
In some embodiments, valve 52 is configured to increase the vented amount of the reformed fuel in response to a decrease in engine power output; and is configured to decrease the vented amount of the reformed fuel in response to an increase in engine power output. Thus, for example, if an increase in engine 12 output were commanded, the amount of flow of reformed fuel vented to air intake 16 would be reduced by valve 52 under the direction of a control system (not shown), thus increasing the amount of reformed fuel delivered to combustion chamber 18 . On the other hand, if a reduction in engine 12 output were commanded, the amount of flow of reformed fuel vented to air intake 16 would be increased by valve 52 under the direction of the control system, thus decreasing the amount of reformed fuel delivered to combustion chamber 18 . Hence, the ratio of the portion of reformed fuel supplied to combustion chamber 18 relative to the portion of reformed fuel supplied to air intake 16 may be changed so that fuel delivery system 14 may be able to respond more quickly to changes the operating point (e.g., power output) of engine 12 , and in some embodiments, without adversely affecting catalyst 36 , for example, by otherwise creating an off-design transient condition by attempting to follow demand for reformed fuel more quickly than fuel delivery system 14 can readily respond. In some embodiments, by avoiding off-design transient conditions, the adverse effects of operation at off-design transient conditions on the life of catalyst 36 may be reduced or eliminated. In addition, in some embodiments, the ability to more quickly respond to changing demand by controlling the venting of reformed fuel flow, e.g., to air intake 16 , may increase the ability of fuel delivery system 14 to respond to other changing conditions, such as a change in fuel composition, humidity or an engine or engine system component output.
In some embodiments, it may be desirable to limit the amount of reformed fuel provided to air intake 16 , in which case fuel delivery system 14 may be configured to supply no reformed fuel to air intake 16 at or above a selected engine 12 operating point. In some embodiments, this may be the maximum power operating point of engine, below which reformed fuel is provided via valve 52 to air intake 16 , e.g., in proportion to the output of engine 12 , with greater amounts of reformed fuel being provided to air intake 16 at lower power points. In other embodiments, fuel delivery system 14 may be configured to supply no reformed fuel to air intake 16 at or above a other selected engine 12 operating points. In some embodiments, fuel delivery system may be configured to reduce or terminate the flow of reformed fuel to air intake 16 , e.g., once stable engine operation has been achieved.
Embodiments of the present invention include a method for operating an engine, comprising: providing a combustion chamber of the engine with a fuel; starting the engine using the fuel; starting a reformer, wherein the reformer is configured to reform at least some of the fuel; transitioning from the provision of fuel to the combustion chamber to a provision of reformed fuel; and providing only reformed fuel to the combustion chamber.
In a refinement, the combustion chamber is a pre-combustion chamber.
In another refinement, the transitioning is performed after the reformer has reached a catalytic auto-ignition temperature.
In yet another refinement, the engine is an internal combustion engine.
In a further refinement, the fuel is natural gas.
In a yet further refinement, the reformer is a catalytic partial oxidation (CPOX) reformer.
Embodiments of the present invention include a method for operating an engine, comprising: operating a reformer to reform a fuel; supplying a first portion of the reformed fuel to a combustion chamber of the engine during engine operation; venting a second portion of the reformed fuel; wherein the first portion and the second portion are supplied to the respective combustion chamber and venting location at a first ratio; changing an engine operating condition; and supplying the first portion and the second portion to the respective combustion chamber and venting location at a second ratio in response to the change in the engine operating condition.
In a refinement, the combustion chamber is a pre-combustion chamber.
In another refinement, the engine is an internal combustion engine.
In yet another refinement, the fuel is natural gas.
In still another refinement, no reformed fuel is supplied to the venting location at or above a selected engine operating point.
In yet still another refinement, the selected engine operating point is a maximum power operating point.
In a further refinement, the reformer is a catalytic partial oxidation (CPOX) reformer.
Embodiments of the present in engine system, comprising: an engine; a compressor operative to pressurize an oxidant; a reformer in fluid communication with the compressor and a source of fuel, wherein the reformer is configured to receive the oxidant and fuel received from the source of fuel, and to reform the fuel; a cooler in fluid communication with the reformer and configured to reduce the temperature of the reformed fuel output by the reformer; and a combustion chamber of the engine in fluid communication with the cooler, wherein the combustion chamber is configured to receive the cooled reformed fuel from the cooler.
In a refinement, the reformer is a catalytic partial oxidation (CPOX) reformer.
In another refinement, the combustion chamber is a pre-combustion chamber.
In yet another refinement, the engine is a piston engine.
In still another refinement, the engine system further comprises an engine air intake, wherein the compressor is configured to increase the pressure of the oxidant to above the pressure at the engine air intake.
In yet still another refinement, the engine system further comprises an engine air intake and a valve in fluid communication between the reformer and the air intake, wherein the valve is configured to control an amount of flow of the reformed fuel to the combustion chamber by venting a portion of the reformed fuel to the air intake.
In a further refinement, the valve is configured to increase a vented amount of the reformed fuel in response to a decrease in engine power output; and wherein the valve is configured to decrease a vented amount of the reformed fuel in response to an increase in engine power output.
In a yet further refinement, the engine system further comprises a valve configured to control an amount of fuel supplied to the reformer.
In a still further refinement, the engine system further comprises a temperature sensor configured to sense the temperature of the reformed fuel exiting the reformer, wherein the valve is configured to control the amount of fuel supplied based on the temperature of the reformed fuel exiting the reformer.
In a yet still further refinement, the engine system further comprises a valve system configured to transition between 100% unreformed fuel and 0% reformed fuel supplied to the combustion chamber and 0% unreformed fuel and 100% reformed fuel supplied to the combustion chamber.
In an additional further refinement, the reformer includes a catalyst, further comprising a heating system configured to heat the catalyst to a catalytic auto-ignition temperature prior to, during or after startup of the engine.
Embodiments of the present invention include an engine system, comprising: an engine; a reformer configured to receive an oxidant and a fuel and to reform the fuel using the oxidant; a combustion chamber of the engine in fluid communication with the reformer, wherein reformed fuel is received into the combustion chamber; and a valve system configured to transition between 100% unreformed fuel and 0% reformed fuel supplied to the combustion chamber and 0% unreformed fuel and 100% reformed fuel supplied to the combustion chamber.
Embodiments of the present invention include an engine system, comprising: an engine; a reformer configured to receive an oxidant and a fuel and to reform the fuel using the oxidant; a combustion chamber of the engine in fluid communication with the reformer, wherein reformed fuel is received into the combustion chamber; an engine air intake; and a valve in fluid communication between the reformer and the air intake, wherein the valve is configured to control an amount of flow of the reformed fuel to the combustion chamber by venting a portion of the reformed fuel.
In a refinement, the valve is configured to increase a vented amount of the reformed fuel in response to a decrease in engine power output; and wherein the valve is configured to decrease a vented amount of the reformed fuel in response to an increase in engine power output.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment(s), but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims, which scope is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures as permitted under the law. Furthermore it should be understood that while the use of the word preferable, preferably, or preferred in the description above indicates that feature so described may be more desirable, it nonetheless may not be necessary and any embodiment lacking the same may be contemplated as within the scope of the invention, that scope being defined by the claims that follow. In reading the claims it is intended that when words such as “a,” “an,” “at least one” and “at least a portion” are used, there is no intention to limit the claim to only one item unless specifically stated to the contrary in the claim. Further, when the language “at least a portion” and/or “a portion” is used the item may include a portion and/or the entire item unless specifically stated to the contrary.
|
One embodiment of the present invention is a unique method for operating an engine. Another embodiment is a unique engine system. Other embodiments include apparatuses, systems, devices, hardware, methods, and combinations for engines and engine systems. Further embodiments, forms, features, aspects, benefits, and advantages of the present application will become apparent from the description and figures provided herewith.
| 8
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a catalyst for producing an α-olefin comprising a metallocene, an organoaluminum compound, an ionizing ionic compound, and a Lewis base compound. The present invention also relates to a process for producing an α-olefin polymer employing the above catalyst.
2. Description of the Relate Art
For polymerization of olefins, special active catalysts are known which comprise combination of a cyclopentadienyl derivative of a metal such as titanium, zirconium, and hafnium (Group 4B of Periodic Table) with aluminoxane.
This type of catalyst is not used practically in commercial production of olefin polymers mainly because of the following disadvantages: the aluminoxane cannot readily be synthesized with high reproducibility, and therefore preparation of the catalyst and production of the polymers cannot be conducted with sufficient reproducibility; and aluminoxane is required to be used in a high ratio to the transition metal compound to achieve sufficient catalyst activity although the raw material of aluminoxane, e.g., trimethylaluminum, is expensive.
To offset the disadvantages, ionic metallocene catalysts are reported. JP-A-3-207704 discloses an ionic metallocene compound prepared by reacting a metallocene compound with an ionizing ionic compound. WO92/01723 discloses an α-olefin polymerization process employing a catalyst system prepared by reacting a halogenated metallocene compound with an organometallic compound and further bringing the product into contact with an ionizing ionic compound, the catalyst system having sufficient catalytic activity.
The catalyst system employing an ionizing ionic compound, which has a high initial activity, loses its activity with progress of polymerization, disadvantageously.
After comprehensive study to solve the above problems, the inventors of the present invention have found that a catalyst prepared by reacting an ionic metallocene catalyst with a Lewis base compound has a stable catalytic species, and exhibits improved productivity of polymers without deterioration of the catalytic activity.
SUMMARY OF THE INVENTION
The present invention intends to improve productivity of polymers by stabilizing the active species of the catalyst to prevent deterioration of the catalyst activity without the above disadvantages of the prior art.
The present invention provides a catalyst for polymerization of olefin, comprising a) a metallocene compound, b) an ionizing ionic compound, c) an organoaluminum compound, and d) a Lewis base compound:
a) the metallocene compound being represented by General Formula (1) or (2): ##STR1## where Cp 1 , Cp 2 , Cp 3 and Cp 4 are independently a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group; R 1 is a substituted or unsubstituted alkylene, dialkylsilanediyl, dialkylgermanediyl, alkylphosphinediyl, or alkylimino group, and R 1 links Cp 1 with Cp 2 by bridging; M is a titanium atom, a zirconium atom, or a hafnium atom; and R 2 , R 3 , R 4 and R 5 are independently a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, or aryloxy group;
b) the ionizing ionic compound being a compound which is capable of changing the above metallocene compound (a) into a cationic metallocene compound and does not react further the formed cationic metallocene compound;
c) the organoaluminum compound being represented by General Formula (3): ##STR2## where R 6 , R 6' , and R 6" are independently a hydrogen atom, a halogen atom, an amino group, an alkyl group, an alkoxy group, or an aryl group, and at least one of R 6 , R 6' , and R 6" is an alkyl group;
d) the Lewis base compound being capable of donating an electron to the formed cationic metallocene compound.
The present invention also provides a process for producing an α-olefin polymer by polymerizing α-olefin in the presence of the above catalyst.
DETAILED DESCRIPTION OF THE INVENTION
The metallocene compound (a) employed in the present invention is represented by General Formula (1) or (2). The specific examples thereof include:
bis(cyclopentadienyl)titanium dichloride,
bis(cyclopentadienyl)zirconium dichloride,
bis(cyclopentadienyl)hafnium dichloride,
bis(methylcyclopentadienyl)titanium dichloride,
bis(methylcyclopentadienyl)zirconium dichloride,
bis(methylcyclopentadienyl)hafnium dichloride,
bis(butylcyclopentadienyl)titanium dichloride,
bis(butylcyclopentadienyl)zirconium dichloride,
bis(butylcyclopentadienyl)hafnium dichloride,
ethylenebis(indenyl)titanium dichloride,
ethylenebis(indenyl)zirconium dichloride,
ethylenebis(indenyl)hafnium dichloride,
dimethylsilanediylbis(2,4,5-trimethylcyclopentadienyl)titanium dichloride,
dimethylsilanediylbis(2,4,5-trimethylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(2,4,5-trimethylcyclopentadienyl)hafnium dichloride,
dimethylsilanediylbis(2,4-dimethylcyclopentadienyl)titanium dichloride,
dimethylsilanediylbis(2,4-dimethylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(2,4-dimethylcyclopentadienyl)hafnium dichloride,
dimethylsilanediylbis(3-methylcyclopentadienyl)titanium dichloride,
dimethylsilanediylbis(3-methylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(3-methylcyclopentadienyl)hafnium dichloride,
dimethylsilanediylbis(4-t-butyl-2-methylcyclopentadienyl)titanium dichloride,
dimethylsilanediylbis(4-t-butyl-2-methylcyclopentadienyl)zirconium dichloride,
dimethylsilanediylbis(4-t-butyl-2-methylcyclopentadienyl)hafnium dichloride,
diethylsilanediylbis(2,4,5-trimethylcyclopentadienyl)titanium dichloride,
diethylsilanediylbis(2,4,5-trimethylcyclopentadienyl)zirconium dichloride,
diethylsilanediylbis(2,4,5-trimethylcyclopentadienyl)hafnium dichloride,
diethylsilanediylbis(2,4-dimethylcyclopentadienyl)titanium dichloride,
diethylsilanediylbis(2,4-dimethylcyclopentadienyl)zirconium dichloride,
diethylsilanediylbis(2,4-dimethylcyclopentadienyl)hafnium dichloride,
diethylsilanediylbis(3-methylcyclopentadienyl)titanium dichloride,
diethylsilanediylbis(3-methylcyclopentadienyl)zirconium dichloride,
diethylsilanediylbis(3-methylcyclopentadienyl)hafnium dichloride,
diethylsilanediylbis(4-t-butyl-2-methylcyclopentadienyl)titanium dichloride,
diethylsilanediylbis(4-t-butyl-2-methylcyclopentadienyl)zirconium dichloride,
diethylsilanediylbis(4-t-butyl-2-methylcyclopentadienyl)hafnium dichloride,
isopropylidene(cyclopentadienyl)(fluorenyl)titanium dichloride,
isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride,
isopropylidene(cyclopentadienyl)(fluorenyl)hafnium dichloride,
diphenylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,
diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,
methylphenylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,
methylphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,
methylphenylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,
isopropylidene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)titanium dichloride,
isopropylidene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride,
isopropylidene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dichloride,
diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)titanium dichloride,
diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dichloride,
methylphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)titanium dichloride,
methylphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride,
methylphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dichloride,
isopropylidenebis(cyclopentadienyl)titanium dichloride,
isopropylidenebis(cyclopentadienyl)zirconium dichloride,
isopropylidenebis(cyclopentadienyl)hafnium dichloride,
diphenylmethylenebis(cyclopentadienyl)titanium dichloride,
diphenylmethylenebis(cyclopentadienyl)zirconium dichloride,
diphenylmethylenebis(cyclopentadienyl)hafnium dichloride,
methylphenylmethylenebis(cyclopentadienyl)titanium dichloride,
methylphenylmethylenebis(cyclopentadienyl)zirconium dichloride,
methylphenylmethylenebis(cyclopentadienyl)hafnium dichloride,
isopropylidene(cyclopentadienyl)(tetramethylcyclopentadienyl)titanium dichloride,
isopropylidene(cyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride,
isopropylidene(cyclopentadienyl)(tetramethylcyclopentadienyl)hafnium dichloride,
diphenylmethylene(cyclopentadienyl)(tetramethylcyclopentadienyl)titanium dichloride,
diphenylmethylene(cyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl)(tetramethylcyclopentadienyl)hafnium dichloride,
ispropylidenebis(indenyl)titanium dichloride,
ispropylidenebis(indenyl)zirconium dichloride,
ispropylidenebis(indenyl)hafnium dichloride,
diphenylmethylenebis(indenyl)titanium dichloride,
diphenylmethylenebis(indenyl)zirconium dichloride,
diphenylmethylenebis(indenyl)hafnium dichloride,
methylphenylmethylenebis(indenyl)titanium dichloride,
methylphenylmethylenebis(indenyl)zirconium dichloride,
methylphenylmethylenebis(indenyl)hafnium dichloride,
ethylene bis(tetrahydroindenyl) titanium dichloride
ethylene bis(tetrahydroindenyl) zirconium dichloride
ethylene bis(tetrahydroindenyl) hafnium dichloride
dimethylsilanediyl bis (indenyl) titanium dichloride
dimethylsilanediyl bis (indenyl) zirconium dichloride
dimethylsilanediyl bis (indenyl) hafnium dichloride
dimethylsilanediyl bis(2-mehyl-indenyl) titanium dichloride
dimethylsilanediyl bis(2-mehyl-indenyl) zirconium dichloride
dimethylsilanediyl bis(2-mehyl-indenyl) hafnium dichloride
bis(indenyl) titanium dichloride
bis(indenyl) zirconium dichloride
bis(indenyl) hafnium dichloride
bis(cyclopentadienyl) titanium dichloride
bis(cyclopentadienyl) zirconium dichloride
bis(cyclopentadienyl) hafnium dichloride
and the like, but the metallocene compounds are not limited thereto.
The ionizing ionic compound (b) is exemplified by:
tri(n-butyl)ammonium tetrakis(p-tolyl)borate,
tri(n-butyl)ammonium tetrakis(m-tolyl)borate,
tri(n-butyl)ammonium tetrakis(2,4-dimethyl)borate,
tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate,
tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,
N,N-dimethylanilinium tetrakis(p-tolyl)borate,
N,N-dimethylanilinium tetrakis(m-tolyl)borate,
N,N-dimethylanilinium tetrakis(2,4-dimethylphenyl)borate,
N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)borate,
N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,
triphenylcarbenium tetrakis(p-tolyl)borate,
triphenylcarbenium tetrakis(m-tolyl)borate,
triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate,
triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate,
triphenylcarbenium tetrakis(pentafluorophenyl)borate,
tropylium tetrakis(p-tolyl)borate,
tropylium tetrakis(m-tolyl)borate,
tropylium tetrakis(2,4-dimethylphenyl)borate,
tropylium tetrakis(3,5-dimethylphenyl)borate,
tropylium tetrakis(pentafluorophenyl)borate,
lithium tetrakis(pentafluorophenyl)borate,
lithium tetrakis(phenyl)borate,
lithium tetrakis(p-tolyl)borate,
lithium tetrakis(m-tolyl)borate,
lithium tetrakis(2,4-dimethylphenyl)borate,
lithium tetrakis(3,5-dimethylphenyl)borate,
lithium tetrafluoroborate,
sodium tetrakis(pentafluorophenyl)borate,
sodium tetrakis(phenyl) borate,
sodium tetrakis(p-tolyl)borate,
sodium tetrakis(m-tolyl)borate,
sodium tetrakis(2,4-dimethylphenyl)borate,
sodium tetrakis(3,5-dimethylphenyl)borate,
sodium tetrafluoroborate,
potassium tetrakis(pentafluorophenyl)borate,
potassium tetrakis(phenyl)borate,
potassium tetrakis(p-tolyl)borate,
potassium tetrakis(m-tolyl)borate,
potassium tetrakis(2,4-dimethylphenyl)borate,
potassium tetrakis(3,5-dimethylphenyl)borate,
potassium tetrafluoroborate,
tri(n-butyl)ammonium tetrakis(p-tolyl)aluminate,
tri(n-butyl)ammonium tetrakis(m-tolyl)aluminate,
tri(n-butyl)ammonium tetrakis(2,4-dimethyl)aluminate,
tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)aluminate,
tri(n-butyl)ammonium tetrakis(pentafluorophenyl)aluminate,
N,N-dimethylanilinium tetrakis(p-tolyl)aluminate,
N,N-dimethylanilinium tetrakis(m-tolyl)aluminate,
N,N-dimethylanilinium tetrakis(2,4-dimethylphenyl)aluminate,
N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)aluminate,
N,N-dimethylanilinium
tetrakis (pentafluorophenyl)aluminate,
triphenylcarbenium tetrakis(p-tolyl)aluminate,
triphenylcarbenium tetrakis(m-tolyl)aluminate,
triphenylcarbenium tetrakis(2,4-dimethylphenyl)aluminate,
triphenylcarbenium tetrakis(3,5-dimethylphenyl)aluminate,
triphenylcarbenium tetrakis(pentafluorophenyl)aluminate,
tropylium tetrakis(p-tolyl)aluminate,
tropylium tetrakis(m-tolyl)aluminate,
tropylium tetrakis(2,4-dimethylphenyl)aluminate,
tropylium tetrakis(3,5-dimethylphenyl)aluminate,
tropylium tetrakis(pentafluorophenyl)aluminate,
lithium tetrakis(pentafluorophenyl)aluminate,
lithium tetrakis(phenyl)aluminate,
lithium tetrakis(p-tolyl)aluminate,
lithium tetrakis(m-tolyl)aluminate,
lithium tetrakis(2,4-dimethylphenyl)aluminate,
lithium tetrakis(3,5-dimethylphenyl)aluminate,
lithium tetrafluoroaluminate,
sodium tetrakis(pentafluorophenyl)aluminate,
sodium tetrakis(phenyl)aluminate,
sodium tetrakis(p-tolyl)aluminate,
sodium tetrakis(m-tolyl)aluminate,
sodium tetrakis(2,4-dimethylphenyl)aluminate,
sodium tetrakis(3,5-dimethylphenyl)aluminate,
sodium tetrafluoroaluminate,
potassium tetrakis(pentafluorophenyl)aluminate,
potassium tetrakis(phenyl)aluminate,
potassium tetrakis(p-tolyl)aluminate,
potassium tetrakis(m-tolyl)aluminate,
potassium tetrakis(2,4-dimethylphenyl)aluminate,
potassium tetrakis (3,5-dimethylphenyl)aluminate,
potassium tetrafluoroaluminate,
However, the ionizing ionic compound is not limited thereto in the present invention.
The organic aluminum compound (c) employed in the present invention is a compound represented by General Formula (3), and exemplified specifically by trimethylaluminum, triethylaluminum, triisopropylaluminum, diisopropylaluminum chloride, isopropylaluminum dichloride, tributylaluminum, triisobutylaluminum, diisobutylaluminum chloride, isobutylaluminum dichloride, tri(t-butyl)aluminum, di(t-butyl)aluminum chloride, t-butylaluminum dichloride, triamylaluminum, diamylaluminum chloride, amylaluminum dichloride, and the like, but is not limited thereto.
The Lewis base compound (d) employed in the present invention is a compound capable of donating an electron to the formed cationic metallocene compound, and exemplified specifically by
esters such as methyl formate, ethyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, hexyl acetate, cyclohexyl acetate, benzyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, 3-ethylhexylacetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, butyl propionate, isopentyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isopentyl butyrate, isobutyl isobutyrate, ethyl isovalerate, isobutyl isovalerate, butyl stearate, pentyl stearate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isopentyl benzoate, benzyl benzoate, ethyl cinnamate, diethyl oxalate, dibutyl oxalate, dipentyl oxalate, diethyl malonate, dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, and triacetin;
amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, diisopropylamine, butylamine, isobutylamine, dibutylamine, tributylamine, pentylamine, dipentylamine, tripentylamine, 2-ethylhexylamine, allylamine, aniline, N-methylaniline, N,N-dimethylaniline, N,N-diethylaniline, toluidine, cyclohexylamine, dicyclohexylamine, pyrrole, piperidine, pyridine, picoline, 2,4-lutidine, 2,6-lutidine, 2,6-di(t-butyl)pyridine, quinoline, and isoquinoline;
ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, anisole, phenetole, butyl phenyl ether, methoxytoluene, benzyl ethyl ether, diphenyl ether, dibenzyl ether, veratrole, 2-epoxypropane, dioxane, trioxane, furan, 2,5-dimethylfuran, tetrahydrofuran, tetrahydropyrane, 1,2-diethoxyethane, 1,2-dibutoxyethane, and crown ethers;
ketones such as acetone, methyl ethyl ketone, methy propyl ketone, diethyl ketone, butyl methyl ketone, methyl isobutyl ketone, methyl pentyl ketone, dipropyl ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, and acetophenone;
thioethers such as dimethyl sulfide, diethyl sulfide, thiophene, and tetrahydrothiophene;
silyl ethers such as tetramethoxysilane, tetraethoxysilane, tetra(n-propoxy)silane, tetra(isopropoxy)silane, tetra(n-butoxy)silane, tetra(isopentoxy)silane, tetra(n-hexoxy)silane, tetraphenoxysilane, tetrakis(2-ethylhexoxy)silane, tetrakis(2-ethylbutoxy)silane, tetrakis(2-methoxyethoxy)silane, methyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, sec-butyltrimethoxysilane, t-butyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, norbornyltrimethoxysilane, cyclohexyltrimethoxysilane, chloromethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, chlorotrimethoxysilane, triethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, n-butyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane, ethyltri(isopropoxy)silane, isopentyl(n-butoxy)silane, methyl(tri-n-hexoxy)silane, methyldimethoxysilane, diemthyldimethoxysilane, n-propylmethyldimethoxysilane, n-propylethyldimethoxysilane, di(n-propyl)dimethoxysilane, isopropylmethyldimethoxysilane, di(isopropyl)dimethoxysilane, n-propylisopropyldimethoxysilane, n-butylmethyldimethoxysilane, n-butylethyldimethoxysilane, n-butyl-n-propyldimethoxysilane, n-butylisopropyldimethoxysilane, di(n-butyl)dimethoxysilane, isobutylmethyldimethoxysilane, diisobutyldimethoxysilane, sec-butylethyldimethoxysilane, di(sec-butyl)dimethoxysilane, t-butylmethyldimethoxysilane, t-butyl-n-propyldimethoxysilane, di(t-butyl)dimethoxysilane, t-butyl-n-hexyldimethoxysilane, diisoamyldimethoxysilane, n-hexyl-n-propyldimethoxysilane, n-decylmethyldimethoxysilane, norbornylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilne, dimethyldiethoxysilane, diethyldiethoxysilane, di(isopropyl)diethoxysilane, sec-butylmethyldiethoxysilane, t-butylmethyldiethoxysilane, dimethyl(n-butoxy)silane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, trimethyl-n-propoxysilane, trimethyl-t-butoxysilane, trimethylisobutoxysilane, trimethyl-n-butoxysilane, trimethyl-n-pentoxysilane, and trimethylphenoxysilane;
phosphines such as methylphosphine, ethylphosphine, phenylphosphine, benzylphosphine, dimethylphosphine, diethylphosphine, diphenylphosphine, methylphenylphosphine, trimethylphosphine, triethylphosphine, triphenylphosphine, tri(n-butyl)phosphine, ethylbenzylphenylphosphine, ethylbenzylbutylphosphine, trimethoxyphosphine, and diethylethoxyphosphine;
phosphine oxides such as triphenylphosphie oxide, dimethylethoxyphosphie oxide, and triethoxyphosphine oxide;
nitriles such as acrylonitrile, cyclohexanedintirile, and benzonitrile;
nitro compounds such as nitrobenzene, nitrotoluene, and dinitrobenzene;
acetals such as acetone dimethylacetal, acetophenone dimethylacetal, benzophenone dimethylacetal, and cyclohexanone dimethylacetal;
carbonate esters such as diethyl carbonate, diphenyl carbonate, and ethylene carbonate;
thioacetals such as 1-ethoxy-1-(methylthio)cyclopentane, thioketones such as cyclohexanethione;
and the like, but the Lewis base compound is not limited thereto.
The α-olefin in the present invention includes specifically ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and styrene, but is not limited thereto, and two or more thereof may be used in combination.
The catalyst may be prepared in the present invention by mixing the aforementioned components of a metallocene compound (a), an ionizing ionic compound (b), an organoaluminum compound (c) and a Lewis base compound (d), for example, in an inert solvent. The method of catalyst preparation is not limited thereto.
The ionizing ionic compound (b) is used in an amount of preferably not less than one mole per mole of the metallocene compound (a) in the present invention to obtain a desirable catalyst activity. Although the upper limit is not specified, the amount of the ionizing ionic compound to be used is preferably not more than 100 moles per mole of the metallocene compound in consideration of the ash content of the produced polymer, or not more than 30 moles per mole of the metallocene compound in consideration of the cost.
The organic aluminum compound (c) is used in an amount of preferably not less than 10 moles per mole of the metallocene compound (a) in terms of aluminum to obtain a desirable catalyst activity, and not more than 100000 moles to suppress the chain transfer causing lowering of molecular weight and not to increase the ash content, although the amount is not limited thereto.
The Lewis base compound (d) is used in an amount of preferably not less than 0.1 mole per mole of the metallocene compound (a) to stabilize the active species and to prevent loss of the catalyst activity and raise polymer productivity, and preferably not more than 1000 moles not to retard the polymerization reaction.
The process for the polymerization is not specially limited, and includes slurry processes, gas phase processes, bulk processes, solution processes, and high-temperature high-pressure processes. The temperature of the polymerization is not specially limited, but is preferably not lower than 0° C. to obtain high productivity, and not higher than 300° C. to suppress the chain transfer causing lowering of molecular weight and maintain the catalyst efficiency. The pressure of the polymerization is not specially limited, but is preferably atmospheric pressure or higher to obtain high productivity.
The present invention is described more specifically by reference to examples without limiting the invention thereto.
The procedures of polymerization, reaction, and solvent purification were conducted in an inert atmosphere. The solvent used in the reaction was purified, dried, and/or deoxygenated by conventional methods. The compounds used in the reactions were synthesized and identified by conventional methods.
EXAMPLE 1
In a 1-liter reactor, was placed 600 ml of an aliphatic hydrocarbon (IP Solvent 1620, produced by Idemitsu Petrochemical Co.). The temperature of the reactor was maintained at 150° C. Ethylene was fed to the reactor at a pressure of 20 kg/cm 2 . Separately, a solution of 0.25 μmol of diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride in toluene was placed in another vessel, and thereto a solution of triisobutylaluminum in toluene (triisobutyl-aluminum: 20% by weight) was added in an amount of 62.5 μmol in terms of aluminum. The mixture was stirred for one hour. Then the mixture was added to a solution of 0.5 μmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate in toluene, and the mixture was stirred for 10 minutes. To this mixture, a solution of 2.5 μmol of diisobutyl phthalate in toluene was added, and the mixture was stirred for 10 minutes. The resulting mixture was introduced into the aforementioned reactor by nitrogen pressure. The reactor was maintained at 150° C. with stirring at a rate of 1500 rpm for one hour. The resulting reaction product was dried at 100° C. under vacuum for 6 hours to obtain an ethylene polymer. The result is shown in Table 1.
EXAMPLE 2
An ethylene polymer was obtained in the same manner as in Example 1 except that 12.5 μmol of diphenyldimethoxysilane was used in place of 2.5 μmol of the diisobutyl phthalate. The result is shown in Table 1.
COMPARATIVE EXAMPLE 1
An ethylene polymer was obtained in the same manner as in Example 1 except that 2.5 μmol of diisobutyl phthalate was not used. The result is shown in Table 1.
EXAMPLE 3
In a 1-liter reactor, was placed 600 ml of an aliphatic hydrocarbon (IP Solvent 1620, produced by Idemitsu Petrochemical Co.). The temperature of the reactor was maintained at 150° C. Ethylene was fed to the reactor at a pressure of 20 kg/cm 2 . Separately, a solution of 1.0 μmol of ethylenebis(indenyl)zirconium dichloride in toluene was placed in another vessel, and thereto a solution of triisobutylaluminum (triisobutylaluminum: 20% by weight) was added in an amount of 250 μmol in terms of aluminum. The mixture was stirred for one hour. Then the mixture was added to a solution of 2 μmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate in toluene, and the mixture was stirred for 10 minutes. To this mixture, a solution of 50 μmol of diisobutyl phthalate in toluene was added, and the mixture was stirred for 10 minutes. The resulting mixture was introduced into the aforementioned reactor by nitrogen pressure. The reactor was maintained at 150° C. with stirring at a rate of 1500 rpm for one hour. The resulting reaction product was dried at 100° C. under vacuum for 6 hours to obtain an ethylene polymer. The result is shown in Table 1.
EXAMPLE 4
An ethylene polymer was obtained in the same manner as in Example 3 except that 10 μmol of diphenyldimethoxysilane was used in place of 50 μmol of the diisobutyl phthalate. The result is shown in Table 1.
EXAMPLE 5
An ethylene polymer was obtained in the same manner as in Example 3 except that 50 μmol of diphenyldimethoxysilane was used in place of 50 μmol of the diisobutyl phthalate. The result is shown in Table 1.
EXAMPLE 6
An ethylene polymer was obtained in the same manner as in Example 3 except that 250 μmol of diphenyldimethoxysilane was used in place of 50 μmol of the diisobutyl phthalate. The result is shown in Table 1.
COMPARATIVE EXAMPLE 2
An ethylene polymer was obtained in the same manner as in Example 3 except that 50 μmol of diisobutyl phthalate was not used. The result is shown in Table 1.
The ionic metallocene catalyst of the present invention, as described above exhibits excellent catalytic activity in polymerization of α-olefin, and enables production of α-olefin polymer with high efficiency.
TABLE 1______________________________________ Lewis base YieldZr complex compound LB/Zr (g)______________________________________Examples1 Ph.sub.2 C(Cp)(Flu)ZrCl.sub.2 DIBP 10 362 Ph.sub.2 C(Cp)(Flu)ZrCl.sub.2 DPDMS 50 363 Et(Ind).sub.2 ZrCl.sub.2 DIBP 50 644 Et(Ind).sub.2 ZrCl.sub.2 DPDMS 10 465 Et(Ind).sub.2 ZrCl.sub.2 DPDMS 50 406 Et(Ind).sub.2 ZrCl.sub.2 DPDMS 250 48Compara-tiveExamples1 Ph.sub.2 C(Cp)(Flu)ZrCl.sub.2 -- -- 182 Et(Ind).sub.2 ZrCl.sub.2 -- -- 29______________________________________ DIBP: Diisobutyl phthalate DPDMS: Diphenyldimethoxysilane
|
A catalyst for olefin polymerization is provided which comprises, as the components, a) a metallocene compound, b) an ionizing ionic compound, c) an organoaluminum compound, and d) a Lewis base compound. This catalyst has a stable active species and improves productivity of an olefin polymer without deterioration of the catalytic activity.
| 2
|
FIELD OF THE INVENTION
This invention relates to erosion-resistant titanium carbide composites, and to processes for making them.
BACKGROUND OF THE INVENTION
Titanium carbide (TIC) composites, and tungsten carbide (WC) composites are well recognized for their resistance to wear, and general corrosion and resistance to softening at high temperature. Products of of widely varying nature and utility are made from them, and in many applications they serve very well. In many or most cases, the TiC composites function as well as WC composites and frequently cost and weigh less.
However, there are some applications which until this invention have have been better served by WC composites than by TiC composites. For example, previously-known TiC composites are not sufficiently resistant to erosion to be useful in applications such as valves, seals, and bearing surfaces, feed screws, concrete spraying and sandblasting nozzles which will be exposed to severely erosive fluids, particles, and fluid streams. Examples are encountered in, mining, geothermal drilling, and coal liquefication industries.
This field of applications has been primarily served by WC composites in which WC particles are sintered into a cobalt matrix. Even as to these, wherever hydrogen sulfide is likely to be encountered, such as in most deep hole drilling, the cobalt matrix is subject to severe chemical erosion, although that was accepted as an unavoidable circumstance, because there was no alternative.
Over the years conditions have changed. The supply of cobalt has become increasingly unreliable, and as a consequence increasingly expensive. This is because it mostly comes from the country of Zaire, whose social conditions are not conducive to reliability of mining and export operations. This combined with the high specific gravity and inferior erosion resistance (to some conditions) of WC--Co composites, has led the instant inventor to invent a new composite of lesser weight and cost, and with improved erosion resistance.
Lightness of weight becomes important when the composite is incorporated in a moving part. The lighter the composite is, the less energy is needed to move it in operation. The more resistant the composite is to erosion, the longer its life, and the longer the period will be between repair and replacement.
This invention provides a lighter weight composite with erosion resistance at least equivalent to cobalt/WC composites, it utilizes constituents which are readily available in the United States at normal prices. It also can utilize various matrices with high concentrations of TiC capable of being resistant to many chemical erosive conditions which may be damaging to WC/cobalt such as H 2 S.
BRIEF DESCRIPTION OF THE INVENTION
A composite according to this invention comprises titanium carbide grains sintered in a matrix. The matrix is a high chrome tool steel, or a nickel/molybdenum alloy, or cobalt. The TiC provided constitutes between at least 70% and about 95% by volume of the composite, the remainder being the matrix. The preferred range is between 80 and 95 percent by volume.
This is a sintered product. The TiC and the matrix are provided as powder Granules, and are mixed and formed as a rigid body as a consequence of applied heat and pressure. According to the preferred process of this invention, the mixture of the components will be presintered to form a rigid body, and in the presintered condition is machined oversize. The resulting presintered and machined body is then sintered at an appropriate temperature and pressure to its final shape and condition.
This invention will be fully understood from the following detailed description.
DETAILED DESCRIPTION OF THE INVENTION
This invention is a sintered product (and a powder prepared for sintering) which is predominantly TiC sintered in a matrix. In this invention, the content of TiC will variously be given as volume percent, or by weight percent. The specific gravity of TiC is lower compared to the specific gravity of the matrix material, so that the volumetric percentage generally is much higher than its weight percentage.
This is an important observation as it applies to composites which are to resist erosion by fine particles. Solid particles are the principal source of damage to composites, because of their collision with the matrix. Both TiC and WC can withstand this erosion, however it is the matrix which is at risk. The risk can be minimized by reducing the exposed matrix to the erosive particles. One way to accomplish this is to increase the volume percentage of the carbide.
Composites comprising titanium carbide (TIC) embedded in various matrices are well known. Mal U.S. Pat. No. 3,977,837, issued Aug. 31, 1976, shows TiC composites which are valued for their resistance to wear, to thermal shock, and to impact. Also they can provide improved anti-friction properties. The Mal patent also shows various processes for making these composites, generally by sintering. The Mal patent is incorporated herein in its entirety by reference for its showing of such composites and processes for making them.
WC--Co composites are known which have as high as 94% WC by volume, with the remainder cobalt. These function well enough in many erosive environments except where hydrogen sulfide is present. In addition, on a volume basis of product, more WC (by weight) is needed than would be required if TiC could be used. If instead of a cobalt matrix a nickel/chromium matrix were to be substituted for the WC composites, a lesser volume percentage of WC might be used, and the erosion resistance would be significantly reduced. This invention can use not only cobalt for a matrix, but also other matrices in which WC can not be sintered in amounts sufficient for the intended usage.
Composites of TiC with various matrices are well known and have been used by Alloy Technology International, Inc., of 169 Western Highway, West Nyack, N.Y. 10994, under its trademark Ferro-TiC. The highest volumetric percentage of TiC of which the instant inventor is aware is less than 70% in such composites. They are not intended for severely erosive applications. Despite the fact that TiC is much harder and much lighter than WC, the market acceptance of WC--Co composites, and the considerable doubt that a suitably high volume percentage of TiC could be gotten into a matrix for erosion resistance, dissuaded from any thought of using TiC in such applications. The suitability of the composite of this invention has taken its inventor by considerable surprise.
Table I shows the chemical composition of six TiC composites, of which three exemplify the invention (C, D and E), and three are other composites for comparison (A, B and F). This table includes one example of WC in a cobalt matrix, for comparison (G):
TABLE I__________________________________________________________________________ Chemistry, Wt % Hard Phase MatrixI.D. Matrix Alloy Type TiC WC C Cr Mo Ni Co Fe__________________________________________________________________________A High Chrome Tool Steel 60.10 -- .85 10.00 3.00 -- -- Bal.B* High Chrome Tool Steel 60.10 -- .85 10.00 3.00 -- -- Bal.C High Chrome Tool Steel 85.20 -- .85 10.00 3.00 -- -- Bal.D Nickel-Molybdenum 83.00 -- -- -- 10.00 Bal. -- --E Cobalt 83.20 -- -- -- -- -- 100 --F High Chrome Tool Steel 34.50 -- .85 10.00 3.00 -- -- Bal.G Cobalt -- 90 -- -- -- -- 100 --__________________________________________________________________________
Table II shows certain of the physical characteristics of these composites, and it describes their erosion mechanisms.
TABLE II__________________________________________________________________________ Density Hardness Erosion RateI.D. g/cc HRC cc/g × 10 -6 Erosion Mechanism__________________________________________________________________________ A 5.77 74.2 2.08 Matrix Extrusion, Carbide Fragmentation, and Ductile CuttingB 5.79 72.2 2.42C 5.21 77.7 0.96D 5.38 76.5 1.47 Matrix Extrusion, Carbide FragmentationE 5.35 75.8 1.17F 6.46 69.6 3.10 Matrix Extrusion, Ductile Cutting, and Carbide FragmentationG 14.60 75.0 1.46 Preferential Binder Erosion, Carbide__________________________________________________________________________ Fracture
Table III shows the comparative erosion rates of the various composites.
TABLE III______________________________________Alloy Erosion Rate (cc/g × 10.sup.-6)______________________________________A 2.08B 2.42C 0.96D 1.47E 1.17F 3.10G 1.46.______________________________________
It will be observed that the erosion rates of examples A, B, and F (TiC in tool steel), greatly exceed the rates of examples C, D, and E, all of which have a much higher TiC volume percentage. By way of comparison, example G (Cobalt and WC) equals the performance of example D, but is much less resistant than examples C and E. Here it may be commented that the density of examples C, D and E are 5.21, 5.38 and 5.35g/cm 3 , respectively. The density of example G is 14.6 g/cm 3 . Considered on a volumetric basis, to create a body, the example G will require nearly three times as much material by weight (principally because of the greater density of WC compared to TiC.) The weight of the body is nearly tripled, and so is the cost, unless the product is sold at less than its correct value. In table I, the percentage of TiC is given by weight. It can instead as conveniently be referred to by volume percentage. A hard phase TiC on the order of 83-85% by weight will be on the order of 90% by volume. In examples A and B, the weight percentage of about 60% is above 70% by volume.
Composites according to this invention will have at least 70% by volume of TiC. A volume percentage between about 80%-95% is preferred. The remainder is the matrix material.
The high chrome steel matrix will have between about 8% to about 20% chromium, 3 to 10% molybdenum, 0.3 to 1.2% carbon, the balance being iron.
The nickel molybdenum matrix will have about 5% to about 20% molybdenum, the balance being nickel.
To prepare the composites, the defined weights of the various elements and of the TiC are supplied in powder form to a ball mill which is run fop a sufficient time to insure homogenization and proper particle size. The milling fluid is removed, and the homogeneous mixture of powder is dried under vacuum to prevent oxidation. A small amount of wax, perhaps 2% can be added as a binder but this evaporates during the final sintering and is not considered as part of the formulation.
The powder is screened prior to pressing. The resulting powder will then be pressed to an oversized shape, and to achieve a green state sufficient to handle.
There follows a pre-sintering at approximately 1,000 degrees C. for about 2 hours in a vacuum of about 150 to 200 microns of mercury.
Importantly, even with its very high carbide percentage, this pre-sintered body can be machined. It will be machined oversized, because after the final sintering and subsequent hot isostatic pressing 15% to 20% shrinkage will occur. Experience with the manufacturing parameters and with the proportions of constituents will give the processor ample guidance for repeated manufacture of near net shape parts.
The presintered composites are then sintered at about 1,450 degrees C. for about two hours in a vacuum of between about 150 and 200 microns of mercury. Then the composite is hot isostatically pressed at about 1,350 degrees C. for about 4 hours in an argon atmosphere, at an applied steady pressure of about 15 ksi.
Composites A, B, C and F will thereafter be isothermically annealed at about 800 degrees C. for about 4 hours. All composites were machined to near net shape.
Composite A, B, C and F (Tool Steel Matrix) will be heat treated under protective conditions at about 1,080 degrees C. for 1 hour per inch of thickness, followed by quenching in air and double tempering at about 525 degrees C. for one hour (twice). This treatment will give martensitic properties to the tool steel matrix. Composites D and E will be stress-relieved at about 900 degrees C. for about 4 hours, and cooled. The heat treatment discoloration will be removed by grinding and polishing.
It has been observed that polishing the surface of the composite article improves its erosion resistance. Polishing with successively finer grit silicon carbide papers, followed by diamond-paste and alumina powder using known techniques, appears to be beneficial.
The above manufacturing techniques can be varied when the percentage of TiC or matrix composition is changed, but do produce a useful product as described.
Scanning electron microscope studies have shown that densities of at least 99% of the theoretical density are obtained.
This invention thereby provides TiC composites having a surprisingly high percentage of TiC, a percentage not therefore believed to be known, certainly not for a composite to be exposed to severe erosion. In the course of its processing, machining to close tolerences can be attained, on compositions which, if machining was thought of at all, would not have been thought to be attainable.
This invention is not to be limited to the embodiments described in the description, but only on accordance with the scope of the appended claims.
|
A composite, a sintered product of the composite, and a process for producing products from this composite. The composite has a very high volummetric proportion of TiC, and its remainder of a matrix. The TiC constitutes at least 70% by volume and as much as 95% by volume of the ultimate product. The process includes making a green body which can be handled and is thereafter pre-sintered to form a pre-form. The pre-form is oversized relative to the ultimate product. It is sintered and machined, again oversize. Then it is again sintered and subjected to hot isostatic compression, to assume at least a close approximation to the pre-determined dimension of the product. It is characterized by its light weight, resistance to erosion, and resistance to chemical attack.
| 2
|
FIELD OF THE INVENTION
[0001] The present invention relates generally to handlebars for use on human powered vehicles.
BACKGROUND
[0002] Human powered devices, most commonly bicycles, have migrated from a utilitarian purpose to a sport and recreation purpose over the course of the last 100 years.
[0003] The huge majority of bicycles sold and available in the marketplace today are pedal powered, driving a pair of cranks to which a chainring is connected that carries a chain that is operatively coupled to a toothed cog attached to a wheel, thereby transferring power to the wheel. Meanwhile the upper body is stabilised by providing the arms with a pair of handlebars located so the arms can be approximately perpendicular to the trunk of the body and able therefore to provide a leverage point and proper stability to the torso and the possibility to drive the hips when the rider is aiming to produce maximum power.
[0004] The nature of the handlebar is that is it positioned to provide stability to the torso while at the same time allowing the rider to steer the vehicle. On a standard safety bike or diamond frame bicycle the placement of the handlebars is such that the arms (or at least upper arms) are positioned somewhat parallel to the steering axis. This allows the bars to be pushed by one hand and pulled with the other hand while keeping the steering and balance of the bike under control. A rider sprinting to the finish line cants the frame left and right in time with her pedalling stroke and is enabled to do this by the particular structure and placement of the steering axis and handlebar system.
[0005] The mechanical solution of the handlebar and the cultural interpretation of its use is deeply embedded in cycling as a sport, the bicycle industry, and in the psychology of the general community in its attitudes to this mechanical object.
[0006] There is, however, one fundamental drawback to the handlebar that is acutely experienced by Time Trial (TT) riders who need to lower their upper body, narrow their elbows and point their forearms forward in an effort to reduce aerodynamic drag and allow greater speed with the same power output. On these bikes, a second pair of grips is often provided on a second pair of bars attached perpendicularly to the standard handlebar and at a spacing of approximately one hands width either side of the bicycle stem much closer together than the other provided pair of bars. Collectively handlebars including two pairs of bars, one inboard of the other pair, are often referred to as one or both of time trail bars and triathlon bars. To the rear end of these additional inboard bars are often mounted a pair of shaped pads that support the forearm close to the elbow. The drawback of this arrangement is that the bike carries two sets of grips, so at all times the superfluous pair of grips and their supporting framework is creating aerodynamic drag and adding weight thereby requiring power from the rider's limited supply and thus preventing the rider from achieving their best or fastest time.
[0007] Triathlon bars typically place thumb shift levers on the ends of the inboard bars as a user is likely going to be resting his hands on these bars most often during a time trail or a triathlon preventing the need for the user to move his or her hands and disrupt aerodynamic flow to change gears. The brakes are not used nearly as often during a time trial and as such the brake levers are most often placed on the outboard pair of bars at their respective distal ends. While moving a user's arms from the inboard to outboard position will induce drag that will use energy, the amount lost will be much less than the kinetic energy the user is intending to lose through the application of the brakes anyhow.
[0008] Problems can arise when the user is on one set of the bars and desires to effect a change requiring one or both of his/her hands to be on the other set of bars. For instance, while climbing and using the outer bars for leverage, the user must reach in to the inner bars to change the gear which can have a deleterious effect on momentum especially when the user is using the bars as a leverage point to assist in propulsion.
[0009] More significantly, if the rider is crouched low on the inner bars and is at speed when a dangerous road hazard is identified, there is a critical delay while the rider moves their hand to the outer bars in order to apply the brakes. The European standard for bicycle braking performance is consistent with a de-acceleration at half the acceleration due to gravity, or in simple numbers, 5 meters per second squared (5 m/s 2 ). Road safety studies and simple calculations of the distance travelled at 46.8 kph, or 13 m/s during the time it takes to apply the brakes shows how critical reaction time is. At 46.8 kph or 13 m/s, a speed that is easily attained on a time trial bicycle, the braking distance is 16.9 m.
[0010] A study titled ‘Evaluation of brake reaction times on a motorcycle’ was produced by the Promocycle Foundation in Quebec, Canada in Jan. 5, 2003 (FMQ-BRT 0.154). This study shows that if the hand is positioned over the front brake lever an average reaction time of 0.359 seconds was recorded, while if the hand was not covering the lever, an average braking reaction time of 0.545 was found, a difference of 0.186 seconds—it takes valuable time to lift the right fingers or right foot over the brake levers of a motorcycle. At 13 m/s, a rider will travel 2.4 m during the reaction time, so the total stopping distance is unlikely to be less than 19.3 m.
[0011] There are no studies known to the inventor on the braking reaction time taken by a time trial rider if the body is in the aero position with hands on the inner grips or the inboard bars while the brake levers are on the outer bars. We can note that having the right hand fingers over the front brake lever of a motorcycle is a very close analogue for having the fingers of either or both hands over the brake levers on a bicycle. We can note the 0.186 second improved time if the rider covers the lever with the fingers rather than wrap the fingers on the handlebar, so we know that even very small preparatory movements cost valuable time. It is conservative to expect that a time trial rider will take at least one second to use her back muscles to lift her upper body weight and allow her hands to transfer to the outer grips whereupon the brake levers can be actuated. For the purposes of illustration, we can calculate the stopping distance when one second is added to the reaction time caused by the rider moving their hands to the outer grip position in order to apply the brakes.
[0012] A further one second delay to begin applying the brakes causes the rider to overshoot the possible stopping distance by 13 meters, if the rider is travelling at 13 m/s. This distance of 13 m is not far short of the total stopping distance of a rider who is ready to apply the brakes, 19.3 m. At the stopping point achieved by a rider at 13 m/s braking at 0.5 g with a normal reaction time, a similar rider with a reaction time delayed by one seconds will be still travelling 11.4 m/s or 41 kph, fast enough to do serious injury to the rider in a situation where a bicycle without this fundamental flaw would have pulled up safely. This is fundamentally dangerous.
[0013] To address this fundamental danger to the time trial rider, especially when time trial bikes are ridden in traffic rather than on controlled courses, it is possible to install a second brake lever pair to the inner bars.
[0014] Folding handlebars that permit a user to fold a bicycle for transport or storage are known in the prior art; however, the prior art does not disclose handlebars that can be moved from an outer position to a more aerodynamic position. The prior art further fails to disclose or suggest handlebars in which the movement of the bars can be accomplished while the bicycle is being ridden.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] Exemplary embodiments are illustrated in referenced figures of the drawings. It is intended that the embodiments and figures disclosed herein are to be considered illustrative rather than limiting.
[0016] FIG. 1 is a isomeric view of the handlebar in a folded configuration with control components attached according to an embodiment of the present invention.
[0017] FIG. 2 is a side view of the handlebar in a folded configuration with control components attached according to an embodiment of the present invention.
[0018] FIG. 3 is a top view of the handlebars in the folded position with control components attached according to an embodiment of the present invention.
[0019] FIG. 4 is a side view illustration showing the location of the handlebar on a typical time trail/triathlon bicycle according to an embodiment of the present invention.
[0020] FIG. 5 a side elevation of the unfolded handlebar with control components attached according to an embodiment of the present invention.
[0021] FIG. 6 is an exploded isometric diagram of the handlebar with control components according to an embodiment of the present invention.
[0022] FIG. 7 is a section through one arm of the handlebar showing the actuator mechanism according to an embodiment of the present invention.
[0023] FIG. 8 is an exploded isometric diagram of a bar end shifter with internal cable routing according to an embodiment of the present invention.
[0024] FIG. 9 is a side view illustration showing the location of the handlebar on a typical time recumbent bicycle according to an embodiment of the present invention.
[0025] FIG. 10 is a side elevation of the handlebar with control components attached configured for use with a recumbent bicycle according to an embodiment of the present invention.
[0026] FIG. 11 is an isometric view drawing of the handlebar with control components attached configured for use with a recumbent bicycle according to an embodiment of the present invention.
[0027] FIG. 12 is an isometric view of the handlebar with control components attached according to another embodiment of the present invention.
[0028] FIG. 13 is an isometric view of fixed handlebar with internal cable control system according to yet another embodiment of the present invention.
[0029] FIG. 14 is an isomeric view of the handlebar in a unfolded configuration with control components attached according to an embodiment of the present invention.
[0030] FIG. 15 is a side elevation of the handlebar in the unfolded configuration with control components attached according to an embodiment of the present invention.
DETAILED DESCRIPTION
[0031] Embodiments of the present invention comprise handlebars that include only two bar extensions (or sections) instead of the four common in prior art time trial bars. The two bar extensions (referred herein as left and right arm sections) can be folded (or pivoted) while the rider is in motion between an aerodynamic position with the handholds placed relative close together and a second position permitting the rider to apply greater leverage using his/her hands, arms and upper body where the handholds are more widely spaced apart.
[0032] Embodiments of the handlebars place both brake and shift levers on each of the left and right arm sections wherein a rider can cover the brakes with his/her hands whether in either handlebar position and shift easily without having to move his/her hands from one bar/section to another. This is in contrast to prior art time trial bars wherein two pairs of bar extensions or arm sections are provided wherein a rider has to move to the aerodynamic position to shift gears and the wide position to brake. As discussed above, this can have serious safety implications. In placing the brake controls and shift controls on the same arm sections, embodiments of the invention include a novel bar end shifter that routs the associated shift cable internally through the body of the shifter directly into the internal cavity of an associated hollow interior of the left or right arm section. The new shifter eliminates the need to run a shift cable and its associated housing over the outside of the arm section in the handgrip/handhold portion thereof resulting in a smoother and rounder grip region that is more comfortable to hold for long periods.
Terminology
[0033] The terms and phrases as indicated in quotation marks (“ ”) in this section are intended to have the meaning ascribed to them in this Terminology section applied to them throughout this document, including in the claims, unless clearly indicated otherwise in context. Further, as applicable, the stated definitions are to apply, regardless of the word or phrase's case, to the singular and plural variations of the defined word or phrase.
[0034] The term “or” as used in this specification and the appended claims is not meant to be exclusive; rather the term is inclusive, meaning either or both.
[0035] References in the specification to “one embodiment”, “an embodiment”, “another embodiment, “a preferred embodiment”, “an alternative embodiment”, “one variation”, “a variation” and similar phrases mean that a particular feature, structure, or characteristic described in connection with the embodiment or variation, is included in at least an embodiment or variation of the invention. The phrase “in one embodiment”, “in one variation” or similar phrases, as used in various places in the specification, are not necessarily meant to refer to the same embodiment or the same variation.
[0036] The term “approximately,” as used in this specification and appended claims, refers to plus or minus 10% of the value given.
[0037] The term “about,” as used in this specification and appended claims, refers to plus or minus 20% of the value given.
[0038] The terms “generally” and “substantially,” as used in this specification and appended claims, mean mostly, or for the most part.
[0039] The term “couple” or “coupled” as used in this specification and the appended claims refers to either an indirect or direct connection between the identified elements, components or objects. Often the manner of the coupling will be related specifically to the manner in which the two coupled elements interact.
[0040] The phrases “upright-style bicycle” and “upright-style bicycle frame” and similar phrases refer to bicycles and frames respectively wherein the rider typically sits upright on a small seat/saddle typically leaning forwardly bracing his/her arm/hands against a pair of handlebars. The “upright-style bicycle” is the most common and well-known type of bicycle and accordingly the phrase as used herein does not deviate from its commonly held meaning. In contrast, a “recumbent bicycle” is one in which the rider leans generally rearwardly in a supine position and the seat typically includes a backrest for support.
[0041] The term “road bike” refers to the racing style of bike that conforms to the prescriptions of the Union International Cyclist governing competitive road racing.
[0042] The terms “left arm section” and “right arm sections” as used herein refer to extensions of the handlebar that include a handhold or handgrip portion on which a rider holds the bar with his/her hands. In many variations of the arm sections, they have hollow interiors although variations are contemplated where this is not necessarily the case.
[0043] The term “base section” as used herein refers to a portion of the handlebars that is positioned generally transverse or normal to the direction of travel of a bicycle when installed thereon. It is through the base section that the handlebars are most typically coupled to a bicycle often through a stem. As with the arms sections, the base section in many variations has a hollow interior although other variations that are not hollow and/or tubular are also contemplated. The left and right ends of the base section (also referred to as left and right base ends) are coupled with the proximal ends of respective arm sections through a respective left or right “pivot mechanism”.
[0044] The terms “left pivot mechanism” and “right pivot mechanism” as used herein refer to the pivoting joints between the respective left and right arm sections with the base section. The pivot mechanisms permit a rider to move each arm section between at least first and second positions.
[0045] The terms “first left arm position” and “first right arm position” as used herein refers to the position of the respective arm sections when they are in a folded position with each arm parallel to the other and spaced closely together. The “first position” is used by a rider to maximize aerodynamic efficiency. A top view with both arm sections in the first positions is provided in FIG. 3 .
[0046] The terms “second left arm position” and “second right arm position” as used herein refers to the position of the respective arm sections when they are in an unfolded position with each arm diverging outwardly from the base section and each other. The “second position” is used by a rider to maximize stability and leverage. A view with both arm sections in the second positions is provided in FIG. 14 .
[0047] The terms “actuator mechanism”, “left actuator mechanism” and “right actuator mechanism” as used herein refer to mechanical devices that selectively lock and release the respective pivot mechanisms to permit a rider to move the arm sections between the first and second positions.
[0048] The term “brake lever assembly” as used herein refers to a brake lever, and the clamp or mounting structure used to secure the assembly including the lever to the respective left or right arm section. Depending on context, the term “brake lever assembly” may also include the associated brake cable and housing that is routed from the bars to the appropriate brake callipers on the bicycle.
[0049] The terms “thumb shifter” or “shift lever assembly” as used herein refers to the actuator used by a rider to change gears. The embodiment of an actuator described herein includes a shift lever, a base to which the shift lever is rotatably coupled and a clamping or wedge mechanism to secure the assembly to the associated arm section.
[0050] The term “driveline transmission device” as used herein refers to a derailleur or any other device that functionally causes the gearing of the bicycle to change responsive to input from a rider through a thumb shifter or shift lever assembly.
[0051] The term “arm rests” as used herein refer to pads and associated structure that are positioned behind the handgrips on the handlebars that permit a rider to rest his/her forearms proximate his/her elbows thereon when riding in the first position.
A First Embodiment of a Folding Handlebar
[0052] Referring primarily to FIGS. 1-3 , 5 & 6 , a first embodiment of the handlebar 100 comprises three primary sections: a base section 104 having left and right ends; a left arm section 102 A having a proximal end and a distal end; and a right arm section 102 B also having a proximal end and a distal end. As illustrated each of these sections is of substantially tubular construction and includes a substantially hollow interior. Concerning the left and right arm sections as shown, they are bent at an intermediate location with the portion of the sections forward of the bend comprising the location that a rider would grip the bars during use i.e. handholds or handgrips.
[0053] The base and arm sections 104 & 102 can be fabricated from any suitable material but are typically comprised of an aluminium alloy or a carbon fiber composite laminate. The bend in the arm sections can be (i) molded in place, such as when the arm sections are comprised of a composite material, (ii) formed by bending a straight tube, such as with an aluminium tube section, or (iii) fabricated by welding or otherwise joining two tubular pieces of material together at the desired angle.
[0054] The left and right ends of the base section 104 are both bent downwardly relative to the middle portion such that the bent ends are substantially symmetrical with each other relative to the middle portion. As with the bend in the arm sections, the bends in the base section can be formed by any suitable means. The angle of the bent portion relative to the middle portion of the base section can vary depending on the desired positioning of the left and right arms section when they are moved between first and second positions as will become clear from the disclosure below. Typically, the left and right ends include a cylindrical portion 180 with an annular outer surface of a specific diameter. These cylindrical portions form part of the respective left or right pivot mechanism 106 that joins the left and right arm sections 102 A & B with the base section 104 and permit the desired movement of the arm sections between the first and second positions. These respective left and right cylindrical portions 180 of the left and right ends of the base section are also referred to as the left pivot inner cylinder and the right pivot inner cylinder and have a longitudinal axis (or axis of rotation) that defines the rotational path of the arm section 102 when moved from the first position to the second position.
[0055] At the proximal ends of the arm sections 102 A&B a cylindrical tube portion 182 is provided. The cylindrical tube is relatively short having a length that generally corresponds to the length of the cylindrical portions 180 of the base section described above. The cylindrical tube portions include an annular inner surface having a diameter at least slightly greater than that of the diameter of the annular outer surface of the cylindrical portions described in the preceding paragraph. The cylindrical tube portions also form part of the respective left and right pivot mechanisms 106 and are adapted to be received over the corresponding cylindrical portions of the left and right pivot inner cylinders to permit rotational or pivotal movement relative to each other. The longitudinal axis of the cylindrical tube portion is generally normal to the longitudinal or rotational axis of the adjacent portion of the corresponding arm section, although the angle between the axes can vary depending on the particular design. The cylindrical tube can be attached/joined to the remainder of the arm section by any suitable means including welding, adhesive bonding, brazing and even in situ molding.
[0056] In addition to the respective left or right cylindrical portion 180 and the respective left or right cylindrical tube portion 182 , the pivot mechanisms typically include one or more bushings/bearings 184 & 186 to help ensure a proper fit between the base section 104 and the respective arm section 102 as well as facilitate the rotation of the arm section as desired. To secure the arm sections in place on the cylindrical portions, a circular snap ring 188 is provided that fits within an annular groove 190 of the cylindrical portion proximate the outer edge thereof.
[0057] Considering the illustrated pivot mechanisms 106 and particular the exploded view provided in FIG. 6 , assembly of an arm section 102 to the base section 104 comprises sliding a first annular bushing 184 over the cylindrical portion 180 until it is flush against an associated annular shoulder provided on the cylindrical portion. Next, a shoulder-less second bushing 186 is slid onto the cylindrical portion. The outer cylindrical tube portion 182 of the associated arm section is then slid over the bushings and the underlying cylindrical portion. Finally, the snap ring 188 is placed in the annular groove 190 to secure the arm section to the base section.
[0058] Of particular note as most clearly illustrated in FIG. 6 , each of the cylindrical portions 180 include two radially extending bores 192 that are similarly longitudinally positioned relative to the axis of rotation of the cylindrical portion but our spaced apart circumferentially on the cylindrical portion's surface. These bores are adapted to selectively receive a lock pin 148 of an associated actuator mechanism therein depending on the positioning of the respective arm section 102 as is described in greater detail below.
[0059] Each of the outer cylindrical tube portions 182 includes a radially extending tube bore 194 located at a similar longitudinal position as the radially extending bores 192 relative to the axis of rotation when the arm section is received on and mounted to the base section 104 . The aforementioned lock pin 148 is received in this bore such that the lock pin is adapted to move radially therein when an actuator lever 116 of the actuator mechanism is actuated as is also described in greater detail below.
[0060] As can be appreciated, it is imperative with the illustrated design that the bushings do not cover the radially extending bores 192 on the cylindrical portions 180 as this would hinder the movement of the lock pin 148 in and out of the bores. As is evident from the illustrations, the interaction of the annular shoulder on the first bushing 184 with an inside edge of the outer cylindrical tube portion prevents the bushing from moving over and covering the bores. Concerning the second bushing 186 , it is received on an outer portion of the cylindrical portion that has an outside diameter that is diameter slightly less than the diameter of the remainder of the cylindrical portion. Correspondingly, the inside diameter of the second bushing is slightly smaller to fit properly over the outer portion but it also has a slightly greater thickness such that its outside diameter is substantially similar to the outside diameter of first bushing 184 . As can be expected, the inside edge of the second bushing butts up with the edge formed at the transition between the outer portion of the cylindrical portion and the remaining portion of slightly greater diameter preventing the bushing from sliding inwardly and covering the bore holes 192 .
[0061] As described above, each arm section 102 pivots or rotates around its attachment point to move the left and right arm sections between the first and second positions. The respective actuator mechanisms that include the lock pin 148 mentioned above act to secure the arm sections in the desired position and help limit the range of movement of the arm sections to that which is necessary to move between the two positions. As will become apparent in the review of this disclosure, the actuator mechanism of each arm section can be independently operated so that each section can be moved independently. This enhances safety as a rider can move the arm sections one at a time with the other arm section being locked in place to provide for rider stability and control.
[0062] The actuator mechanism and each of its components is best illustrated in FIGS. 6 & 7 . Each of the left and right actuator mechanisms comprises a lock pin assembly 148 , 150 , 154 , 156 & 158 , an actuator lever 122 , a connector cable 124 coupling the lock pin assembly with the actuator lever and a biasing mechanism 152 .
[0063] The lock pin assembly includes the lock pin 148 that has a conically shaped end adapted to slide in and out of the bore holes 192 of the cylindrical portion 180 while also being resident in the radially extending tube bore 194 of the outer cylindrical tube portion 182 . When received in both the tube bore 194 and one of the pivot bore holes 192 , the lock pin effectively locks the respective arm section 102 in place relative to the base section 104 . The lock pin is typically coupled or integral with a smaller diameter rigid tubular shaft 150 that extends from one end of the lock pin. A radially extending bore 154 is provided in the lock pin to receive a set screw 156 therein that is tightened to secure the connector cable 124 in place.
[0064] A disk-shaped stop 158 is provided distally of the lock pin 148 and includes an aperture into which the tubular shaft is received. As can best be seen in FIG. 7 , the disk is fixedly secured in place within the hollow interior of the arm section 102 at an intermediate location along the section's length. The disk acts as the distal stop for the biasing mechanism, which typically comprises a coil spring 152 that is received over the tubular shaft. The back edge of the lock pin serves as a proximal stop for the coil spring.
[0065] As is clear from the figures, as the lock pin 148 is retracted from the bores 192 of the cylindrical portion 180 , the coil spring 152 is compressed and applies a restorative force to the pin to urge it back into place against either the surface of the cylindrical portion or into one of the associated bore holes. Retraction is accomplished by operation of the actuator lever 122 , which is typically located distally of the lock pin assembly on the outside of the arm section 102 and is connected thereto by way of a connector cable 124 that is typically threaded through the interior of the arm section. The distal end of the cable includes a cable stop that is received in an appropriately configured slot on one end of the lever to hold the cable in place. In variations, the connector cable can be replaced with another type of connector including but not limited to a shaft.
[0066] As illustrated the actuator lever 122 is pivotally secured to a corresponding brake lever assembly 110 through a cylindrical boss 142 (see FIG. 6 ) that extends from the assembly. This location allows for the easily actuation of the lever by the finger of a rider without the rider having to move his/her hand off of the bar or even change the position of his/her hand relative to the bar substantially. In variations and other embodiments, the lever can be attached to the bar's arm section directly by way of a clamp that includes an appropriate mounting boss or by way of a boss that is directly attached to the surface of the corresponding bar section. Other actuator mechanisms are contemplated as well. For instance in one variation the lever could be replaced with a push button that is adapted to retract the lock pin when depressed.
[0067] Referring primarily to FIG. 1 , the handlebar assembly is typically specified with several control systems. The first control system, as has been discussed in detail above, comprises the left and right actuator mechanisms that lock and unlock the respective arm sections 102 to permit a rider to rotate or pivot the arm sections between first and second positions.
[0068] The second control system comprises the left and right brake lever assemblies 110 . As mentioned above, in certain variations these levers include bosses 142 mounted on the associated bar clamps 120 to facilitate the mounting of the actuator levers 122 of the actuator mechanisms. The brake levers 118 and their mounting orientation is notable in that the levers extend distally from the clamp 120 away from the rider in sharp contrast to typical prior art levers for use on time trail bars wherein the levers extend generally proximally towards the rider. Accordingly, when riding the rider grips the arm sections 102 in front of the brake clamps 120 with the brake cables and associated housing 130 extending rearwardly from the clamp region, they will not interfere with the rider's hands.
[0069] The third and final control system comprises one or more thumb shifter assemblies 108 . An exploded view of a thumb shifter is shown in FIG. 8 . In contrast to prior art thumb shifter assemblies wherein the cable and associated housing are routed generally outwardly and away from the shifter body, embodiments of the shifter assemblies described herein route the cable through the body 114 and through the associated wedge nut or mounting assembly 160 - 164 . Accordingly, the cable and its associated housing 132 & 168 can be routed within the hollow interior of the arm section 102 especially through the portion of the arm sections that are gripped by a rider during use. In the illustrated embodiment as can be seen in FIG. 2 , the shift lever cable and housing 132 exits the arm section proximate the proximal end thereof through a provided opening 136 . The cable and housing 132 along with the brake lever housing 130 and cable are routed into the hollow interior of the base section 104 . The cables exit from the base section near its center through a provided opening 140 as best shown in FIG. 3 . From there the cables and housings are routed to the brake callipers and derailleurs of the bike.
[0070] With primary reference to FIG. 8 , the thumb shifter assembly 108 comprises a shift lever 116 including a bore and/or channel adapted to receive the shift lever cable therein. As can be appreciated, the shift lever may interface with a ratcheting or indexing mechanism 174 that controls the amount of rotation of the lever between tactile stops. The amount of rotation is indexed based on the amount of cable that is pulled or pushed as is necessary to effectuate a gear change in the associated front or rear derailleur. The lever and indexing mechanism are secured to a tang 172 by one or more suitable fasteners 170 & 176 . The tang extends from the shifter body 114 . The mounting configuration permits the rotational or pivotal movement of the lever relative to the indexing mechanism and the body.
[0071] The body includes a threaded longitudinal bore 173 that is adapted to receive the externally threaded hollow shaft of a wedge nut 164 . Referring to FIG. 8A , the end of the wedge nut's hollow shaft includes a recessed hexagonal socket 165 adapted to receive a socket wrench therein to selectively loosen or tighten the wedge nut within the body's threaded bore with a hex key/wrench.
[0072] Two or more partially annular wedge pieces 160 are provided over the surface of the shaft of the wedge nut 164 . Together the pieces form the shape of a cylinder. The pieces are held together by an annular o-ring 162 or spring. The top and bottom surfaces of the assembled wedge pieces form frustoconical indentations 163 A&B that mat respectively with frustoconical protrusions 167 A&B on the bottom of the body 114 and on the head of the wedge nut. Operationally, when the wedge nut is tightened into the shifter body, the frustoconical protrusions on the wedge nut and body press against the frustoconical indentations and cause the wedge pieces to expand typically against an inside surface of a corresponding arm section 102 thereby securing the thumb shifter 108 therein.
[0073] The shifter cable extends through the interior of the wedge nut 164 that extends through the threaded bore 173 of the shifter body and is at least partially wrapped around and received in an annular channel 177 provided around the lever's axis of rotation where its end is secured in a provided cable stop. Of important note, the shift lever is secured to the tang 172 at a position wherein the axis of the longitudinal wedge nut 164 , and incidentally the path of the shifter cable 168 within the wedge nut, intersects with the annular channel tangentially. This is in contrast to many prior art thumb shifters wherein the longitudinal axis of the wedge nut, which does not have a cable running therethrough, generally intersects normally with the axis of rotation of the shift lever. Moving the position of the wedge nut's axis relative to the lever's axis of rotation permits the shift cable to be run through a hollow wedge nut without requiring the cable to bend significantly to be received into an annular channel. As can be appreciated any tight and significant bends in the cable proximate the lever would induce a significant amount of friction that would detract from the smooth operation of the thumb shifter.
[0074] Still referring to FIG. 8 , the shift cable's housing 132 butts up against the bottom end of the wedge nut 164 and in most variations is received in a shallow cavity (not shown). The housing with the cable 168 contained therein extends through the hollow interior of the respective arm section until exiting the arm section 102 through opening 136 .
[0075] As illustrated, typical variations of the handlebar assembly 100 include a pair of arm rests 112 . As shown in FIG. 1 , a left or right clamp 126 is secured to a proximal location on the respective left or right arm section 102 . A generally concavely-shaped plate 128 is provided on which a rider rests his/her forearms proximate his/her elbows while riding with the bars in the first position. Typically, foam or gel-type padding is provided to enhance comfort. The clamps permit the rider to move the arm rests fore and aft to adjust their position to accommodate a particular rider. It can be appreciated that variations are contemplated wherein no arm rests are provided or wherein the arm rests are provided separately from the bar.
[0076] As indicated, the configuration of the bars illustrated in FIGS. 1-7 is optimized for use on a traditional upright-style bicycle and more particularly for a time trial or triathlon bicycle. FIG. 4 provides an illustration of the bars installed on a time trial bicycle 500 , which is illustrated in broken line.
A Second Embodiment of a Folding Handlebar
[0077] FIGS. 9-11 provide illustrations from several vantage points of a variation of the first embodiment handlebars configured for use with a recumbent bicycle. Of significance, the arm sections 102 A&B, base section 104 , the pivot mechanisms 106 and the three control systems are typically substantially identical or similar to those described above with reference to the first embodiment. The second embodiment recumbent style handlebars differ from the first in the absence of the arm section mounting arm rests and the inclusion of a recumbent arm rest extension 200 that extends rearwardly of the base section to provide an new location to mount arm rests that is more suitable for recumbent bicycles and riders. The handlebar assembly installed on a recumbent bicycle is illustrated in FIG. 9 with the recumbent bicycle 600 illustrated in broken lines.
[0078] The recumbent arm rest extension 200 comprises a clamp section 214 that secures the assembly to the base section 104 . It is to be appreciated that the clamp section is configured not to interfere with the clamp on a stem of the recumbent bicycle that also interfaces with the base section to secure the handlebar assembly to the bicycle. The clamp section is also configured not to interfere with the routing of the various brake and shifter cables and housing as they exit the base section.
[0079] An inverted T-section 202 & 212 typically comprised of tubing is secured to the clamp section 214 by welding, brazing or some other suitable means. The leg 202 of the inverted-T extends generally downwardly and rearwardly of the base section. In the illustrated variation, the leg has an arcuate shape but in other variations it can be straight. At the distal end of the leg an arm tube 212 extends to the left and the right to form the arms of the inverted-T. Arm rest assemblies 206 , comprising clamps 210 and concavely-shaped plates 208 , that are generally similar to the arm rest assemblies described with reference to the first embodiment are mounted to the arm tube.
A Third Embodiment of a Folding Handlebar
[0080] FIG. 12 illustrates a third embodiment 300 of folding handlebars wherein left and right extension tubes 302 extend rearwardly from the corresponding cylindrical tube portions 182 of the pivot mechanisms 106 . The arm rest assemblies 112 are mounted to the extensions rather than to the arm sections 102 .
A Fourth Embodiment of a Folding Handlebar
[0081] FIG. 13 illustrates a four embodiment 400 comprising pair of time trail bars (also known as bullhorn bars) incorporating the control thumb shifters 108 of the first embodiment and a pair of inverted brake levers 310 similar to those described with reference to the first embodiment sans the actuator levers of the actuator mechanism. By relocating and inverting the brake levers as shown and using thumb shifters with internal cable routing, the bars in the vicinity of the handgrips are free of exposed cables that can act to hamper rider comfort.
A Method of Using the First, Second or Third Embodiment Handlebar Assemblies
[0082] The folding handlebars of the first and second embodiments permit a rider to move his/her hands from a primarily aerodynamic position on the bars to a second position where the hands and arms are spaced further apart to facilitate free breathing and provide the rider with increased leverage and control as is desirable during pack riding, climbing and sprinting. FIGS. 1 & 3 provide two views of the bars in the first position while FIG. 14 provides a view of the bars in the second position.
[0083] To move either arm section 102 from a first position to a second position, a rider need only push the actuator lever 122 for the particular arm section and then apply pressure with his/her hand in the direction that he/she desires to rotate the arm section. Once the pin is retracted and the arm section has been moved slightly relative to its former position, the rider can release the actuator lever. Accordingly, the lock pin 148 is biased against the outside surface of the cylindrical portion 180 of the associated pivot mechanism 106 . As the arm section is rotated into the second position, the lock pin is biased into the appropriate bore hole 192 as they become aligned thereby locking the arm section in the desired position.
[0084] While it is possible to actuate both actuator levers simultaneously and simultaneously move the left and right arm sections into the other position, this action is not particularly recommended while riding as the rider's control of the bicycle may be compromised while the arms section can freely pivot between positions. A preferred manner of moving the bars from one position to another while riding, comprises first moving one of the left and right arm sections, and then when that section is secured in the new position, moving the other arm section to its new position. Accordingly, the rider can maintain control of the bicycle since at least one arm section is always locked into one of the first and second positions.
Methods of Making the First Embodiment Handlebar Assembly
[0085] Numerous methods of making a folding handlebar assembly, such as the one described as the first embodiment, are contemplated as would be obvious to one or ordinary skill in the art given the benefit of this disclosure. The following describes the fabrication of the assembly generally.
[0086] Initially, the various elements and components of the assembly will be sourced and provided including the left and right arm sections, the base section, the left and right pivot mechanisms and the left and right actuator mechanisms. Further, the left and right brake lever assembly and left and right thumb shifter assemblies can be provided.
[0087] It is to be appreciated that the various components listed above can contain various parts that are also sourced and that the various components are assembled as well. For instance, the arm sections can comprise several tube sections that are welded together at the bend discussed supra and the cylindrical tube portion 182 is also permanently affixed to the arm section typically through welding before the arm section is in a condition to be used in the assembly of the handlebar. In yet another variation of the arm section the bend is provided by bending a provided tube rather than joining two separate tube sections.
[0088] The various sections are assembled together. The actuator mechanisms are secured in the interiors of the respective arm sections 102 by securing the disk-shaped stop 158 in place proximate the opening 136 provided in the arm section, such that the lock pin is biased into the radially extending tube bore 194 of the outer cylindrical tube portion 182 . The brake lever assemblies 110 are clamped in place on the outside of the arm sections and the cable stop 134 of the connector cable 124 is placed into a receiving slot in the actuator lever 122 .
[0089] The cylindrical tube portion 182 is received over the cylindrical portion 180 and bushings 184 & 186 of the pivot mechanism and rotatably secured in place with a circular snap ring 188 . Next, the thumb shifter assemblies 108 are secured in place along with their respective cables 132 and housings 168 . To complete the process, as necessary, the cables and housings for both the brakes and the shifters are routed through the base section 104 .
Other Embodiments and Variations
[0090] The various embodiments of the handlebar assembly, the combination of the assembly with a bicycle, and the methods of use and making of the handlebar assembly as illustrated in the accompanying figures and/or described above, are merely exemplary and are not meant to limit the scope of the invention. It is to be appreciated that numerous variations to the invention have been contemplated as would be obvious to one of ordinary skill in the art with the benefit of this disclosure. All variations of the invention that read upon the claims are intended and contemplated to be within the scope of the invention.
|
Embodiments of the present invention comprise a folding handlebar to allow the rider to adopt an aerodynamic riding position without superfluous bars protruding left and right and a control system so the rider has full access to braking and gear changing whether riding in the aero or non aero position.
| 8
|
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is continuation of copending International Application No. PCT/GB06/002727 filed Jul. 21, 2006, which designated the United States, the disclosure of which is incorporated herein by reference, and which claims priority to Great Britain Patent Application Nos. 0524181.5 filed Nov. 28, 2005; and 0515266.5, filed Jul. 26, 2005.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to a separator assembly for removing material that is entrained in a gas stream such as liquid in an aerosol form.
SUMMARY OF THE INVENTION
[0003] Removal of material from a gas stream can be required to ensure that the gas is sufficiently clean for a subsequent application, or to minimise adverse effects of impurities on components of the system. For example, removal of compressor oil can be required to minimise chemical contamination and accumulation on valves which might lead to malfunction of the valves, and removal of particulate solid material can be required to minimise abrasion. Also, removal of liquid such as water droplets from a gas stream can be required in order to minimise contaminant loading in downstream filters.
[0004] There are many known separator assemblies for use in a compressed gas systems which are designed to remove material from a gas stream prior to a downstream application. Such separator assemblies include water separators which utilise centrifugal forces caused by a helically flowing gas stream to separate bulk liquid, such as water, from the gas stream. Such water separators assemblies generally comprise a housing having inlet and outlet ports at an upper end of the housing for the gas stream that is to be filtered, a plurality of baffles arranged to impart a helical flow to gas entering the housing, and a shield located between the inlet and outlet ports and an reservoir area at the lower end of the housing at which separated material collects. A liquid drainage port can be provided at the lower end of the housing through which liquid can be removed from the housing. The shield is typically a flat plate and is suspended within the housing by a tie rod extending from the top end of the housing. A gas stream enters the housing through the inlet port. Liquid separated from the gas stream falls to the bottom of the housing where it gathers at the lower end of the housing. The shield acts to quell the turbulent air flow so as to create a “quiet space” between itself and the lower end. This quiet space helps to minimise the amount of liquid becoming re-entrained in the gas stream. Also, when a drainage port is present, the quiet space can allow the drainage port to function properly.
[0005] It can be important to minimise the pressure drop across a separator assembly. Typically, the higher the pressure drop across a separator assembly in a compressed gas system, the lower the efficiency of the system and the higher the operating costs of the system.
[0006] It can also be important to minimise the re-entrainment of material that has been removed from the gas stream.
[0007] According to a first aspect of the invention, there is provided a separator assembly for removing material that is entrained in a gas stream comprising: a housing having a head part which provides the upper end of the housing and a body part which provides the lower end of the housing; and a shield which extends across the housing towards the lower end thereof so as to leave a collection space between it and the lower end in which material that is separated from the gas stream can collect, with at least one opening in or around the shield through which the material can flow past the shield into the collection space, a liner sleeve which covers at least a part of the inside wall of the body part between the shield and the upper end of the body part.
[0008] It is an advantage of the present invention that the use of a liner sleeve can improve the efficiency of a separator assembly. For example, the use of a liner sleeve can reduce the re-entrainment of material separated from the gas stream, back into the gas stream. This is because the inside wall of the body part is made from materials which provide the necessary strength required to withstand internal pressures resulting from the flow of gas through the assembly. The properties of the material from which the wall of the body part is made are such that the material removed from the gas stream can tend to cling to the inside wall, rather than falling down the inside wall past the shield to the quiet space, and so gives rise to the possibility of the material becoming re-entrained in the gas stream. The liner sleeve does not need to have the strength and rigidity of the body part. Accordingly, the liner sleeve can be made from materials having properties which reduce the tendency of the material to cling to the liner sleeve, thereby reducing the chance of the material becoming re-entrained in the gas stream. Also, many different types of liner sleeve can be made having different properties. Accordingly, a liner sleeve can be selected for a separator apparatus depending on the application in which the separator assembly is to be used, so that the properties of the liner sleeve are most suited to that application.
[0009] Preferably, the liner sleeve extends completely annularly around the inside wall of the body part. Accordingly, the liner sleeve can in the form of a tubular structure with a closed-loop cross-section. Optionally, the liner sleeve can be made from a sheet of material that can be wrapped around to form a tubular structure having an overlapping cross-section.
[0010] Preferably, the outer side of the liner sleeve is shaped and sized so that it is a snug fit within the housing body part.
[0011] Preferably, the liner sleeve extends from the face of the shield which is directed toward the upper end of the housing to a point proximal the upper end of the body part. Preferably, the liner sleeve extends along the length of the body part for at least 50% of the distance between the face of the shield which is directed toward the upper end of the housing and the upper end of the body part, more preferably at least 75%. Most preferably, the liner sleeve extends from the face of the shield which is directed toward the upper end of the housing to the upper end of the body part.
[0012] Preferably, the liner sleeve is located in the body part of the housing so that it can be removed from the body part. This is advantageous as it provides for the removal, cleaning, maintenance and interchanging of the liner sleeve.
[0013] Preferably, the liner sleeve is approximately round, especially approximately circular, in shape when viewed from above. This can help to minimise disturbance of the flow of gas due to discontinuities in the path defined by the liner sleeve. It has been found that a circular liner sleeve can help to maintain the helical flow of gas, thereby maintaining the separating property of helical flow of gas caused by centrifugal force. Further, a circular shaped liner sleeve can provide less resistance to a helical gas stream flowing within it. As a result, it has been found that the pressure drop experienced across the separator assembly is less with a circular liner sleeve.
[0014] It can be preferable that the surface of the inner side wall of the liner sleeve, that is the side of the liner sleeve that does not face the internal side wall of the housing has formations which reduces the tendency of liquid to cling to the surface of the inner side wall of the liner sleeve. For example, it can be preferable that the surface of the inner side wall of the liner sleeve, is roughened. This is because liquid will tend to cling to a smooth surface due to surface tension, and therefore not readily fall down the surface of the liner sleeve, past the shield into the quiet space. This can cause problems with the liquid becoming re-entrained within the gas stream. Preferably, the texture of the surface of the inner side of the liner sleeve is rough. Roughened surfaces have been found to reduce the tendency of liquid to collect due to surface tension effects.
[0015] It can also be preferable that the surface of the inner side wall of the liner sleeve has at least one groove formed in it. Again, the use of grooves has been found to aid drainage of the material from the surface of the inner side wall of the liner sleeve. The at least one groove can extend substantially parallel to the axis of the body part when in use. Optionally, the at least one groove extends helically around the surface of the inner side wall of the liner sleeve. Accordingly, the at least one groove can extend at an angle to the axis of the body part when in use. Preferably, the at least one groove extends along at least 50% of the length of the liner sleeve, more preferably at least 75% of the length of the liner sleeve, especially preferably at least 90% of the length of the liner sleeve. When there is more than one groove, preferably the grooves are spaced equally around the liner sleeve. When the groove extends substantially parallel to the axis of the body part when in use, preferably, the groove extends vertically.
[0016] It can be preferable to provide a liner sleeve having formations which reduce the tendency of liquid to cling to the surface of the inner side wall of the liner sleeve, such as a rough inner side surface, rather than providing a housing body having such formations because the housing body will typically be made from materials in which it can be difficult to form such formations. In contrast, the liner sleeve can be made from different materials in which it can be easier to form such formations. For example, the housing body will typically be made from metallic materials, whereas the liner sleeve will typically be made from polymeric materials. The grooves can be created as a result of moulding with an appropriately shaped mould. The rough texture can be created as a result of moulding with an appropriately roughened surface. Optionally, the rough texture can be created as a result of a physical abrading process. For example, the rough texture can be created as a result of colliding the surface of the inner side wall of the liner sleeve with hard particles, or by rubbing it against a harder roughened surface, such as a surface coated with abrasive particles. When the liner sleeve is made from metal, rough surfaces can be made by spark erosion or similar techniques.
[0017] It can be preferable that the surface of the inner side wall of the liner sleeve has a helically extending rifle formation. This can be advantageous because it can help to maintain the helical flow of gas as it flows through the assembly. Preferably, the rifle formation is provided by at least one ridge which is provided on the surface of the inner side wall of the liner sleeve. Optionally, the rifle formation can be provided by at least one groove which is provided on the surface of the inner side wall of the liner sleeve.
[0018] Features of the separator assembly in which the shield is located within the body part of the housing through engagement between at least one of (a) the edge of the shield and the internal side wall of the housing, and (b) the shield and the base of the housing, can be considered for incorporation in the separator assembly which includes a liner sleeve.
[0019] Preferably, the cross-sectional size of the shield taken perpendicularly to a shield axis that extends through and perpendicular to the centre point of the shield, changes along the length of shield axis. Preferably, the liner sleeve has a constant cross-section along its entire length.
[0020] It can be preferable to provide the liner sleeve as a separate piece to the shield because it can allow the interchanging of different liner sleeve having different properties, or removal of the shield wall for maintenance and/or cleaning, without the need to remove the shield from the housing.
[0021] The liner sleeve can be provided as a wall of the shield that extends around its perimeter on its face which is directed toward the upper end of the housing. Accordingly, the liner sleeve and the shield can be removed from the housing as one piece. When the liner sleeve is provided as a wall of the shield, preferably, the wall extends around the entire perimeter of the shield. The shield and the shield wall can be provided as a single moulded piece. Optionally, the shield and the shield wall can be formed as separate pieces that have been fastened together.
[0022] The shield can be located within the body part of the housing against forces in a direction towards the lower end of the housing as a result of the action against it by the gas stream through engagement between the shield, and/or when provided the shield wall and the internal side wall of the housing.
[0023] The shield can be located within the body part of the housing through engagement between a plurality of ribs extending from the shield or the side wall of the housing body. The shield can be located within the body part of the housing through engagement between a plurality of ribs provided on one of the shield or the side wall of the housing body, and corresponding grooves into which the ribs can be received on the other.
[0024] The shield can be located within the body part of the housing through engagement between a plurality of ribs that extend away from its perimeter toward the internal side wall of the housing and the side wall of the housing. The shield and ribs can be one piece. For example, the shield and ribs can be provided as a single moulded piece. Optionally, the shield and ribs can be separate pieces that can be fastened together.
[0025] Preferably, there are provided at least three ribs, more preferably at least four ribs, especially preferably at least five ribs, for example six ribs. Preferably, the ribs are arranged so that they are equally spaced around the perimeter of the shield. When a shield wall is provided, the ribs can be provided on the shield wall. The ribs can vary in shape and size. This can be advantageous if it is important to locate the shield in a particular orientation within the housing. In this case, the ribs can be shaped and sized so that the shield properly fits within the housing in only one orientation. The ribs can be located at any point along the length of the shield wall. For example, the ribs can be located at the end of the shield wall proximal the shield. Preferably, the ribs are located at the end of the shield wall distal to the shield.
[0026] The internal side wall can comprise a plurality of grooves into which the ribs can be slidingly received so as to locate the shield within the body part. Optionally, the width of the interior of the housing can decrease towards its lower end so that the shield is located within the body part by way of a wedge fit between the ribs and the internal side wall.
[0027] The shield can be located within the body part of the housing through engagement of the shield with at least one support member provided by the body part of the housing. For example, the shield can be located within the body part of the housing through engagement of the shield with at least one ledge extending at least partially around the internal side wall. For example, the shield could be located within the body part by the contact between the face of the shield that faces toward the base of the housing and a ledge on the internal side wall. There can be provided a plurality of ledges spaced around the internal side wall. There can be provided one ledge that extends annularly around the internal side wall.
[0028] Optionally, the at least one support member can be at least one upstand support that extends between the base of the housing and the face of the shield that faces toward the lower end of the housing. Preferably, there are provided a plurality of upstand supports. When there are a plurality of upstand supports, preferably they are located so that their top surfaces which the shield engages, are spaced around the face of the shield that faces toward the lower end of the housing, towards the perimeter of that face of the shield. Preferably the plurality of upstand supports are located so that their top surfaces are spaced equally around that face.
[0029] Preferably, the face of the shield that faces toward the lower end of the housing provides at least one socket into which the at least one support member can be received. This can be advantageous because the socket can have side walls which the top end of the support member that is received in the socket can engage to prevent rotation of the shield within the housing. Accordingly, the provision of a socket can reduce the amount the shield can spin within the housing.
[0030] In some circumstances it can be preferred that the socket and the support member are shaped and dimensioned so that the top end of the support member is a tight fit in the socket. This is so that the once the shield has been located in the body part so that the support member is received in the socket, the shield cannot rotate at all within the housing. The tight fit can also help to anchor the shield to the support member.
[0031] It can be preferable for the shield and the at least one support member to be configured so that the shield can be fixed to the support member by an element in addition to the shield and the at least one support member. For example, preferably the shield can be screwed to the support member by a screw that extends through the shield and into the upstand support. For example, the shield and/or the support member can have holes pre-drilled in them at the locations where the shield and the support member engage each other so as to easily allow a screw to be screwed into them to anchor the shield to the support member. This can be advantageous as it can help to ensure that the shield does not lift from the support member during use.
[0032] The engagement between the shield and the housing can be direct engagement. For example, the engagement can be provided by a surface or part of the shield contacting a surface or part of the internal side wall of base of the housing. Optionally, the engagement between the shield and the housing can be indirect. For example, a support can be provided that extends between, and engages both, the housing and the shield. In particular, an upstand support can be provided that extends between the base of the housing and the face of the shield that faces toward the lower end of the housing.
[0033] The opening can be a gap between the shield and the housing. The gap can exist as a result of a difference in at least one of the shape and size of the shield and housing. The gap can extend only part way around the shield. The gap can extend annularly around the shield. When the shield is be located within the body part of the housing through engagement between a plurality of ribs that extend away from its perimeter toward the internal side wall of the housing and the side wall of the housing, then the openings can be defined by the gap between the shield, ribs and the internal side wall.
[0034] When the shape and size of the shield and the housing are such that the shield is a sung fit within the housing so that there is little or no gap between the perimeter of the shield and the housing side wall, then preferably the opening is provided in the shield. When the opening is in the shield, preferably the opening is located toward the perimeter of the shield. The shape of the opening can be any regular or irregular shape. For example, the opening can be circular or square in shape. Preferably, the shape of the opening follows the shape of the perimeter of the shield. For example, is the shape of the perimeter of the shield is curved, preferably the shape of the opening is curved. Preferably the opening is located toward the perimeter of the shield. The closer the opening is toward the perimeter of the shield, the less disturbance caused to the helical flow by the opening. Preferably, the ratio of (a) the distance from the perimeter of the shield to its centre point, to (b) the distance of the perimeter of the shield to edge of the opening at its point closest to the centre of the shield (both distances being measured along the surface of the shield) is not less than about 2, more preferably not less than about 4, especially preferably not less than about 8.
[0035] When a shield wall is provided, then preferably the opening is provided in the shield. Preferably, the opening is provided towards its perimeter where the shield wall meets the shield.
[0036] Preferably the separator assembly further comprises a flow director located between the inlet port and the shield, wherein the flow director is configured to impart a helical flow to the incoming gas stream. This can be advantageous as the separator assembly can be used to separate material entrained in a gas stream as a result of centrifugal forces arising from the helical flow.
[0037] A generally helical path is any path which extends around an axis so that material entrained in a gas is forced outward away from the axis, toward the wall of the housing, as a result of centrifugal forces. It is not necessarily that the helical path is a perfect helix. For example, the distance between the helical path of the gas stream and the wall of the housing could increase or decrease as the gas stream flows around the housing axis. For example, the helix spiral shaped so that the helical path tightens towards its leading or trailing end. Further, the angle of the gas stream to a plane perpendicular to the axis about which it flows could increase or decrease along the axis.
[0038] Preferably, the separator assembly includes an outlet tube which extends from the inside of the housing to the outlet port, through which gas flows between the inside of the housing and the outlet port. The provision of an outlet tube can isolate the flow of gas which is travelling toward the outlet port and away from the shield, from the flow of gas which is travelling away from the inlet port and toward the shield. This is advantageous as it can prevent the gas flowing away from the shield interfering with the gas flowing toward the shield. This can be particularly important when the separator assembly comprises a flow director located between the inlet port and the shield, wherein the flow director is configured to impart a helical flow to the incoming gas stream. This is because separating the flow of gas toward and away from the shield can minimise disturbances to the helical flow of the gas. As a result, the helical flow of gas in maintained, thereby maintaining the separating property caused by the helical flow of the gas, and also thereby minimising the pressure drop across the separator assembly.
[0039] Preferably the outlet tube is formed from a polymeric material. Preferred polymeric materials include polyolefins (especially polyethylene and polypropylene), polyesters, polyamides, polycarbonates and the like. Polymeric materials used for the outlet tube can be reinforced, for example by fibrous materials (especially glass fibres or carbon fibres). Materials other than polymeric materials can be used, for example metals.
[0040] Preferably the outlet tube is formed by moulding, for example, by injection moulding.
[0041] Preferably, the outlet tube is located within the housing against forces as a result of the action against it by the gas stream through engagement between inter-engaging formations provided on the outlet tube and the housing body. The inter-engaging formations can be in the form ribs provided on one of the outlet tube and the housing body, and grooves provided on the other. Preferably, the ribs are provided on the outlet tube.
[0042] When a shield wall is provided, it can be preferred that the outlet tube is located within the housing against forces as a result of the action against it by the gas stream through engagement between inter-engaging formations provided on the outlet tube and the shield wall. The inter-engaging formations can be in the form ribs provided on one of the outlet tube and the shield wall, and corresponding grooves into which the ribs can be slidingly received provided on the other. Preferably, the ribs are provided on the outlet tube.
[0043] The cross-sectional shape of the outlet tube taken perpendicular to its longitudinal axis can be any regular or irregular shape. Preferably, the cross-sectional shape of the outlet tube is generally rounded. Preferably, the cross-sectional shape of the outlet tube is constant along its length. The size of the cross-sectional shape of the outlet tube need not necessarily be constant along its length. For example, when the cross-sectional shape of the outlet tube is generally rounded, the diameter of the outlet tube can vary along its length.
[0044] Preferably, the flow director is fastened to the outlet tube. The flow director and the outlet tube can be provided as a single piece. For example, the flow director and the outlet tube can be created from a single mould. This can enable easy manufacturing and putting together of the assembly. The flow director and the outlet tube can be provided as separate pieces, which can be fastened together. This can allow different flow directors to be used with different outlet tubes.
[0045] When there is provided a flow director, preferably the outlet tube and flow director are located within the housing against forces as a result of the action against them by the gas stream through engagement between inter-engaging formations provided on the flow director and the housing body. The inter-engaging formations can be in the form ribs provided on one of the flow director and the housing body, and grooves provided on the other. Preferably, the ribs are provided on the flow director.
[0046] When a shield wall is provided, it can be preferred that the outlet tube and flow director are located within the housing against forces as a result of the action against it by the gas stream through engagement between inter-engaging formations provided on the flow director and the shield wall. The inter-engaging formations can be in the form ribs provided on one of the flow director and the shield wall, and corresponding grooves into which the ribs can be slidingly received provided on the other. Preferably, the ribs are provided on the flow director. When the flow director comprises a plurality of vanes (as described in more detail below), preferably at least one of the ribs is a vane.
[0047] If the outlet tube is formed separately from the flow director, then preferably the flow director and the outlet tube are formed form the same material. Preferably, the flow director outlet tube can be fastened to the outlet tube so that it can be subsequently removed. For example, preferably the flow director is fastened to the outlet through the use of a mechanical fastening such as a latch, co-operating screw threads, or engaging bayonet formations. More preferably, the outlet tube and the flow director are shaped and sized so that the outlet tube is held within the flow director by the friction forces between the outlet tube and the flow director.
[0048] It can be advantageous in some applications to fasten the flow director to the outlet tube so that the flow director cannot be subsequently removed from the outlet tube. In this case, preferably the flow director is fastened to the outlet tube without the use of a material which is different from the materials of the flow director and outlet tube. For example, preferably, the flow director is fastened to the outlet tube through the use of a welding technique, for example, ultrasonic or heat welding. However, it will be appreciated that the flow director can be fastened to the outlet tube through the use of a third party material such a bonding agent, for example an adhesive.
[0049] Preferably, an axis extending through the centre of the outlet tube and parallel to the outlet tube at its inlet end, and an axis extending through and perpendicular to the centre point of the face of the shield which is directed towards the upper end of the housing, are coaxial. This can help to ensure that gas travelling away from the shield enters the outlet tube. When the face of the shield which is directed towards the upper end of the housing, preferably the inlet end of the outlet tube faces toward the bowl-shaped face of the shield.
[0050] The faces of the shield can be planar. Preferably, the face of the shield which is directed towards the upper end of the housing is bowl-shaped. This is particularly advantageous when the separator assembly comprises a flow director located between the inlet port and the shield, wherein the flow director is configured to impart a helical flow to the incoming gas stream. This is because the bowl-shaped face of the shield can help to accelerate the helical flow of gas and to direct it back toward the outlet port. By maintaining the helical flow of gas, accelerating it, and directing it back toward the outlet port in a uniform manner, it has been found that the pressure drop across a separator assembly according to the present invention can be less than that across current separator assemblies. Details of a separator assembly in which the face of the shield which is directed towards the upper end of the housing is bowl-shaped are disclosed in the application entitled Separator Assembly which is filed with the present application bearing agent's reference P211193WO and claiming priority from UK Patent Application numbers 0515264.0 and 0524173.2. Subject matter that is disclosed in that application is incorporated in the specification of the present application by this reference.
[0051] Preferably, the flow director comprises a plurality of vanes which are arranged around the axis of the housing and inclined to that axis so that incoming gas is made to follow a generally helical path within the housing, in which the vanes are arranged in an array around the outlet tube. It has been found that the position of the shield relative to the outlet port and the vanes can affect the efficiency of the assembly. If the shield is located too far away from the outlet port then a significant proportion of gas travelling away from the shield can miss the outlet tube. If the shield is located too close to the outlet port then the advantages of accelerating the cyclone, when the face of the shield which is directed towards the upper end of the housing is bowl-shaped, can be reduced. Preferably, when the face of the shield which is directed towards the upper end of the housing is bowl-shaped, the ratio of the distance between the vanes and the bottom of the shield to the distance between the end of the outlet tube which faces the shield and the bottom of the shield is at least about 1, more preferably at least about 1.2, especially preferably at least about 1.5, for example at least about 1.7. Preferably, the ratio of the distance between the vanes and the bottom of the shield to the distance between the end of the outlet tube which faces the shield and the bottom of the shield is not more than about 2.5, more preferably not more than about 2.2, especially preferably not more than about 2, for example not more than 1.8. Preferably, the assembly includes a flow deflector so that gas flowing into the housing flows over the flow deflector so that the incoming gas is forced toward the side walls of the housing. Preferably, the flow deflector is located downstream of the flow director, so that the gas stream flowing into the housing flows over the flow director first, and then flows over the flow deflector. Accordingly, preferably, the flow deflector is located on the side of the flow director that is distal to the inlet port.
[0052] Preferably, the flow deflector extends annularly around the outlet tube. Preferably, the flow deflector comprises a ledge portion proximal the flow director which extends away from the outlet tube, substantially perpendicularly to the axis of the housing. Preferably, the flow conduit further comprises an side skirt which extends away from the free end of the ledge portion, in a direction substantially parallel to the axis of the housing.
[0053] Preferably, the flow deflector is fastened to the outlet tube. The flow deflector and the outlet tube can be provided as a single piece. For example, the flow deflector and the outlet tube can be created from a single mould. This can enable easy manufacturing and putting together of the assembly. The flow deflector and the outlet tube can be provided as separate pieces, which can be fastened together. This can allow different flow deflector to be used with different outlet tubes.
[0054] If the outlet tube is formed separately from the flow deflector, then preferably the flow deflector and the outlet tube are formed form the same material. Preferably, the flow deflector outlet tube can be fastened to the outlet tube so that it can be subsequently removed. For example, preferably the flow deflector is fastened to the outlet through the use of a mechanical fastening such as a latch, co-operating screw threads, or engaging bayonet formations. More preferably, the outlet tube and the flow deflector are shaped and sized so that the outlet tube is held within the flow deflector by the friction forces between the outlet tube and the flow deflector.
[0055] It can be advantageous in some applications to fasten the flow deflector to the outlet tube so that the flow deflector cannot be subsequently removed from the outlet tube. In this case, preferably the flow deflector is fastened to the outlet tube without the use of a material which is different from the materials of the flow director and outlet tube. For example, preferably, the flow deflector is fastened to the outlet tube through the use of a welding technique, for example, ultrasonic or heat welding. However, it will be appreciated that the flow deflector can be fastened to the outlet tube through the use of a third party material such a bonding agent, for example an adhesive.
[0056] Preferably the flow deflector is formed from a polymeric material. Preferred polymeric materials include polyolefins (especially polyethylene and polypropylene), polyesters, polyamides, polycarbonates and the like. Polymeric materials used for the flow deflector can be reinforced, for example by fibrous materials (especially glass fibres or carbon fibres). Materials other than polymeric materials can be used, for example metals.
[0057] Preferably the flow deflector is formed by moulding, for example, by injection moulding.
[0058] Preferably, the housing includes a drain outlet for material which has been separated from the gas stream. The outlet will generally provide for removal of material which has collected in a reservoir at the base of the housing. The drain should preferably be capable of opening without depressurising the housing. A suitable drain mechanism is disclosed in EP-A-81826.
[0059] This application also describes a separator assembly for removing material that is entrained in a gas stream comprising: a housing having a head part which provides the upper end of the housing and a body part which provides the lower end of the housing, and a shield which extends across the housing towards the lower end thereof so as to leave a collection space between it and the lower end in which material that is separated from the gas stream can collect, with at least one opening in or around the shield through which the material can flow past the shield into the collection space, in which the shield is located within the body part of the housing against forces in a direction towards the lower end of the housing as a result of the action against it by the gas stream through engagement between at least one of (a) the edge of the shield and the internal side wall of the housing, and (b) the shield and the base of the housing.
[0060] This assembly has the advantage that, as the shield is mounted on the body rather than the head, it is not necessary to use a tie rod extending from the head to secure the shield in the housing. It has been found that by removing the need for a tie rod in the housing, gas flowing through the housing can be subject to less resistance. Accordingly, this can enable the efficiency of the assembly the invention to be enhanced compared with known assemblies.
[0061] It has also been found that this can reduce the likelihood of liquid becoming re-entrained in the gas stream. This is because it has been found that liquid can cling to a tie-rod which can subsequently be caught in the gas stream, thereby becoming re-entrained in it. The absence of the tie rod eliminates this risk.
[0062] It is also an advantage that the separator assembly is easier to manufacture and assemble. Also, tie rods are prone to rusting and therefore require replacing regularly. Further, nuts which secure the tie rod to the housing and/or the shield can become loose, which can cause performance and safety problems. Accordingly, separator assemblies using tie rods require regular maintenance and servicing. The described assembly overcomes these disadvantages by removing the need for a tie rod.
[0063] The shield can be made from polymeric materials or from metallic materials. It should have sufficient rigidity to ensure that the shield does not flex or move during operation. Suitable materials should not have any adverse reaction with fluids with which the element will come into contact when in use.
[0064] The shape of the shield when viewed from above can be, for example, square, rounded, hexagonal. Preferably, the shape of the shield when viewed from above is rotational symmetrical. When the face of the shield that faces toward the upper end of the housing is bowl-shaped, and a helical flow is imparted gas entering the separator assembly, as discussed in more detail below, preferably the shield is approximately rounded, especially approximately circular, when viewed from above. What is meant by approximately circular is that the shield is sufficiently close to circular so that gas can flow over the shield without disturbing the helical nature of the gas flow. This can help to minimise disturbance to the flow of gas due to discontinuities in the path defined by the bowl-shaped shield. Further, it has also been found that a circular shaped shield can provide better acceleration of the helical flow of gas back towards the outlet port over other shaped shields. Both of these factors can result in a smaller pressure drop across the separator assembly. Preferably, the shape of the shield when viewed from above is approximately the same shape as the housing when viewed from above.
[0065] The shield can be formed as part of the body part. Preferably, the shield is and the body part are formed as separate parts. This can be advantageous as it can allow the use of different types of shields within a housing. Preferably, the shield is removable from the body part. This can be advantageous as it can allow for the replacement of shields within the housing. Preferably, the shield is held within the body by way of a press-fit in the body. This can allow for easy assembly of the housing.
[0066] The term “engagement” in the expression “. . . the shield is located within the body part of the housing . . . through engagement between . . . (a) the edge of the shield and the internal side wall of the housing, and (b) the shield and the base of the housing” does not necessarily mean that the shield is interlocked with the side wall or the base of the housing. Rather, it means that there is a mechanical contact, between the shield and either the side wall or the base of the housing, which holds the shield in a location in the housing against the forces of the gas stream acting in a direction toward the lower end of the housing. The shield can be locked against movement toward the upper end of the housing, but this is not as important as locking the shield against movement toward the lower end of the housing. The mechanical contact can be any form of mechanical contact. Accordingly, the engagement could be provided by a mechanical fastening which interlocks the shield to the housing. The mechanical fastening could be an element in addition to the shield and the housing. For example, the element could be a screw that extends through the shield and into the housing. Optionally, the engagement could be provided by the mere physical contact between the shield and the housing. Further, the engagement could be provided by an adhesive.
[0067] It can be preferable that the internal side wall of the housing is roughened. This is because liquid will tend to cling to a smooth surface due to surface tension, and therefore not readily fall down the internal side wall past the shield to the quiet space. This can cause problems with the liquid becoming re-entrained within the case stream. Preferably, the texture of the surface of the internal side wall of the housing between the shield and the upper end of the housing is rough. Roughened surfaces have been found to reduce the liquid to collect due to surface tension effects. Therefore, the liquid tends to fall down the internal side wall's surface more readily, reducing the chance of the liquid becoming re-entrained in the gas stream. The rough texture can be created as a result of moulding with an appropriately roughened surface. When the mould is made from metal, rough surfaces can be made by spark erosion or similar techniques.
[0068] A liner sleeve can be provided which covers at least a part of the inside wall of the body part between the shield and the upper end of the body part. The liner sleeve can be provided as a wall of the shield that extends around its perimeter on its face which is directed toward the upper end of the housing. The shield can be located within the body part of the housing against forces in a direction towards the lower end of the housing as a result of the action against it by the gas stream through engagement between the wall of the shield and the internal side wall of the housing. Preferably, the texture of the surface of the inner side wall of the liner sleeve is rough. Preferably, the liner sleeve extends from the shield to a point proximal the upper end of the body part.
[0069] The housing should be formed from a material which is capable of withstanding the internal pressures to which it is subjected when in use. Metals will often be preferred, for example aluminium and alloys thereof, and certain steels.
BRIEF DESCRIPTION OF THE DRAWINGS
[0070] Embodiments of the invention will now be described, by way of example only, and with reference to the accompanying drawings, in which:
[0071] FIG. 1 is a sectional side elevation through a separator assembly according to the present invention;
[0072] FIG. 2 is perspective view of the separator assembly shown in FIG. 1 , without the housing;
[0073] FIG. 3 is a schematic sectional side elevation through the separator assembly shown in FIG. 1 , illustrating the flow of gas through the assembly;
[0074] FIG. 4 is a sectional side elevation through the shield of the separator assembly shown in FIG. 1 ;
[0075] FIG. 5 is a sectional side elevation through the shield and the shield wall of the separator assembly shown in FIG. 1 ;
[0076] FIG. 6 is a cut-away perspective view of the separator assembly shown in FIG. 1 , without the housing;
[0077] FIG. 7 , is a sectional side elevation through the lower end of the body part of a separator assembly according to the present invention;
[0078] FIG. 8 , is a cut-away perspective view of the separator assembly shown in FIG. 7 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0079] Referring to the drawings, FIG. 1 shows a separator assembly 2 , which comprises a housing 4 defining an inner volume 6 . The housing 4 comprises a head part 12 , and a body part 14 which can be connected to one another by means of cooperating screw threads at their interfaces 16 , 18 . The housing 4 further comprises inlet 20 and outlet 22 ports located in the head part 12 , for gas to enter and exit the separator assembly 2 , a reservoir 8 located at a second end of the housing opposite the first end, and a liquid drainage port 10 . The separator assembly further comprises a flow director 24 , a flow deflector 26 , a shield 28 , a flow conduit device 30 which includes a conduit portion 32 , all located within the body part 14 of the housing 4 .
[0080] The head part 12 and body part 14 are formed from a metallic material, especially aluminium or an alloy thereof. They can be formed by machining or by techniques such as casting.
[0081] The body part 14 comprises a cylindrical wall 34 , an end wall 36 at one end of the cylindrical wall 34 , and an open end at the opposite end of the cylindrical wall. Liquid separated from a gas stream flowing through the separator assembly is collected in the reservoir 8 . The liquid drainage port 10 allows liquid collected in the reservoir 8 to drain from the housing 4 . An example of a suitable liquid drainage port 10 is disclosed in EP-A-0081826.
[0082] A plurality of fins 38 are provided in the body part 14 towards its second end. The fins 38 extend part way along the cylindrical wall 34 from the second end of the housing toward the first end of the housing, parallel to the axis of the body part. Each fin 38 provides a ledge 40 , toward its end proximal the head end of the housing, on which the shield 28 can sit, as described in more detail below.
[0083] The head part 12 contains a primary chamber 44 within it having a first end 46 communicating with the outlet port 22 and a second end 48 having an opening communicating with the inner volume 6 of the housing 4 when the separator assembly 2 is assembled. The primary chamber 44 is defined by an internal cylindrical wall 42 extending transversely through within the head part and an internal end wall 50 opposite the outlet port 22 .
[0084] The shield 28 has a bowl-shaped face 53 and a dome-shaped face 55 . The perimeter of the shield 28 is circular in shape. The shield has a plurality of windows 52 cut out of it towards its circumference. The windows 52 allow liquid to pass the shield 28 from the space in the inner volume 6 above the shield to the reservoir 8 , as described in more detail below.
[0085] The diameter of the shield 28 decreases away from its perimeter towards its centre point 54 . The diameter of the shield 28 decreases monotonically for part way towards its centre point, and then progressively decreases for the rest of the way towards its centre point. Therefore, when taken in cross-section as shown in FIGS. 1 , 3 and 4 , the faces of the shield define a rounded V-shape, having straight edges 96 towards its ends 98 and a rounded bottom towards its centre point 54 .
[0086] As best shown in FIG. 4 , the angle A between the straight edges 96 of the shield and the plane in which the perimeter of the shield lies, is approximately 45°. Further, the ratio of the diameter X of the shield 28 to the depth Y of the shield 28 is approximately 2.8.
[0087] The shield 28 is formed from a polymeric material, such as nylon. It can be formed by techniques such as injection moulding.
[0088] A shield wall 82 is provided that extends around the circumference of the shield 28 . The shield wall 82 extends from the shield 28 to an open end proximal the open end of the housing body part 14 . The shield wall 82 is generally cylindrical in shape, and is a snug fit within the housing body part 14 . The surface of the inner side 84 of the shield wall 82 is rough in texture. The open end of the shield wall 82 comprises an annularly extending lip 88 . When assembled, the lip 88 rests on the open end of the housing body part 14 as described in more detail below.
[0089] A plurality of grooves 92 are provided around the inner side 84 of the shield wall 82 at its open end for receiving ribs 70 of the flow conduit device 30 as described in more detail below. In the embodiment shown, two grooves 92 are spaced 180° around the open end of the shield wall 82 . As best shown in FIGS. 2 and 6 , there are also provided ribs 86 spaced around the outer side 90 of the open end of the shield wall 82 . In the embodiment shown, the grooves 92 also act as the ribs 86 , and therefore there are provided two ribs 86 that are spaced 180° around the open end of the shield wall 82 . When assembled, the ribs 86 are slidingly received within corresponding grooves 56 in the cylindrical wall 34 of the housing body part 14 .
[0090] In the embodiment shown, the shield wall 82 and the shield 28 are provided as a single piece. However, as discussed above the shield wall 82 and the shield 28 can be provided as separate pieces. Accordingly, it will be understood that in such an embodiment both the shield 28 and the shield wall 82 will have formations which enable them to be located in the housing body part 14 .
[0091] The flow conduit device 30 has a first opening 58 that is directed towards the outlet port 22 and has a first axis A, and a second opening 60 that is directed toward the body part 14 of the housing and has a second axis B. The angle between the axes A, B of the first 58 and second 60 openings is 90°. The flow conduit device 30 provides a continuous flow path between the two openings, and therefore provides a smooth change of direction for gas flowing through it when in use. The flow conduit device 30 turns about an axis C which extends perpendicularly to the axes A, B of the first 58 and second 60 openings. (As shown in FIG. 1 , the axis C extends perpendicularly to the plane along which the cross-section of the separator assembly 2 is taken).
[0092] An O-ring 78 is provided around the flow conduit device 30 , within an annular recess that extends around the external surface of the flow conduit device at its second opening 62 end.
[0093] The flow conduit device 34 contains first 62 , second 64 and third 66 curved vanes extending perpendicularly across the flow conduit device 34 . Each vane 62 , 64 , 66 curves around its own axis and the radius of curvature is the same for each vane. Further, the length of the vanes 62 , 64 , 66 , measured between their leading and trailing edges, is the same for each vane. The axes around which the vanes 62 , 64 , 66 curve extend parallel to the axis C around which the flow conduit device 30 curves. For example, the second vane 64 curves around an axis D. The vanes 62 , 64 , 66 each have concave and convex surfaces, wherein the concave surface of each vane faces the first 58 and second 60 openings of the flow conduit device 30 . Accordingly, the vanes 62 , 64 , 66 help guide the flow of gas between the first 58 and second 60 openings.
[0094] The flow conduit device 30 further includes a conduit portion 32 which, when the separator assembly 2 is assembled, extends into the housing body part 14 . In this embodiment, the flow conduit device 30 and the conduit portion 32 are one piece. However, it will be appreciated that they need not be one piece. The conduit portion 32 defines a flow path 68 for gas leaving the inner volume 6 and is in fluid communication with the second opening 60 of the flow conduit device 30 . The walls of the conduit portion 32 are cylindrical. The diameter of the conduit portion 32 is narrower towards its end proximal the second opening 60 .
[0095] The flow director 24 comprises plurality of baffles 72 provided around the conduit portion 32 . When the flow conduit device 30 is located within the housing body part 14 , the baffles 72 extend between the conduit portion 32 and the inner side of the cylindrical wall 34 of the body part. The baffles are rectangular in shape and are arranged so that their planar faces extend at an angle to the longitudinal axis of the housing body part 14 when the flow conduit device 30 is located in the body part 14 .
[0096] The flow conduit device 30 further comprises a plurality of ribs 70 that extend away from the conduit portion 32 at its end proximal the second opening 60 . The ribs 70 can slide into the grooves 92 in the shield wall 28 in order to hold the flow conduit device 30 within body part 14 . In the embodiment shown two ribs 70 are provided spaced 180° around the conduit portion 32 . Also in the embodiment shown, each of the ribs 70 is also a baffle 72 . However, it will be appreciated that the ribs 70 can have a different configuration to the baffles 72 and therefore not be baffles.
[0097] The flow deflector 26 extends annularly around the conduit portion 32 , and is shaped and sized so that it extends away from the conduit portion part way toward the inner side of the shield wall 82 , when the flow conduit device 30 is located in the body part. The flow deflector 26 is located on the side of the baffles 72 distal to the second end 62 of the flow conduit device 30 . The flow deflector 26 comprises a ledge portion 74 proximal the baffles 72 which extends away from the conduit portion 32 , substantially perpendicularly to the axis of the conduit portion 32 , and an side skirt 76 which extends away from the end of the ledge portion, substantially parallel to the axis of the conduit portion.
[0098] The flow conduit device 30 is formed from a polymeric material, for example nylon. The flow conduit device 30 can be formed by techniques such as injection moulding. The different parts of the flow conduit device 30 , such as the conduit portion 32 , the ribs 70 , the flow director 24 and the flow deflector 26 can be formed together as one piece, as different pieces, or as a combination of single and different pieces (i.e. the conduit portion 32 and the flow deflector 26 can be formed as one piece and the flow director 24 as a separate piece subsequently fastened to the conduit portion).
[0099] The separator assembly 2 is assembled by locating the shield 28 and shield wall 82 in the housing body part 14 by sliding them through the body part until the portions between the windows 52 of the dome-shaped face 55 of the shield 28 rest on the ledges 40 of the fins 38 , and until the ribs 86 are received within the grooves 56 in the cylindrical side wall 34 of the housing body part 14 . Once the ribs 86 have been fully received by the grooves 56 , the shield 28 and shield wall 82 are securely suspended within the housing body part 14 , and the lip 88 should rest on the open end of the housing body part 14 . The shield 28 and shield wall 82 are then securely suspended within the housing body part 14 , and rotation of the shield 28 and shield wall 82 within the housing body part 14 is restricted by the interlocking of the ribs 86 with the grooves 56 .
[0100] The flow conduit device 30 is then located in the housing body part 14 by sliding the ribs 70 into the grooves 92 until they sit on the bottom of the grooves. Once the ribs 70 have been fully received by the grooves 92 , the flow conduit device 30 is securely suspended within the housing body part 14 . Therefore, the axial position of the flow conduit device 30 within the housing body part 14 can be controlled by the shape and size of the ribs 70 and the grooves 92 . Further, rotation of the flow conduit device 30 is restricted by the interlocking of the ribs 70 with the grooves 92 . The flow conduit device 30 can be removed from the housing body part 14 by pulling the flow conduit device away from the body part along its axis.
[0101] The housing head part 12 is secured to the housing body part 14 by locating the flow conduit device 30 in the primary chamber 44 of the head part through the opening at the primary chamber's second end 48 . The O-ring 78 is received by the opening, and is compressed by the walls of the primary chamber 44 to form a fluid tight seal.
[0102] The housing head part 12 and body part 14 are secured by rotating one relative to the other so that their cooperating screw threads at their interfaces 16 , 18 are tightened to interlock with each other. An O-ring 80 is provided at the interfaces 16 , 18 which is compressed by the interfaces to form a fluid tight seal. When assembled, the inlet port 20 is in fluid communication with an inner volume 6 of the housing 4 .
[0103] The separator assembly 2 can be disassembled by rotating the bousing head part 12 and body part 14 relative to each other so that their cooperating screw threads are loosened. Any rotational force that is imparted on the flow conduit device 30 by frictional and related forces (for example arising from physical or chemical interactions or both) between the O-ring 78 on the flow conduit device and the primary chamber 44 of the head part 12 is negated by the opposite rotational drive that is provided by the ribs 70 acting against the grooves 92 in the shield wall 28 . Therefore, as the housing head part 12 and body part 14 are rotated relative to each other, the flow conduit device 30 will tend to reside in the body part rather than be drawn away from the body part with the head part. Accordingly, when the head part 12 and the body part 14 are separated from each other, the flow conduit device 30 will remain located within the body part 14 .
[0104] Referring to FIGS. 7 and 8 , a section of an alternative embodiment of the separator assembly is shown. In this embodiment housing body part 114 is formed by an extrusion process rather than casting a casting process and the end wall of the body part is provided by a closure plate 136 . A drainage port 110 is provided that allows liquid collected in the reservoir 108 to drain from the housing. A plurality of upstand supports 102 are provided that extend between the closure plate 136 and the face of the shield 128 that faces toward the lower end of the housing. The upstand supports 102 are located so that their top surfaces 104 are spaced around the face of the shield 128 that faces toward the closure plate of the housing, towards the perimeter of that face.
[0105] The shield 128 provides a plurality of sockets 106 on its face that faces towards the lower end of the housing, in which the upstand supports 102 can be received. The walls 112 of the sockets 106 are shaped and sized so that the upstand supports 102 are a tight fit in the socket. The shield 128 is anchored to the upstand supports 102 by screws 116 that extend through the shield 128 into the upstand supports 102 .
[0106] In use, the separator assembly is used in a substantially vertical position, with the housing head part 12 being above the body part 14 . A gas having an entrained material that is to be removed from the gas enters the separator assembly through the inlet port 20 . In the embodiment described, the gas is air and the material is water. The air flows away from the inlet port 20 , and passes over the baffles 72 of the flow director 24 . The configuration and arrangement of the baffles 72 impart a helical flow to the gas stream as illustrated by line 84 . Once the gas has passed through the flow director 24 , over the baffles 72 , the gas then flows over the flow deflector 26 . The configuration and arrangement of the flow deflector 26 forces the gas to flow outwards towards the shield wall 28 .
[0107] Due to the water entrained in the gas being heavier than the gas, the water is pushed outward towards the shield wall 82 as the gas stream spins in a helical manner. This is due to the centrifugal force on the water as the gas/water mixture turns. The water then falls down the inner side 84 of the shield wall 82 , passes past the shield 28 through the windows 52 , and collects in the reservoir 8 at the bottom of the housing body part 14 . The water can be drained from the reservoir 8 by operating the liquid drainage port 10 .
[0108] The gas continues to travel away from the inlet port 20 in a helical motion, until it reaches the shield 28 . At this point, the gas is reflected off the shield 30 back toward the housing head part 12 , as illustrated by line 86 . Due to the bowl-shape of the shield 30 , the helical flow of the gas stream is maintained. Further, the shield acts to accelerate the helical flow of gas toward the conduit portion 32 of the flow conduit device 30 .
[0109] The shield 28 acts as a barrier to the gas flowing past it. The turbulence in the volume of gas in the area below the shield 28 , i.e. between it and the housing body part's 14 end wall 36 , is less than the turbulence in the volume of gas above the shield. Accordingly, the space between the shield 28 and the housing body part's 14 end wall 36 is known as a “quiet space”.
[0110] The gas stream then passes through the conduit portion 32 , the flow conduit device 30 , and finally through the primary chamber 44 before being discharged from the separator assembly 2 by the outlet port 22 . The smooth change of direction provided by the flow conduit device 30 , and also the vanes 62 , 64 , 66 , help to turn the gas as it passes through the flow conduit device. This helps to reduce turbulence in the flow conduit device 30 and thereby helps to reduce the drop in pressure across the flow conduit device caused by the change of direction.
|
A separator assembly for removing material that is entrained in a gas stream. The separator assembly comprises a housing having a head part which provides the upper end of the housing and a body part which provides the lower end of the housing. The separator assembly also comprises a shield which extends across the housing towards the lower end thereof so as to leave a collection space between it and the lower end in which material that is separated from the gas stream can collect. There is at least one opening in or around the shield through which the material can flow past the shield into the collection space. The separator assembly further comprises a liner sleeve which covers at least a part of the inside wall of the body part between the shield and the upper end of the body part.
| 1
|
[0001] This application claims the benefit of U.S. Provisional Application No. 60/419,685 filed Oct. 16, 2002.
TECHNICAL FIELD
[0002] This application relates to measurement of birefringence properties of optical elements, and primarily to large-format elements, such as large sheets of material used for liquid crystal displays (LCDs).
BACKGROUND
[0003] Many important optical materials exhibit birefringence. Birefringence means that different linear polarizations of light travel at different speeds through the material. These different polarizations are most often considered as two components of the polarized light, one component being orthogonal to the other. Birefringence is an intrinsic property of many optical materials, and may also be induced by external forces applied to the material.
[0004] Retardation or retardance represents the integrated effect of birefringence acting along the path of a light beam traversing the sample. If the incident light beam is linearly polarized, two orthogonal components of the polarized light will exit the sample with a phase difference, called the retardance. The fundamental unit of retardance is length, such as nanometers (nm). It is frequently convenient, however, to express retardance in units of phase angle (waves, radians, or degrees), which is proportional to the retardance (nm) divided by the wavelength of the light (nm). An “average” birefringence for a sample is sometimes computed by dividing the measured retardation magnitude by the thickness of the sample.
[0005] Oftentimes, the term “birefringence” is interchangeably used with and carries the same meaning as the term “retardance.” Thus, unless stated otherwise, those terms are also interchangeably used below.
[0006] The two orthogonal polarization components described above are parallel to two orthogonal axes, which referred to as the “fast axis” and the “slow axis” of the optical material. The fast axis is the axis of the material that aligns with the faster moving component of the polarized light through the sample. Therefore, a complete description of the retardance of a sample along a given optical path requires specifying both the magnitude of the retardance and its relative angular orientation of the fast (or slow) axis of the sample.
[0007] The need for precise measurement of birefringence properties has become increasingly important in a number of technical applications. For instance, it is important to specify linear birefringence in optical elements that are used in high-precision instruments employed in semiconductor and other industries.
[0008] Moreover, some applications require that the retardation measurements be made across the surface of large-format optical elements or samples. For example, a manufacturer may wish to examine the retardance across the area of a large sheet of such material, thereby to determine whether the material is satisfactory (from a birefringence standpoint) before incurring further expense in processing the panel into a plurality of units.
[0009] The measurement of the birefringence across such large-format samples raises problems relating to the precise handling of the sample and instrumentation that is employed for such measurement. For example, it is impractical to move such large-format samples relative to the birefringence measurement instrument. Instead, the necessary optical components of the system can be moved relative to a stationary sample. One problem that arises with such a system is the need to ensure that components of the birefringence measurement system move precisely relative to one another and relative to the sample, thereby to provide consistently accurate birefringence measurement data irrespective of the amount the system components need to be moved in traversing large-format samples.
[0010] As noted above, external forces acting on the optical element or sample can induce birefringence. Such forces arise, for example, when a sample is bent or otherwise stressed while being held. The mass of the sample can induce some birefringence as a result of gravitational force, especially in instances where the sample is oriented with a significant amount of its mass vertically aligned. Thus, accurate measurement of the intrinsic birefringence of large-format samples requires that the optical element or sample of concern be held or supported in a manner that does not induce birefringence in the sample, which would produce an erroneous measure of the intrinsic birefringence. Specifically, such support requires that a flat sample be substantially uniformly supported in a plane without stress applied to the sample.
[0011] In addition to the need for adequately supporting the sample in a plane, the mechanism for supporting the sample must permit the passage of a light beam through the sample without interfering with that beam. The unhindered passage of a light beam through the sample and to an associated detection assembly is a critical aspect of accurate birefringence measurement. Moreover, it is most often desirable to measure the birefringence of a sample at closely spaced locations across the area of the sample. The design for a large-format sample holder, therefore, must strike a balance between adequately supporting the sample to prevent stress-induced birefringence, while still presenting a large area of the sample to the unhindered passage of light for birefringence measurement.
[0012] Of course, the ease and cost of manufacture, as well as the requirements for shipping and assembling a birefringence measurement system that includes a large-format sample holder are also important design considerations.
SUMMARY OF THE INVENTION
[0013] The present invention is directed to systems and methods for precisely measuring birefringence properties of large-format samples of optical elements.
[0014] In one preferred embodiment, a gantry-like configuration is employed for precise Y-direction movement of birefringence measurement system components relative to the sample. The components are mounted for precise X-direction movement. Accordingly, the entire area of the sample is traversed by the birefringence measurement components.
[0015] There is also provided an effective large-format sample holder that adequately supports the sample to prevent induced birefringence therein while still presenting a large area of the sample to the unhindered passage of the light beam of the birefringence measurement system.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] [0016]FIG. 1 is a diagram of one embodiment showing a preferred arrangement of the optical components of a birefringence measurement system that is used for measuring large-format optical elements in accordance with the present invention.
[0017] [0017]FIG. 2 is a block diagram of the signal processing components of the system depicted in FIG. 1.
[0018] [0018]FIG. 3 illustrates one preferred apparatus for holding a large-format optical element (sample) and for securing and moving certain of the components of the system of FIGS. 1 and 2 for measuring the birefringence at locations across the area of the sample.
[0019] [0019]FIGS. 4 and 5 are enlarged, detailed sectional views of one part of the sample holder portion of the apparatus of FIG. 3.
[0020] [0020]FIG. 6 is an enlarged, detailed section view showing an alternative embodiment of part of the sample holder of the present invention.
DETAILED DESCRIPTION
[0021] One embodiment of a system for measuring birefringence is described with reference to FIGS. 1 and 2. The system uses a dual photoelastic modulator (PEM) setup to measure low-level linear birefringence in optical elements. This embodiment determines the birefringence magnitude and angular orientation and has specifically designed signal processing, a data collection scheme, and an algorithm for measuring low-level linear birefringence at very high sensitivity.
[0022] As shown in FIG. 1, the dual-PEM setup 20 of this embodiment contains two modules. The source module comprises a light source 22 , a polarizer 24 oriented at 45 degrees, and a PEM 26 oriented at 0 degrees. The light source 22 is a polarized He—Ne laser that produces a beam having 632.8 nm wavelength and a spot size (diameter) of about 1 mm.
[0023] The detector module includes a second PEM 28 that is set to a modulation frequency that is different from the modulation frequency of the first PEM 26 . The second PEM 28 is oriented at 45 degrees. The detector module also includes an analyzer 30 at 0 degrees and a detector 32 .
[0024] Between the source and detector modules is a sample holder 34 (shown schematically in FIG. 1) that supports an optical element or sample 36 and is described more fully below. The vertically aligned arrows in FIG. 1 represent the path of a light beam emanating from the source 22 to pass through the sample 36 (as well as the other optical elements of the system) and into the detector 32 .
[0025] With continued reference to FIG. 1, the polarizer 24 and analyzer 30 are each a Glan-Thompson-type. A Si-photodiode detector 32 is used in this embodiment. Both PEMs 26 , 28 are bar-shaped, fused silica models having two transducers. The transducers are attached to the fused silica optical element with soft bonding material. To minimize birefringence induced in the optical element, only the transducers are mounted to the PEM housing. The two PEMs 26 , 28 have nominal resonant frequencies of 50 and 55 KHz, respectively.
[0026] With reference to FIG. 2, the electronic signals generated at the detector 32 contain both “AC” and “DC” signals and are processed differently. The AC signals are applied to two lock-in amplifiers 40 , 42 . Each lock-in amplifier, referenced at a PEM's fundamental modulation frequency (IF), demodulates the IF signal provided by the detector 32 . In a preferred embodiment, the lock-in amplifier is an EG&G Model 7265.
[0027] The DC signal is recorded after the detector signal passes through an analog-to-digital converter 44 and a low-pass electronic filter 46 . The DC signal represents the average light intensity reaching the detector 32 . The DC and AC signals are recorded at different PEM retardation settings.
[0028] The theoretical analysis underlying the measurement of the birefringence properties of the sample 36 in this embodiment is based on a Mueller matrix analysis and associated light-intensity signal processing to provide data representing the magnitude and angular orientation of the birefringence. Such processing does not form part of the present invention.
[0029] With reference to FIG. 3, the particulars of the large-format birefringence measurement system of the present invention are now described. The birefringence measurement system includes a cabinet 49 that has a top 51 . The sample 36 is supported on the top 51 of the cabinet by the holder 34 . The sample 36 is in a large format and may be, for example, a 1250 mm×1100 mm sheet of LCD material having a thickness of about 0.5 mm. The thickness of the sample is greatly exaggerated in FIG. 3.
[0030] The sample 36 remains stationary, supported by the holder 34 . In one preferred embodiment, the holder comprises a plurality of spaced-apart, taut wires 37 strung between two support beam assemblies 39 , 41 , one beam assembly on either side of an opening 63 in the top surface of the cabinet. The particulars of the holder are described more fully below.
[0031] An optical path “P” is provided between a source module 50 and a detector module 52 (FIG. 3). The source module 50 is an encasement of the components that make up that module as described above, and the detector module 52 , is an encasement of the above-described components that make up that module.
[0032] The source module 50 is mounted to an upper beam member 56 that spans, in an X-direction, the width of the sample holder 34 (hence, the sample 36 ). That upper beam member is supported at its opposite ends by vertical gantry columns 58 . The beam member 56 is fastened to move with the columns in the Y-direction. Each column extends through an elongated clearance slot 60 formed near the side edges of the cabinet top 51 .
[0033] The detector module 52 is mounted to a lower beam member 62 that is beneath the sample holder 34 and connected between (to move with) the gantry columns 58 .
[0034] The slots 60 permit the gantry columns 58 to move in the Y-direction to span the length of the sample 36 . To this end, the lower ends of the gantry columns are mounted to a matched pair of actuators 64 (only one seen in FIG. 3) such as a ballscrew linear actuator of sufficient length to traverse the length of the sample. Suitable position sensors and processor-controlled motors are also provided for ensuring synchronous movement of the gantry columns; hence uniform movement of the source and detector modules in the Y-direction.
[0035] The upper beam member 56 and lower beam member 62 are both configured to carry a servo motion control unit 66 , to which each module 50 , 52 is connected. The units 66 include suitable encoders, and associated motion controllers for ensuring that, as respects the X-direction motion, both modules 50 , 52 move in unison.
[0036] It will be appreciated that the precisely controlled X-Y movement of the source and detector modules as described above ensures repeatable birefringence measurements. For example, such movement ensures that the optical path “P” will not change relative to the detector aperture, which change might otherwise introduce systematic errors into the birefringence measurement results.
[0037] With reference to FIGS. 3 - 5 , the holder 34 includes a fixed beam assembly 39 that includes a flat base plate 70 that is attached to the top 51 of the cabinet 49 . The base plate 70 is attached near an edge of the opening 63 in the top 51 . A number of spacer plates 72 (see FIG. 3) are fixed to the upper surface of the base plate 70 to extend therefrom and support an anchor plate 74 above the base plate 70 . The anchor plate 74 is generally “L” shaped in cross section with a flat leg 76 and an up upwardly projecting flange 78 . The underside of the leg 76 is fixed to the tops of the spacer plates 72 . The uppermost edge 77 of the flange 78 is rounded.
[0038] One end of each of the wires 37 mentioned above is fixed to the anchor plate 74 . In particular, the wire ends (only a single wire end appearing in FIGS. 4 and 5) pass through an aperture 80 made in the leg 76 and through a hollow, cylindrical stop sleeve 82 . The sleeve 82 is crimped to fix the sleeve to the wire end and, since the sleeve diameter exceeds that of the aperture 80 , the wire 37 can thereafter be tensed with the sleeve abutting the leg 76 of the anchor plate 74 to anchor the end of the wire. The wire 37 is drawn by the tension over the rounded edge 77 to the other beam assembly 41 described below.
[0039] In a preferred embodiment the wire 37 is stainless steel wire rope that may or may not be coated with low-friction coatings such as Teflon. Nylon-coated wire rope and a number of other materials may also be used for the wires.
[0040] Preferably, the diameter of the wire 37 is selected to be small enough (for example 1 or 2 mm) to minimize the amount of space across the window 63 that is occupied by the wires (and that will interfere with the light beam path “P,” FIG. 3). The wire material and the uniform spacing between each wire is selected so that, depending on the weight of the sample, sufficient tension can be placed on each wire (as described more below) to ensure that the sample is held in a plane without any bending stress, which might be introduced if the sample were permitted to sag.
[0041] The spacing between individual wires 37 in the holder is as large as possible (depending upon the unit weight and flexibility of the sample) so that, as just mentioned, space across the window 63 that is occupied by the wires is minimized. The spacing between wires may be a few millimeters to several centimeters, depending, as mentioned, on the physical characteristics of the sample. Preferably, a minimum spacing (for example, 5 mm) is maintained to ensure that there remains between each wire a sufficiently large gap so that contaminants (glass particles, coatings debris etc.) that could interfere with the light beam do not become trapped between the wires.
[0042] In FIGS. 4 and 5 the thickness of the sample 36 is depicted in a scale that, unlike the relatively thick sample 36 shown in FIG. 1 for illustrative purposes, reflects the relatively thin nature of at least some types of samples that are used with the present holder 34 , such as the 0.5 mm-thick LCD material mentioned above.
[0043] As shown in FIG. 5, the other end of each wire 37 is connected to the tension beam assembly 41 that permits the wire tension to be established and maintained. The tension beam assembly 41 includes a flat base plate 90 that is attached to the top 51 of the cabinet 49 . The base plate 90 is attached near the edge of the opening 63 in the top 51 . A number of cylindrical spacer posts 92 are fixed at spaced-apart intervals to the upper surface of the base plate 90 to extend therefrom and support an anchor plate 94 above the base plate 90 . The anchor plate 94 is generally “L” shaped with a flat leg 96 and an up upwardly projecting flange 98 . The underside of the leg 96 is fixed to the tops of the spacer posts 92 . The uppermost edge 97 of the flange 98 is rounded.
[0044] The end of each of the wires 37 is pulled over the rounded edge 97 and connected to the leg 96 of the anchor plate 94 in a manner that both anchors the end and that permits the application of tension to the wire. One way for making this connection is to employ a conventional wire end fitting, such as a stud end fitting 100 shown in FIG. 5. The stud end fitting 100 captures the end of the wire in an externally threaded sleeve 102 that threads into a hex-ended stud 104 . The threaded shaft 106 of the stud passes through an aperture in the leg 96 and through a lock nut 108 that bears against the underside of the leg. The nut is tightened once sufficient tension is placed on the wire 37 .
[0045] The beam assemblies 39 , 41 are configured and arranged so that the uppermost parts of the respective rounded edges 77 , 97 (FIGS. 4 and 5) are in a common plane such that the taut wires 37 extending between those assemblies will hold the sample flat, without bending stress, thereby ensuring that the light beam passing through the sample is unaffected by birefringence that would otherwise be induced in the sample by such bending.
[0046] It will be appreciated that in the course of manufacturing the present holder, it is only necessary to ensure that the top edges 77 , 97 of the beam assemblies are in a common plane and that suitable tension is placed on the wires to precisely maintain the flatness of the sample that the holder supports. This can be compared to the complexities of, for example, manufacturing a large, rigid, precisely flat support plate with openings machined therethrough for permitting the passage of light.
[0047] It is contemplated that, as an alternative to the taut wires 37 , other thin elongated members may be employed. For example, as depicted in FIG. 5, small-diameter cylindrical rods 110 can span the window 63 . In one such embodiment, the rods are rotatably mounted, as at bearings 112 , between members like the above discussed anchors 74 , 94 that are mounted to opposing edges of the window 63 . The rotatable rods minimize the contact between the holder and the sample and also provide a way for easily rolling a sample onto and off the holder.
[0048] It is also contemplated that the sample holder could be constructed in a manner that permits a relatively rapid application of tension to the wires and a correspondingly rapid release, thereby to facilitate assembly and disassembly of the holder as may be desired for shipping. One embodiment directed to this aspect of the invention is illustrated in FIG. 6.
[0049] [0049]FIG. 6 depicts a way of anchoring the ends of the support wires 37 so that the entire set of wires can be tensioned and released by adjusting a movable tension plate 190 to which the ends are fastened. In this embodiment, the beam assembly 139 comprises a base plate 170 that is attached close to an edge of the opening 63 in the top 51 . That plate may be attached by attachment bolts 171 , for example, that can be removed to permit the detachment of the entire assembly 139 from the cabinet 49 . In this regard, a beam assembly substantially identical to the fixed beam assembly 39 of FIG. 4, or like the assembly 41 of FIG. 5, may be used on the opposite edge of the window 63 to fasten the other ends of the wires.
[0050] A number of spacer plates 172 are fixed to the upper surface of the base plate 170 to extend therefrom and support an anchor plate 174 above the base plate 170 . The anchor plate 174 is generally “L” shaped with a flat leg 176 that extends inwardly beyond the spacers 172 and terminates in an upwardly projecting flange 178 .
[0051] The uppermost edge 177 of the flange 178 is rounded. One end of each of the wires 37 mentioned above is passes through an aperture 180 made in the inwardly projecting section of the leg 176 and then through a hole in the center of a rigid tension plate 190 that is located between the top 51 of the cabinet and the inwardly extending part of the anchor plate 174 . The ends of the wire are captured in stop sleeves 182 , which, like sleeves 82 in the earlier described embodiment are crimped to fix the sleeve to the wire end. Similarly, since the sleeve diameter exceeds that of the aperture in the tension plate, the wire 37 can thereafter be tensioned with the sleeve abutting the underside of that plate 190 .
[0052] It is contemplated that grooves, such as shown at 179 in FIG. 6, may be formed in the top edge 177 of the beam assembly (as well as in the earlier discussed edges 77 , 97 ) and sized to receive the wires 37 thereby to permit and maintain proper spacing of the wires.
[0053] A few spaced-apart tension-adjusting, shoulder-type bolts 192 are passed through clear holes in the tension plate and threaded into the base plate 170 . It will be appreciated, therefore, that the threading and unthreading of these few bolts 192 will respectively increase and decrease the tension in all of the wires 37 . It will also be understood that with the ends of the wires captured as a single set in a single rigid bar member or the like, any of a number of quick release clamping mechanisms could be used for tensioning and releasing the set of wires. Moreover, any of a number of mechanisms can be employed for securing the anchor plate 174 to the cabinet while permitting motion of the tension plate. For example, one can do away with the bolts 192 and connect, via a hinge, a long edge of the plate 190 to the cabinet or to the base plate 170 . A handle can be attached to the plate for moving the plate about the hinge to simultaneously tighten and loosen all of the wires. A toggle or latch mechanism could be included to secure the plate in the wires-tightened position.
[0054] Although preferred and alternative embodiments of the present invention have been described, it will be appreciated that the spirit and scope of the invention is not limited to those embodiments, but extend to the various modifications and equivalents. For example, although the sample holder was discussed above in the context of a birefringence measurement system, it will be understood that the holder can be adapted for use in any of a variety of optical setups or systems.
[0055] Moreover, although the focus here was on a large-format sample, it will be appreciated that the holder of the present invention will also be useable with samples of any size, including quite small ones, without the need for modifying the holder.
|
The disclosure is directed to systems and methods for precisely measuring birefringence properties of large-format samples of optical elements. A gantry-like configuration is employed for precise movement of birefringence measurement system components relative to the sample. There is also provided an effective large-format sample holder that adequately supports the sample to prevent induced birefringence therein while still presenting a large area of the sample to the unhindered passage of light.
| 6
|
OBJECT OF THE INVENTION
[0001] The object of the invention is a process for the preparation of the active ingredients ospemifene and fispemifene.
PRIOR ART
[0002] Ospemifene, the chemical name of which is 2-{4-[(1Z)-4-chloro-1,2-diphenyl-1-buten-1-yl]phenoxy}ethanol (FIGURE), is a non-steroidal selective oestrogen-receptor modulator (SERM) which is the active ingredient of a medicament recently approved for the treatment of menopause-induced vulvar and vaginal atrophy.
[0003] The preparation of ospemifene, which is disclosed in WO96/07402 and WO97/32574, involves the reaction sequence reported in Scheme 1:
[0000]
[0004] The first step involves alkylation of 1 with benzyl-(2-bromoethyl)ether under phase-transfer conditions. The resulting product 2 is reacted with triphenylphosphine and carbon tetrachloride to give chloro-derivative 3, from which the benzyl protecting group is removed by hydrogenolysis to give ospemifene.
[0005] A more direct method of preparing ospemifene is disclosed in WO2008/099059 and illustrated in Scheme 2.
[0000]
[0006] Intermediate 5 (PG=protecting group) is obtained by alkylating 4 with a compound X—CH 2 —CH 2 —O-PG, wherein PG is a hydroxy protecting group and X is a leaving group (specifically chlorine, bromine, iodine, mesyloxy or tosyloxy), and then converted to ospemifene by removing the protecting group.
[0007] Alternatively (WO2008/099059), phenol 4 is alkylated with a compound of formula X—CH 2 —COO—R wherein X is a leaving group and R is an alkyl, to give a compound of formula 6, the ester group of which is then reduced to give ospemifene (Scheme 3)
[0000]
[0008] Processes for the synthesis of ospemifene not correlated with those reported in schemes 2 and 3 are also disclosed in the following documents: CN104030896, WO2014/060640, WO2014/060639, CN103242142 and WO2011/089385.
[0009] Fispemifene, the chemical name of which is (Z)-2[2-[4-(4-chloro-1,2-diphenylbut-1-enyl)phenoxy]ethoxy]ethanol (FIGURE) is a non-steroidal selective oestrogen-receptor modulator (SERM), initially disclosed in WO01/36360. Publications WO2004/108645 and WO2006/024689 suggest the use of the product in the treatment and prevention of symptoms related with male androgen deficiency. The product is at the clinical trial stage for the treatment of male neurological disorders.
[0010] According to an evaluation of the synthesis routes for ospemifene and fispemifene described in the literature, those which use compound 4 (Schemes 2 and 3) are particularly interesting, as 4 is also a key intermediate in the synthesis of toremifene, an oestrogen-receptor antagonist (ITMI20050278).
DESCRIPTION OF FIGURE
[0011] FIGURE: Structural formulas of ospemifene and fispemifene
DESCRIPTION OF THE INVENTION
[0012] We have surprisingly found that ospemifene and fispemifene can be advantageously synthesised by alkylating phenol 4 with an alkylating agent of formula 7
[0000] X—CH 2 CH 2 —Y 7
[0000] wherein X is a leaving group and Y is the —(OCH 2 CH 2 ) n OH group wherein n is zero or 1; or X and Y, taken together, represent an oxygen atom;
[0013] to give a compound of formula 8
[0000]
[0014] wherein Y is as defined above.
[0015] When Y is —(OCH 2 CH 2 ) n OH wherein n is zero, formula 8 represents ospemifene.
[0016] When Y is —(OCH 2 CH 2 ) n OH wherein n is 1, formula 8 represents fispemifene.
[0017] Phenol 4 can therefore be alkylated according to the present invention with no need for protection and subsequent deprotection of the hydroxyl function present in the alkylating reagent.
DETAILED DESCRIPTION OF THE INVENTION
[0018] Leaving group X of the compound of formula 7 is preferably a halogen, such as chlorine, bromine or iodine, or an alkyl or arylsulphonate such as mesyloxy or tosyloxy.
[0019] In one embodiment of the invention, in the compound of formula 7, X is a leaving group as defined above and Y is —(OCH 2 CH 2 ) n OH wherein n is zero, and the reaction of 7 with 4 provides ospemifene, as reported in Scheme 4.
[0000]
[0020] In another embodiment of the invention, in the compound of formula 7, X and Y, taken together, represent an oxygen atom, the compound of formula 7 is ethylene oxide, and the reaction of 7 with 4 provides ospemifene, as reported in Scheme 5.
[0000]
[0021] In another embodiment of the invention, X is a leaving group as defined above and n is 1, and the reaction of 7 with 4 provides fispemifene, as reported in Scheme 6.
[0000]
[0022] The reaction between phenol 4 and alkylating reagent 7, wherein X is a leaving group as defined above and Y is the —(OCH 2 CH 2 ) n OH group as defined above, can be effected in an aprotic solvent preferably selected from ethers such as tetrahydrofuran, dioxane, dimethoxyethane, tert-butyl methyl ether, amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone, nitriles such as acetonitrile, and hydrocarbons such as toluene and xylene, in the presence of a base preferably selected from alkoxides, amides, carbonates, oxides or hydrides of an alkali or alkaline-earth metal, such as potassium tert-butoxide, lithium bis-trimethylsilylamide, caesium and potassium carbonate, calcium oxide and sodium hydride.
[0023] The reaction can involve the formation in situ of an alkali or alkaline earth salt of phenol 4, or said salt can be isolated and then reacted with alkylating reagent 7. Examples of phenol 4 salts which can be conveniently isolated are the sodium salt and the potassium salt. Said salts can be prepared by known methods, for example by treatment with the corresponding hydroxides (see preparation of the potassium salt of phenol 4 by treatment with aqueous potassium hydroxide as described in document ITMI20050278), or from the corresponding alkoxides, such as sodium methylate in methanol for the preparation of the sodium salt of phenol 4, as described in the examples of the present application.
[0024] Other salts of phenol 4 which can be prepared in situ or isolated for use in the alkylation reaction are quaternary ammonium salts, preferably tetrabutyl-ammonium salt.
[0025] The reaction between phenol 4 and alkylating reagent 7, wherein X is a leaving group as defined above and Y is the —(OCH 2 CH 2 ) n OH group as defined above, can also be effected in a biphasic liquid-liquid system comprising an organic solvent immiscible with water and an aqueous solution of an inorganic base such as an alkali or alkaline earth hydroxide or carbonate, for example the biphasic system consisting of toluene and an aqueous solution of potassium hydroxide.
[0026] The reaction can also be carried out in a biphasic solid-liquid system comprising an organic solvent such as an aromatic hydrocarbon like toluene or a chlorinated solvent like methylene chloride, an inorganic base as defined above, such as potassium carbonate, and a catalyst among those commonly used for reactions under phase-transfer conditions, such as a quaternary ammonium salt like tetrabutylammonium bromide, benzyltriethylammonium chloride and similar salts.
[0027] The reaction between phenol 4 and ethylene oxide (consisting of formula 7 wherein X and Y, taken together, represent an oxygen atom) can be effected in protic or aprotic solvent in the presence of acid or basic catalysis or can be catalysed by quaternary ammonium or phosphonium salts.
[0028] The reactions are carried out for a time and at a temperature sufficient to obtain the desired product. The most effective reaction conditions to optimise the yield and purity of the products obtained can easily be identified by a skilled person.
[0029] The products of formula 4 and formula 7 are known products.
[0030] The invention will now be illustrated by the following examples.
Example 1
[0031] Sodium hydride (4.2 g) is loaded in portions into a solution of 4-(4-chloro-1,2-diphenyl-buten-1-yl)phenol (10 g) in tetrahydrofuran (120 ml) in an inert gas environment, and the mixture is maintained under stirring at room temperature for 1 h. 2-Iodoethanol (11 ml) is added dropwise, and the reaction mixture is refluxed for about 9 h. Water is added, and the mixture is concentrated and extracted with ethyl acetate. The organic phase is washed with sodium carbonate aqueous solution and then with water, and then concentrated under vacuum. After crystallisation of the residue from methanol-water (about 5:1), 9.9 g of crude ospemifene is obtained.
Example 2
[0032] A solution of sodium methylate in methanol (6.25 ml) is added to a solution of 4-(4-chloro-1,2-diphenyl-buten-1-yl)phenol (10 g) in methanol (100 ml) in an inert gas environment, and maintained under stirring at room temperature for 1 h. The mixture is concentrated under vacuum and taken up with tetrahydrofuran (100 ml). A solution of 2-iodoethanol (3.5 ml) in tetrahydrofuran (30 ml) is added dropwise, and the reaction mixture is refluxed for about 3 h. Water is added, and the mixture is concentrated and extracted with ethyl acetate. The organic phase is washed with a saturated sodium hydrogen carbonate aqueous solution, and finally with water. The resulting solution is then concentrated under vacuum and crystallised from methanol-water to obtain 5.8 g of crude ospemifene.
Example 3
[0033] Potassium tert-butylate (2.0 g) is added to a solution of 4-(4-chloro-1,2-diphenyl-buten-1-yl)phenol (5 g) in tert-butanol (75 ml) in an inert gas environment, and maintained under stirring at room temperature for 1 h. The solvents are concentrated under vacuum, and the concentrate is taken up with tetrahydrofuran (50 ml). A solution of 2-iodoethanol (1.7 ml) in tetrahydrofuran (15 ml) is added in about 30 minutes, and the reaction mixture is then refluxed for about 2 h. The process then continues as described in Example 1, and 2.9 g of crude ospemifene is obtained.
Example 4
[0034] A 50% potassium hydroxide aqueous solution (4.4 ml) is added to a solution of 4-(4-chloro-1,2-diphenyl-buten-1-yl)phenol (2 g) in toluene (20 ml) in an inert gas environment, and maintained under stirring at room temperature for 15 minutes. 2-Iodoethanol (2.2 ml) is added in about 30 minutes, and the reaction mixture is refluxed and maintained at that temperature for about 7 h. After the addition of water, the phases are separated. The organic phase is washed with a saturated sodium hydrogen carbonate aqueous solution, and finally with water. The organic phase is then concentrated under vacuum. After crystallisation of the residue from methanol-water (about 5:1), 0.85 g of crude ospemifene is obtained.
|
Disclosed is a process for the synthesis of the active ingredients ospemifene and fispemifene which comprises reacting phenol 4 with an alkylating agent X—CH 2 CH 2 —Y of formula 7, wherein X is a leaving group and Y is the —(OCH 2 CH 2 ) n OH group wherein n is zero or 1; or X and Y, taken together, represent an oxygen atom; to give ospemifene or fispemifene of formula 8.
| 2
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to outdoor vacuum systems and more particularly, to vacuum systems used to vacuum large areas having uneven terrain such as golf courses. In a preferred embodiment the detachable hopper and vacuum apparatus of this invention is characterized by a detachable hopper fitted with tandem, pivotally-mounted wheels and having a hinged front panel provided with a panel window for receiving the discharge chute of a vacuum apparatus and collecting vacuumed material collected by the vacuum apparatus. The detachable element hopper of the invention is designed for coupling with conventional tractors or other towing vehicles by operation of a slidably-mounted tongue frame having a hitch mechanism on the extending end and adapted to extend for attachment to the towing vehicle and retract for coupling to the vacuum apparatus of this invention. The detachable hopper is also fitted with a dual contact hitch receptacle mechanism for receiving a pair of corresponding spaced, bayonet-type coupling mechanisms mounted on the vacuum apparatus to releasably secure the detachable hopper and vacuum apparatus in operational mode. In another preferred embodiment the detachable hopper is characterized by a collection bin mounted on a hopper bed in tilting or dumping fashion to facilitate easy emptying of the collection bin. The vacuum apparatus element of this invention is characterized by a frame fitted with an engine connected to a blower located in a blower housing and a chute assembly communicates with the blower housing and is provided with offset bellows and wheels located at the extending ends of the bellows for following the contours of an irregular terrain and vacuuming loose material on the terrain. A discharge chute projects from the discharge end of the blower housing and is shaped to engage the panel window in the hinged front panel of the detachable hopper when the vacuum apparatus is secured to the detachable hopper in operational mode.
The proliferation of golf courses in the United States and other parts of the world has created a growing demand for high quality, litter-free, well groomed greens and fairways to entice players. Competition between golf courses, particularly in large metropolitan areas, has resulted in great effort to insure that the greens and fairways are carefully mown, manicured and cleared of all loose liter, debris and refuse during playing hours. The clearing of such a large area of refuse, debris and litter is no small task and various type of equipment have been developed to achieve this end.
Increasing emphasis has also been placed on the care and enhancement of private lawns, as well as the lawns of commercial establishments and the like and particularly on carefully mowing and manicuring the larger lawns, to achieve the best possible visual effect. The care and grooming of such lawns, and particularly estate-size lawns, has required the use of various types of tractors, carts, collection receptacles and the like, to logistically handle the litter, debris, cuttings and other refuse.
2. Description of the Prior Art
Various types of equipment have been developed and are well known in the art for grooming, manicuring and vacuuming lawns and other outdoor surfaces such as golf courses and the like. Typical of this equipment is the apparatus detailed in the following United States patents: U.S. Pat. No. 3,522,695, dated Aug. 4, 1970, to O. Musgrave, entitled "Debris Catcher"; U.S. Pat. No. 3,755,851, dated Sep. 4, 1973, to John K. Williams, entitled "Gas Cleaning Apparatus"; U.S. Pat. No. 3,824,771, dated Jul. 23, 1974, also to John K. Williams entitled "Gas and Particulate Solid Material Separating and Solid Material Discharging Apparatus"; U.S. Pat. No. 3,903,565 dated Sep. 9, 1975, to L. T. Hicks, entitled "Leaf and Grass Cart Bagger"; U.S. Pat. No. 4,062,085, dated Dec. 13, 1977, to I. J. Duncan, entitled "Suction Cleaning Apparatus"; U.S. Pat. No. 4,095,398, dated Jun. 20, 1978, to Richard F. Aumann, et al, entitled "Grass Baggger"; U.S. Pat. No. 4,426,830, dated Jan. 24, 1984, to D. Tackett, entitled "Lawn Clipping Vacuum Collector"; U.S. Pat. No. 4,433,532, dated Feb. 28, 1984, to M. L. McCunn, entitled "Lawn Mower Bagging System Including Air Assist"; U.S. Pat. No. 4,443,997, dated Apr. 24, 1984, to Bahram Namdari, entitled "Apparatus for Vacuum Collection and Compacting of Leaves and Grass Clippings"; U.S. Pat. No. 4,699,393, dated Oct. 13, 1987, to James R. Schweigert, entitled "Multi-Purpose Trailer With Universal Mounting Hitch"; U.S. Pat. No. 4,761,943, dated Aug. 9, 1988, to Richard W. Parker, et al, entitled "Mobile Vacuum System for Use With A Riding Tractor Mower; U.S. Pat. No. 4,787,197, dated Nov. 29, 1988, to James R. Schweigert, entitled "Multi-Purpose Cart and Grass Collector"., U.S. Pat. No. 4,881,362, dated Nov. 21, 1989, to Richard W. Parker, et al, entitled "Mobile Vacuum System for Use With Riding Tractor Mower"., U.S. Pat. No. 4,885,817, dated Dec. 12, 1989, to K. Tanase, entitled "Air-Dust Separation System for Pneumatic Road-Cleaning Vehicle"; U.S. Pat. No. 4,922,696, dated May 8, 1990, to Stephen R. Burns, et al, entitled "Grass Collecting/Utility Cart for Riding Lawn Mower".
It is an object of this invention to provide a new and improved detachable hopper and vacuum apparatus, which includes a detachable hopper having a slidably-mounted tongue for optionally attaching to a conventional towing vehicle or recessing to facilitate coupling to the vacuum apparatus of this invention by means of a bayonet-type coupling mechanism.
Another object of this invention is to provide a new and improved detachable hopper and vacuum apparatus for vacuuming both irregular and smooth terrain, which detachable hopper includes a bayonet coupling hitch receptacle for coupling to the bayonet coupling of the vacuum apparatus, a hinged front panel fitted with a panel window for receiving a corresponding discharge chute provided on the vacuum apparatus, and tandem, pivoting wheels for traversing irregular terrain.
Still another object of this invention to provide a new and improved detachable hopper and vacuum apparatus for vacuuming irregular terrain and collecting the vacuumed refuse, which vacuum apparatus includes a frame, an engine mounted on the frame and coupled to a blower enclosed in a blower housing, which blower housing communicates with a chute assembly provided with flexible bellows at the bottom thereof and wheels at the extending ends of the bellows, for following the contours of the irregular terrain and vacuuming refuse and litter on the terrain in an efficient manner, which litter and refuse is transferred by the blower through the discharge chute into the detachable hopper.
Yet another object of this invention is to provide a detachable hopper for receiving refuse and litter, including grass clippings and other particulate matter, which detachable hopper is fitted with a slidably-mounted tongue for attachment to a towing vehicle when extended, the detachable hopper also having a hinged front panel fitted with a window for receiving the discharge chute of the towing vehicle and tandem, pivotally-mounted wheels for optimum traversal of irregular terrain.
Still another object of this invention is to provide a vacuum apparatus for vacuuming both flat and irregular terrain and delivering the refuse and litter vacuumed from the terrain either to a collection vehicle or to the atmosphere, which vacuum apparatus includes a frame having a blower driven by an engine and a blower housing communicating with a chute assembly provided with bellows projecting toward the ground and a set of wheels provided at the end of the bellows for traversing the ground and maintaining the mouth of the bellows in close proximity to the terrain, wherein grass clippings, litter, refuse and the like may be vacuumed from the terrain forced through the blower housing and expelled from the discharge chute.
SUMMARY OF THE INVENTION
These and other objects of the invention are provided in new and improved detachable hopper and vacuum apparatus towed by a tractor or other vehicle and characterized in a first preferred embodiment by a tiltable detachable hopper element coupled by means of a dual bayonet-type receiver mechanism to a vacuum apparatus, such that grass clippings, refuse and litter vacuumed by the vacuum apparatus is delivered to the detachable hopper for containment. In a preferred embodiment the detachable hopper is characterized by a hopper bed fitted with tandem, pivotally-mounted wheels and a collection bin mounted on the hopper bed in tilting relationship, with a hinged front panel fitted with a panel window for receiving the discharge chute of the vacuum apparatus and transferring the grass clippings, litter and refuse from the vacuum apparatus to the collection bin. In another preferred embodiment the vacuum apparatus is characterized by a frame fitted with an engine coupled to a blower mounted in a blower housing which is positioned in communication with a chute assembly having a collapsible bellows system mounted on the bottom thereof, for facing the terrain and provided with wheels for traversing the terrain and insuring that the mouth of the bellows remain in close proximity to the terrain. Grass clippings, trash and refuse traversed by the bellows are pulled through the chute assembly by operation of the blower to the discharge chute and are delivered from the discharge chute into the panel window of the hinged panel of the detachable hopper.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood by reference to the accompanying drawings, wherein:
FIG. 1 is a perspective view of a preferred embodiment of the detachable hopper element of the detachable hopper and vacuum apparatus of this invention;
FIG. 2 is a left side elevation of the detachable hopper illustrated in FIG. 1 with the vacuum apparatus element in coupled configuration, as illustrated in phantom;
FIG. 3 is a plan view, partially in section, of the front portion of the detachable hopper illustrated in FIGS. 1 and 2;
FIG. 4 is a side view, partially in section, of the detachable hopper illustrated in FIG. 2, more particularly illustrating tilting of the collection bin with respect to the hopper bed;
FIG. 5 is an enlarged side view, partially in section, of a typical plate receptacle attached to the detachable hopper and bayonet coupling extending from the vacuum apparatus, for releasably coupling the detachable hopper and vacuum apparatus of this invention;
FIG. 6 is a side view, partially in section, of the plate receptacle and bayonet coupling in engaged and locked configuration wherein the detachable hopper and vacuum apparatus are coupled in operational mode;
FIG. 7 is a top view of the plate receptacle and bayonet coupling illustrated in FIG. 5;
FIG. 8 is a top view of the plate receptacle and bayonet coupling illustrated in FIG. 6;
FIG. 9 is a side view, partially in section, of a typical caster assembly provided on the vacuum apparatus, with the caster assembly locked to prevent pivoting of the caster wheels;
FIG. 10 is a side view, partially in section, of the caster assembly illustrated in FIG. 9, with the caster wheels in released, pivoting and operational configuration;
FIG. 11 is a sectional view taken along line 11--11 of the caster assembly illustrated in FIG. 10;
FIG. 12 is a front perspective view of a preferred embodiment of the vacuum apparatus element of the detachable hopper and vacuum apparatus of this invention;
FIG. 13 is a sectional view taken along line 13--13 of the vacuum apparatus illustrated in FIG. 12;
FIG. 14 is a side view of the vacuum apparatus illustrated in FIGS. 12 and 13, more particularly illustrating the detachable hopper element of the invention coupled to the vacuum apparatus, as illustrated in phantom; and
FIG. 15 is an enlarged perspective view, partially in section, of caster assembly and bayonet coupling elements of the vacuum apparatus and a corresponding plate receptacle element of the detachable hopper.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring initially to FIGS. 1-8 of the drawings, in a preferred embodiment the detachable hopper of this invention is generally illustrated by reference numeral 1. The detachable hopper 1 is characterized by a hopper bed 2, consisting of a bed frame 2a and bed braces 2b. A pair of hitch receptacles 3 are welded or otherwise attached to the front corners of the hopper bed 2 and each of the hitch receptacles 3 is characterized by a pair of coupling plates 4, having outwardly turned plate lips 8 and spaced by a guide mount plate 10 on the bottom thereof. Curved coupling pin slots 5 are provided in the coupling plates 4 in spaced, parallel relationship and a coupling pin 6 extends transversely through each of the parallel coupling pin slots 5 and is fitted with a washer 7 and a corresponding nut 7a. Accordingly, it will be appreciated from a consideration of the shape of the curved coupling pin slots 5 and the positioning of the coupling pin 6 in each set of coupling pin slots 5, that each coupling pin 6 may be easily manipulated from the top to the bottom of the coupling pin slots 5, as desired, as hereinafter further described. A bayonet guide 9 is welded or otherwise secured to the guide mount plate 10 and extends downwardly in angular relationship from the guide mount plate 10, as further illustrated in FIGS. 5 and 6, for purposes which will be hereinafter further described. As further illustrated in FIGS. 1-4 of the drawings, a collection bin 16 is pivotally attached to the hopper bed 2 by means of collection bin hinges 26, more particularly illustrated in FIG. 4. A pair of lift cylinders 11 are attached to the hopper bed 2 in spaced, pivoting relationship and the cylinder piston 12 of each of the lift cylinders 11 is attached to a corresponding piston bracket 13, welded to the bottom panel stiffener 25 of the collection bin 16, as further illustrated in FIG. 4. Accordingly, operation of the lift cylinders 11 by air or hydraulic means well known to those skilled in the art (not illustrated), pivots the collection bin 16 upwardly with respect to the hopper bed 2 on the collection bin hinges 26, as further illustrated in FIG. 4, to facilitate emptying of the collection bin 16. The collection bin 16 is further characterized by a pair of parallel bin side panels 17, stiffened by spaced panel stiffeners 25 and fitted with a top panel 37, secured to the top panel stiffeners 25 by top panel rivets 38 or alternative means, a rear panel (not illustrated) and a bin front panel 18, having a hinged panel 19 at the top thereof. The hinged panel 19 is further characterized by a hinged panel window 20, which is open and designed to accommodate the discharge chute of the vacuum apparatus element of this invention, as hereinafter further described. In a most preferred embodiment of the invention the hinged panel 19 is secured to the lower portion of the bin front panel 18 by means of spaced panel hinges 21 and corresponding pin brackets 22, attached to the hinge panel 19, and panel brackets 23, attached to the vertical panel stiffeners 25 and receive bracket pins 24 for securing the hinged panel 19 in upward-standing relationship against the bin side panel 17 or in downwardly-folding relationship against the bin front panels 18, as desired.
Referring now to FIG. 14 of the drawings, in a most preferred embodiment of the invention the detachable hopper 1 is designed for attachment to the vacuum apparatus 51 and the vacuum apparatus 51 to a conventional towing vehicle 46, such as a tractor or the like. Alternatively, as illustrated in FIGS. 2 and 3, the detachable hopper 1 can be connected directly to a towing vehicle by means of a sliding tongue 31, which is slidably mounted in a corresponding tongue mount frame 27, attached to the front of the hopper bed 2. The tongue mount frame 27 is fitted with tongue mount frame bolts 28, which project through aligned tongue retainer apertures 29, provided in the torque mount frame 27 and tongue frame 34, to secure the tongue 31 in extended configuration, as illustrated in FIG. 2. The tongue frame 34 is further characterized by frame members 35, fitted with a pair of ball mount plates 32, having a ball frame opening 33 for receiving a pin (not illustrated) and securing the tongue 31 to a towing vehicle (not illustrated). When it is desired to attach the detachable hopper 1 to the vacuum apparatus of this invention, the tongue mount bolts 28 are removed from the corresponding tongue retainer apertures 29 in the tongue mount frame 27 and the tongue frame 34 and the latter is slidably extended inside the hopper bed 2 on the bed frame 2a, as illustrated in FIG. 3. The tongue mount bolts 28 are removed from the matching outside tongue retainer apertures 29 and replaced in the aligned inside tongue retainer apertures 29 to secure the tongue 31 in the hopper bed 2, as further illustrated in FIG. 3.
As illustrated in FIGS. 1, 2 and 4 of the drawings, in another most preferred embodiment of the invention the wheels 43, carrying tires 44, are attached to a common wheel trolley 39, which is pivotally attached to a trolley mount 40, welded or otherwise attached to the bed frame 2a of the hopper bed 2 by means of a trolley pin 41. Accordingly, the wheel trolleys 39 operate to allow the wheels 43 and tires 44 to independently pivot with respect to the hopper bed 2, in order to more efficiently traverse irregular terrain.
Referring now to FIGS. 5-13 and more particularly, to FIGS. 12 and 13, in another preferred embodiment the vacuum apparatus of this invention is generally illustrated by reference numeral 51. The vacuum apparatus 51 is characterized by a vacuum apparatus frame 52, provided with a frame brace 53 and a chute assembly 55, projecting above and below the vacuum apparatus frame 52. The chute assembly 55 further includes a forward intake housing 56, fitted with a set of forward intake bellows 57, and a forward intake wheel frame 58, supporting forward intake wheels 59, as illustrated in FIG. 13. The forward intake wheel frame 58 further includes bellows mount bars 60 and corresponding mount bolts 61, for securing the forward intake bellows 57 to the forward intake wheel frame 58, such that the open end, or mouth of the forward intake bellows 57 faces downwardly, spaced from the ground level by approximately a radius of the forward intake wheels 59. Similarly, a rear intake housing 63 is provided in the chute assembly 55 and extends outwardly beyond forward intake housing 56, as further illustrated in FIGS. 13 and 14. The rear intake housing 63 is likewise fitted with rear intake bellows 64, having a rear intake wheel frame 65, supported by rear intake wheels 66. Both the forward intake bellows 57 and the rear intake bellows 64 are provided with a pair of crossed bellows chains 62, which are mounted to the forward intake housing 56 and rear intake housing 63, respectively, and the corresponding forward intake wheel frame 58 and rear intake wheel frame 65, respectively, as illustrated in FIG. 4, in order to prevent the forward intake bellows 57 and rear intake bellows 64 from hyperextending and tearing the flexible bellows. It will be appreciated from a consideration of FIG. 13 that the forward intake bellows 57 and rear intake bellows 64 are disposed in the forward intake housing 56 and rear intake housing 63, respectively, such that the mouth or open ends of the forward intake bellows 57 and rear intake bellows 64 face the ground and are separated from the ground by approximately the radius of the respective forward intake wheels 59 and rear intake wheels 66, respectively, as heretofore described. Accordingly, it will be appreciated by those skilled in the art from a consideration of FIG. 13, that the forward intake bellows 57 and rear intake bellows 64 facilitate "floating" of the forward intake wheel frame 58 and rear intake wheel frame 65 to follow the contours of the terrain traversed by the detachable hopper and vacuum apparatus and permit vacuuming of the terrain, however irregular, with optimum efficiency.
A blower housing 71 is also mounted on the vacuum apparatus frame in the forward intake housing 56, forward of the chute assembly 55, and includes a round access plate 72, secured in place by access plate bolts 73, with one end of a blower shaft 75 projecting through a blower bearing 74, located in the center of the access plate 72 and secured in place by bearing bolts 76. The blower shaft 75 extends through the blower housing 71 and the collection plenum 68 and beneath the shaft guard 83, for coupling to the engine shaft 81a, projecting through a shaft bearing 82 of the engine 81, also mounted on the vacuum apparatus frame 52 and fitted with a muffler 84. As further illustrated in FIG. 14, a blower 78 is mounted on the blower shaft 75 and includes blower blades 79, projecting outwardly toward the outer periphery of the blower housing 71, for creating a vacuum inside the blower housing 71 and pulling grass clippings, trash, refuse, debris and like material (not illustrated) upwardly through the forward intake bellows 57 and rear intake bellows 64 of the chute assembly 55, into the collection plenum 68 and upwardly into a chute extension 87 element of the discharge chute 86, extending from the discharge of the blower housing 71. The discharge chute 86 is further characterized by flexible chute bellows 88 and an adaptor plate 89, attached to the chute bellows 88 and having a plate opening 90, for extending through the hinge panel window 20 of the hinge panel 19 when the vacuum apparatus 51 is attached to the detachable hopper in operational mode, as hereinafter further described. In another preferred embodiment of the invention, the top portion of the discharge chute 86 is fitted with a chute plate 86a, the chute extension 87 is provided with a cooperating extension plate 87a which matches the chute plate 86a, and the top portion of the discharge chute 86 is attached to the chute extension 87 by means of bolts 91, as illustrated in FIG. 12. Accordingly, it will be appreciated from a consideration of FIG. 12 that the top portion of the discharge chute 86 may be positioned in selected 90 degree rotational configurations with respect to the configuration illustrated in FIG. 12, by removing the bolts 91, rotating the top portion of the discharge chute 86, including the chute bellows 88 and adaptor plate 89, to the desired 90 degree, 180 degree or 360 degree position and reinserting the bolts 91 in matching apertures in the chute plate 86a and extension plate 87a. This design facilitates discharge of material such as trash, debris, grass clippings and the like, either forwardly, rearwardly or to either side of the vacuum apparatus 51, as desired. Referring again to FIGS. 12 and 14 of the drawings, a conventional towing vehicle hitch 92 is provided on the vacuum apparatus frame 52 to facilitate towing of the vacuum apparatus 51 by a tractor or other towing vehicle 46, as desired.
Referring again to FIGS. 9-15 of the drawings, in another most preferred embodiment of the invention, a pair of caster assemblies 94 are provided in spaced relationship on the vacuum apparatus frame 52, immediately above the caster wheels 96. The caster wheels 96 are each provided with a wheel bracket 97 which is shaped at the upper end to define a caster spindle 94a, that projects upwardly in the caster wheel hub 95 in rotatable relationship. The wheel bracket 97 is fitted with a bracket plate 97a, having a bracket plate slot 97b which matches a corresponding hub plate 95a, mounted on the caster wheel hub 95 and provided with a hub plate slot 95b. Accordingly, it will be appreciated that the caster wheels 96 will each rotate with respect to the corresponding caster wheel hub 95, while the bracket plate 97a and bracket plate slot 97b also rotate with respect to the corresponding hub plate 95a and hub plate slot 95b. A wheel lock 99 is shaped in a "T" configuration and is pivotally mounted on a pair of parallel pin mount plates 100a, secured to the caster wheel hub 95 and the hub plate 95a, as further illustrated in FIGS. 9 and 10. A spring peg 102 projects from each caster wheel hub 95 and receives one end of a wheel lock spring 101, the opposite end of the wheel lock spring 101 being secured to the upper leg of the pivotable wheel lock 99. An engaging leg 103 projects downwardly from the wheel lock 99 and normally seats in the aligned hub plate slot 95b of the hub plate 95a and bracket plate slot 97b of the bracket plate 97a. When the wheel lock 99 is in this locked position, the bracket plate 97a cannot pivot with respect to the hub plate 95a and the caster wheels 96 are locked in the orientation illustrated in FIGS. 9 and 12. However, when the lock release bar 45, attached to the hopper bed 2 of the detachable hopper 1, contacts the upper leg of the wheel lock 99 as illustrated in FIG. 10, the wheel lock 99 pivots on the wheel lock pivot pin 100, thus forcing the engaging leg 103 from the aligned hub plate slot 95b and bracket plate slot 97b, to allow 360 degree rotation of the caster wheels 96 with respect to the caster wheel hubs 95, respectively.
Referring again to FIGS. 5-10 and 15 of the drawings, the detachable hopper 1 is coupled to the vacuum apparatus 51 by means of a dual set of bayonet couplings 105, each secured to a caster assembly 94 of the vacuum assembly 51 and a corresponding pair of hitch receptacles 3, provided in spaced relationship on the hopper bed 2 of the detachable hopper 1. As illustrated in FIG. 5, each bayonet coupling 105 is characterized by a pair of spaced, parallel coupling plates 106, connected by a base plate 107 and fitted with a front plate 107a. An elongated bayonet 108 projects forwardly from the front plate 107a and is fitted with a bayonet slot 109 at a point spaced from the front plate 107a. The projecting end of the bayonet 108 is provided with a double taper 110, as further illustrated in FIG. 5. The bayonet 108 is designed for alignment with and insertion between the parallel coupling plates 4 of the hitch receptacles 3, respectively, when the detachable hopper 1 and the vacuum apparatus 51 are oriented for coupling. Accordingly, the towing vehicle 46 is attached to the vacuum apparatus 51 by means of the towing vehicle hitch 92, as illustrated in FIG. 14 and the vacuum apparatus 51 is either backed toward the detachable hopper 1 or the detachable hopper 1 is pulled toward the vacuum apparatus 51, to engage each of the projecting bayonets 108 with the corresponding, aligned hitch receptacles 3. The bayonet taper 110 in each of the bayonets 108 then contacts the downwardly-extending bayonet guide 9 in the respective hitch receptacles 3 and causes each of the bayonets 108 to slide cleanly into the corresponding hitch receptacle 3. Linear extension of the bayonets 108 continues until the respective bayonet slots 109 in the top edges of the bayonets 108 are aligned with the bottom of the corresponding coupling pin slots 5, at which time the respective coupling pins 6 are slidably displaced from the top of the companion coupling pin slots 5, downwardly to the bottom of the coupling pin slots 5, which now correspond with the bayonet slots 109, respectively. This action locks each of the bayonets 108 in the corresponding hitch receptacles 103 and removably secures the detachable hopper 1 to the vacuum apparatus 51, as illustrated in FIGS. 6, 8 and 14.
It will be appreciated from a consideration of the drawings that the detachable hopper and vacuum apparatus of this invention may be towed by substantially any vehicle, including a tractor, truck or other vehicle, by simply connecting this vehicle represented by reference numeral 46 in FIG. 14, to the towing vehicle hitch 92 of the vacuum apparatus 51. Furthermore, it will be also appreciated that the detachable hopper 1 and vacuum apparatus 51 are both designed for traversing irregular terrain, such as the terrain found on golf courses, and maintaining the forward intake bellows 57 and rear intake bellows 64 of the chute assembly 55 in close proximity to the ground for effective vacuuming of the terrain. Moreover, other implements, such as thatching devices and the like, can be coupled to the vacuum apparatus 51 in conjunction with the detachable hopper 1, for treating the golf course or other turf, as desired.
It will be further appreciated by those skilled in the art that the rear panel (not illustrated) of the detachable hopper 1 may be designed to dump the hopper contents in any desired manner. Accordingly, the rear panel may be pivotally mounted or otherwise attached to the collection bin 16 of the detachable hopper 1, according to the knowledge of those skilled in the art.
While the vacuum apparatus 51 is illustrated and described in terms of operation by the engine 81, it will be recognized that the vacuum apparatus 51 can be driven by alternative power sources such as a power take off system from a vehicle such as a tractor, in non-exclusive particular.
It will be recognized by those skilled in the art that a primary advantage of the detachable hopper and vacuum apparatus of this invention is modularity and flexibility, in that both the detachable hopper and vacuum apparatus may be coupled to vehicles and implements of various design to suit the purpose of the users. This allows use of multiple hoppers to speed up the task when extended distances to an appropriate dump site is encountered and use of the detachable hopper 1 for a variety of purposes. Accordingly, while the preferred embodiments of the invention have been described above, it will be recognized and understood that various modifications may be made in the invention and in the use of the inventive elements and the appended claims are intended to cover all such modifications which may fall within the spirit and scope of the invention.
|
A detachable hopper and vacuum apparatus which includes a mobile, detachable hopper adapted for use with the vacuum apparatus of this invention or towed by a tractor or alternative towing vehicle or apparatus, and characterized by a sliding tongue which is extendible in one embodiment for coupling to the towing apparatus and retractable in a second embodiment for coupling to the vacuum apparatus by means of a dual-contact coupling system. The hinged panel defines the upper half of the front panel of the detachable hopper and features a window for receiving the discharge chute of the towing vehicle or vacuum apparatus. Pivoting tandem wheels are provided on the detachable hopper for easily traversing uneven terrain. The vacuum apparatus includes a frame fitted with a blower housing, an engine connected to a blower within the blower housing for sweeping grass clippings and other debris through a chute assembly provided with bellows on the bottom side thereof and wheels for guiding the bellows over uneven terrain. Caster wheels are also provided on the vacuum apparatus and are designed for 360 degree, selectively locking, pivotal operation when the vacuum apparatus is coupled to the detachable hopper by means of the dual-contact coupling mechanism. A discharge chute projects upwardly from the discharge of the blower housing and is adapted to communicate with the panel window of the front panel of the detachable hopper when the vacuum apparatus is coupled to the detachable hopper.
| 4
|
DETAILED DESCRIPTION
The present invention relates to new 1,4-dihydropyridinecarboxylic acid aralkyl esters, to processes for their preparation, and to their use as coronary, spasmolytic and antihypertensive agents.
It is known that 2,6-dimethyl-4-phenyl-1,4-dihydropyridine-3,5-dicarboxylic acid diesters are obtained when benzylideneacetoacetic acid ethyl ester is reacted with β-aminocrotonic acid ethyl ester or acetoacetic acid ethyl ester and ammonia; see e.g., Knoevenagel, Ber. dtsch. chem. Ges. 31, 743 (1898). It is also known that certain 1,4-dihydropyridines exhibit interesting pharmacological properties; see e.g., F. Bossert and W. Vater, Die Naturwissenschaften 58, 578 (1971).
The present invention pertains to a new class of 1,4-dihydropyridines which exhibit especially potent coronary and antihypertensive effects, in particular a greater antihypertensive effective on the blood vessels than any known dihydropyridine.
In particular, the present invention pertains to compounds of the formula: ##STR1## wherein R is a phenyl or naphthyl group unsubstituted or substituted with from one to three sterically permissible substituents selected from the group consisting of phenyl, lower alkyl, alkenyl, alkinyl, alkoxy, halo, trifluoromethoxy, trifluoromethyl, nitro, azido, cyano, hydroxy, amino, carbo(lower alkoxy), carbamido, sulfonamido, (lower alkoxy)thio, (lower alkyl)sulfinyl or (lower alkyl)sulfonyl, or a quinolyl, isoquinolyl, pyridyl, pyrimidyl, thienyl, furyl or pyrryl group unsubstituted or substituted by lower alkyl, lower alkoxy or halo;
R 1 represents alkyl or the --OR 6 group, wherein R 6 represents a straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical which is optionally interrupted by 1 or 2 oxygen atoms in the chain or in which a hydrogen atom is substituted by an hydroxyl or amino group, and the latter optionally carries two identical or different substituents from the group of alkyl, alkoxyalkyl, aryl and aralkyl, and these substituents optionally form a 5-membered to 7-membered ring with the amine nitrogen,
R 2 and R 4 are identical or different and represent hydrogen or a straight-chain or branched alkyl radical,
R 3 is hydrogen, lower alkyl or (lower alkoxy)lower alkyl;
R 5 is a phenyl, phenoxy or phenylthio group unsubstituted or substituted with from one to three sterically permissible substituents selected from the group consisting of lower alkyl, lower alkoxy, halo, trifluoromethyl, trifluoromethoxy, hydroxy, amino, di(lower alkyl)amino, nitro, cyano, carbamido, sulfonamido, (lower alkyl)thio, (lower alkyl)sulfinyl, a (lower alkyl)sulfonyl and
X is lower alkylene.
In one embodiment, the invention pertains to compounds of Formula I wherein
R is pyridyl, phenyl or phenyl unsubstituted or subtituted with lower alkyl, lower alkoxy, halo, trifluoromethyl, nitro, azido or cyano;
R 1 is lower alkyl, lower alkoxy, cycloalkoxy or (lower alkoxy)lower alkoxy;
each of R 2 and R 4 is methyl;
R 3 is hydrogen or methyl;
R 5 is a phenyl or phenoxy group unsubstituted or substituted with one to three sterically permissible substituents selected from the group consisting of lower alkyl, lower alkoxy, halo, trifluoromethyl and nitro; and
X is lower alkylene.
In a further embodiment, the invention pertains to compounds of Formula I wherein
R is pyridyl, phenyl, nitrophenyl, trifluoromethylphenyl, chlorophenyl or cyanophenyl;
R 1 is methyl, methoxy, ethoxy, isopropoxy, isobutoxy, cyclopentoxy, cyclohexoxy or methoxyethoxy;
each of R 2 and R 4 is methyl;
R 3 is hydrogen or methyl;
R 5 is phenoxy, phenyl, chlorophenyl, dichlorophenyl, methylphenyl, t.-butylphenyl, methoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, trifluoromethylphenyl or nitrophenyl; and
X is methylene, ethylene, ethylidene, trimethylene or 1,2-propylene.
In a further embodiment, the invention pertains to compounds of Formula I wherein
R is phenyl or nitrophenyl;
R 1 is methoxy or isopropoxy;
each of R 2 and R 4 is methyl;
R 3 is hydrogen;
R 5 is phenyl, chlorophenyl or trifluoromethylphenyl; and
X is methylene.
In a further embodiment, the invention pertains to compounds of Formula I wherein
R is 2-nitrophenyl or 3-nitrophenyl;
R 1 is methoxy or isopropoxy;
each of R 2 and R 4 is methyl;
R 3 is hydrogen;
R 5 is phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-trifluoromethylphenyl or 4-trifluoromethylphenyl; and
X is methylene.
The term alkyl denotes a univalent saturated branched or straight hydrocarbon chain containing from 1 to 18 carbon atoms. Representative of such alkyl groups are thus methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, isohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and the like.
The term lower alkyl denotes a univalent saturated branched or straight hydrocarbon chain containing from 1 to 6 carbon atoms. Representative of such lower alkyl groups are thus methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, and the like.
The term cycloalkyl denotes a univalent saturated monocyclic hydrocarbon of from 3 to 7 carbon atoms as, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.
The term lower alkoxy denotes a straight or branched hydrocarbon chain of 1 to 6 carbon atoms bound to the remainder of the molecule through a divalent oxygen atom as, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy and hexoxy.
The term lower alkylthio denotes a branched or straight hydrocarbon chain of 1 to 6 carbon atoms bound to the remainder of the molecule through a divalent sulfur as, for example, methylthio, ethylthio, propylthio, isopropylthio, butylthio, and the like.
The term halo denotes the monovalent substituents fluoro, chloro, bromo and iodo.
The compounds of the present invention can exist as optical isomers and both the racemates of these isomers and the individual isomers themselves are within the scope of the present invention. The racemates can be separated into their individual isomers through the well known technique such as forming and separating diastereomeric compounds.
The compounds of the present invention are prepared by a process which comprises allowing (a) an ylidene of the formula ##STR2## or (b) the elements thereof consisting of a β-dicarbonyl compound of the formula
R.sup.7 COCH.sub.2 COR.sup.9
and an aldehyde of the formula RCHO to react with (c) an enaminocarboxylic acid ester of the formula ##STR3## or (d) the elements thereof consisting of a ketocarboxylic acid ester of the formula
R.sup.10 COCH.sub.2 COR.sup.8
and an amine of the formula R 3 NH 2 wherein either (i) R 7 corresponds to R 1 , R 8 corresponds to -OXR 5 , R 9 corresponds to R 2 and R 10 corresponds to R 4 or (ii) R 7 corresponds to -OXR 5 , R 8 corresponds to R 1 , R 9 corresponds to R 4 and R 10 corresponds to R 2 , and each of R, R 1 , R 2 , R 3 , R 4 , R 5 and X are as herein defined.
It will be observed that this process has a number of variables as to reactants. In one of these process variants, a ylidene is allowed to react with an enaminocarboxylic acid ester. The ylidene-β-dicarbonyl compound can correspond to compounds of the formula ##STR4## in which case the enaminocarboxylic acid ester corresponds to compounds of the formula ##STR5##
In lieu of the enaminocarboxylic acid ester, one can employ the elements thereof, namely an amine of the formula
R.sup.3 NH.sub.2 IV
and a β-ketocarboxylic acid ester of the formula
R.sup.4 COCH.sub.2 COOXR.sup.5 V.
alternatively, the ylidene-β-dicarbonyl compound can correspond to compounds of the formula ##STR6## in which case the enaminocarboxylic acid ester will correspond to compounds of the formula ##STR7##
Here again, the elements of the enaminocarboxylic acid can be used in lieu thereof, namely an amine of Formula IV and a β-dicarbonyl compound of the formula
R.sup.2 COCH.sub.2 COR.sup.1 VIII.
alternately the foregoing ylidene compounds can be replaced by the elements thereof. Thus an enaminocarboxylic acid ester of Formula III can be reacted with an aldehyde of the formula
RCHO IX
with the β-dicarbonyl compound of Formula VIII or an enaminocarboxylic acid of Formula VII can be reacted with the aldehyde of Formula IX and the β-ketocarboxylic acid ester of Formula V.
Utilizing 2,6-dimethyl-3-carbisopropoxy-4-(3-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid benzyl ester (IA) as a representative example, the first two of these process variants can be represented as follows: ##STR8##
Utilizing 2,6-dimethyl-3-carbethoxy-4-(2-chlorophenyl)-1,4-dihydropyridine-5-carboxylic acid 4-chlorobenzyl ester (IB) as a representative example, the third and fourth of these process variants can be represented as follows: ##STR9## Utilizing the same example, the fifth and sixth of these process variants can be represented as follows:
The ylidene-β-dicarbonyl compounds of Formula II are known or can be prepared according to known methods; see e.g., Org. Reactions XV, 204 et seq. (1967). Typical examples include benzylideneacetoacetic acid methyl ester, 2'-nitrobenzylideneacetoacetic acid methyl ester, 2'-nitrobenzylideneacetylacetone, benzylideneacetylacetone, 3'-nitrobenzylideneacetoacetic acid methyl ester, 3'-nitrobenzylideneacetoacetic acid propargyl ester, 3'-nitrobenzylideneacetoacetic acid allyl ester, 3'-nitrobenzylideneacetoacetic acid β-methoxyethyl ester, 3'-nitrobenzylideneacetoacetic acid β-ethoxyethyl ester, 3'-nitrobenzylideneacetoacetic acid isopropyl ester, 3'-nitrobenzylideneacetylacetone, 4'-nitrobenzylideneacetylacetone, 4'-nitrobenzylideneacetoacetic acid β-propoxyethyl ester, 4'-nitrobenzylideneacetoacetic acid n-propyl ester, 3'-nitro-6'-chlorobenzylideneacetoacetic acid methyl ester, 2'-cyano-benzylideneacetoacetic acid methyl ester, 2'-cyanobenzylideneacetoacetic acid ethyl ester, 2'-cyanobenzylidenepriopionylacetic acid ethyl ester, 3'-cyanobenzylideneacetoacetic acid methyl ester, 2'-, 3'- or 4'-methoxybenzylideneacetoacetic acid ethyl ester, 2'-, 3'- or 4'-methoxybenzylideneacetylacetone, 2'-methoxybenzylideneacetoacetic acid allyl ester, 2'-methoxybenzylideneacetoacetic acid β-methoxyethyl ester, 2'-isopropoxybenzylideneacetoacetic acid ethyl ester, 3'-butoxybenzylideneacetoacetic acid methyl ester, 3',4',5'-trimethoxybenzylideneacetoacetic acid allyl ester, 2'-methylbenzylidenepropionylacetic acid methyl ester, 2'-, 3'- or 4'-methylbenzylideneacetoacetic acid ethyl ester, 2'-methylbenzylideneacetoacetic acid β-methoxyethyl ester, 2'-methylbenzylideneacetoacetic acid β-propoxyethyl ester, 2'-methylbenzylideneacetylacetone, 2'-cyclopropyl-benzylideneacetoacetic acid ethyl ester, 2'-ethinyl-benzylideneacetoacetic acid ethyl ester, 2'-cyclopentyl-benzylideneacetoacetic acid ethyl ester, 4'-cyclopentyl-benzylideneacetoacetic acid methyl ester, 5'-cyclohexylbenzylideneacetoacetic acid methyl ester, 4'-phenylbenzylideneacetoacetic acid ethyl ester, 2'-, 3'- or 4'-chloro/bromo/fluorobenzylideneacetoacetic acid ethyl ester, 2'-fluorobenzylideneacetoacetic acid methyl ester, 3'-chlorobenzylideneacetylacetone, 3'-chlorobenzylidenepropionylacetic acid ethyl ester, 3'-chlorobenzylideneacetoacetic acid ethyl ester, 2'-chlorobenzylideneacetoacetic acid allyl ester, 2'-, 3'- or 4' -trifluoromethylbenzylideneacetoacetic acid propyl ester, 2'-trifluoromethylbenzylideneacetoacetic acid isopropyl ester, 3'-trifluoromethylbenzylideneacetoacetic acid methyl ester, 2'-trifluoromethoxybenzylideneacetoacetic acid methyl ester, 4'-trifluoromethoxybenzylideneacetoacetic acid ethyl ester, 2'-carbethoxybenzylideneacetoacetic acid ethyl ester, 3'-carbomethoxybenzylideneacetoacetic acid methyl ester, 4'-carboisopropoxybenzylideneacetoacetic acid ethyl ester, 4'-carboisopropoxybenzylideneacetoacetic acid allyl ester, 4'-aminobenzylideneacetoacetic acid ethyl ester, 4'-n-butylaminobenzylideneacetoacetic acid ethyl ester, 4'-dimethylaminobenzylideneacetoacetic acid methyl ester, 4'-hydroxybenzylideneacetoacetic acid methyl ester, 4'-dimethylaminocarbonylbenzylideneacetoacetic acid ethyl ester, 2'-nitrobenzylideneacetoacetic acid β-(dimethylamino)-ethyl ester, 2'-nitrobenzylideneacetoacetic acid β-(N-methylpiperatinyl-1)-ethyl ester, 2'-nitrobenzylidenacetoacetic acid β-(α-pyridyl)-ethyl ester, 3'-nitro-4'-chlorobenzylideneacetylacetone, 3'-nitro-4'-chlorobenzylideneacetoacetic acid t-butyl ester, 3'-nitro-4'-chlorobenzylideneacetoacetic acid methyl ester, 2'-nitro-4'-methylbenzylideneacetoacetic acid ethyl ester, 2'-azidobenzylideneacetoacetic acid ethyl ester, 3'-azidobenzylideneacetylacetone, 2'-methylmercaptobenzylideneacetoacetic acid methyl ester, 2'-methylmercaptobenzylideneacetoacetic acid isopropyl ester, 2'-sulphinylmethylbenzylideneacetoacetic acid ethyl ester, 2'-sulphonylmethylacetoacetic acid allyl ester, 4-sulphonylmethylacetoacetic acid ethyl ester, (1'-naphthylidene)-acetoacetic acid methyl ester, (1'-naphthylidene)-acetoacetic acid ethyl ester, (2'-naphthylidene)-acetoacetic acid ethyl ester, (2'-quinolyl)-methylideneacetoacetic acid ethyl ester, (3'-quinolyl)-methylideneacetoacetic acid methyl ester, (4'-quinolyl)-methylideneacetoacetic acid ethyl ester, (8'-quinolyl)-methylideneacetoacetic acid ethyl ester, (1'-isoquinolyl)-methylideneacetoacetic acid methyl ester, (3'-isoquinolyl)-methylideneacetoacetic acid methyl ester, α-pyridylmethylideneacetoacetic acid methyl ester, α-pyridylmethylideneacetoacetic acid ethyl ester, α-pyridylmethylideneacetoacetic acid allyl ester, α-pyridylmethylideneacetoacetic acid cyclohexyl ester, β-pyridylmethylideneacetoacetic acid β-methoxyethyl ester, γ-pyridylmethylideneacetoacetic acid methyl ester, 6-methyl-α-pyridylmethylideneacetoacetic acid ethyl ester, 4',6'-dimethoxy-(5'-pyrimidyl)methylideneacetoacetic acid ethyl ester, (2'-thienyl)-methylideneacetoacetic acid ethyl ester, (2'-furyl)-methylideneacetoacetic acid allyl ester, (2'-pyrryl)-methylideneacetoacetic acid methyl ester, 3'-nitrobenzylidenepropionylacetic acid ethyl ester, α-pyridylmethylidenepropionylacetic acid methyl ester and α-pyridylmethylideneacetylacetone.
The enaminocarboxylic acid esters of Formula III are similarly known or can be prepared according to known methods; see e.g. A. C. Cope, J. Amer. Chem. Soc. 67, 1017 (1945). The following are typical examples: β-aminocrotonic acid benzyl ester, βmethylaminocrotonic acid benzyl ester, β-ethylaminocrotonic acid benzyl ester, β-(2-methoxyethylamino)-crotonic acid benzyl ester, β-amino-β-ethylacrylic acid benzyl ester, β-amino-β-isopropylacrylic acid benzyl ester, β-aminocrotonic acid 2-phenylethyl ester, β-aminocrotonic acid 1-phenyl-propyl-2 ester, β-aminocrotonic acid 2-phenyl-propyl-1 ester, β-aminocrotonic acid 2-phenoxy ethyl ester, β-aminocrotonic acid 2-(naphthyloxy-1)-ethyl ester, β-aminocrotonic acid 4-methylbenzyl ester, β-aminocrotonic acid 3-methylbenzyl ester, β-aminocrotonic acid 4-isopropylbenzyl ester, β-aminocrotonic acid 3,4-dimethylbenzyl ester, β-aminocrotonic acid 4-methoxybenzyl ester, β-aminocrotonic acid 3-methoxybenzyl ester, β-aminocrotonic acid 3,4-dimethoxybenzyl ester, β-aminocrotonic acid 3,4,5-trimethoxybenzyl ester, β-aminocrotonic acid 4-n-butoxybenzyl ester, β-aminocrotonic acid 4-chlorobenzyl ester, β-aminocrotonic acid 3-chlorobenzyl ester, β-aminocrotonic acid 2-chlorobenzyl ester, β-aminocrotonic acid 3,4-dichlorobenzyl ester, β-aminocrotonic acid 4-fluorobenzyl ester, β-aminocrotonic acid 4-bromobenzyl ester, β-aminocrotonic acid 4-bromo-3-chlorobenzyl ester, β-aminocrotonic acid 3,4,5-trichlorobenzyl ester, β-aminocrotonic acid 3-chloro-4-methylbenzyl ester, β-aminocrotonic acid 3-chloro-4-methoxybenzyl ester, β-aminocrotonic acid 4-trifluoromethylbenzyl ester, β-aminocrotonic acid 3-trifluoromethylbenzyl ester, β-aminocrotonic acid 3-chloro-4-trifluoromethylbenzyl ester, β-aminocrotonic acid 4-trifluoromethoxybenzyl ester, β-aminocrotonic acid 4-hydroxybenzyl ester, β-aminocrotonic acid 4-aminobenzyl ester, β-aminocrotonic acid 4-n-butylaminobenzyl ester, β-aminocrotonic acid 4-dimethylaminobenzyl ester, β-aminocrotonic acid 4-nitrobenzyl ester, β-aminocrotonic acid 4-cyanobenzyl ester, β-aminocrotonic acid 4-carbamoylbenzyl ester, β-aminocrotonic acid 4-sulphamoylbenzyl ester, β-aminocrotonic acid 3-chloro-4-sulphamoylbenzyl ester, β-aminocrotonic acid 4-methylthiobenzyl ester, β-aminocrotonic acid 4-methylsulphinylbenzyl ester and β-aminocrotonic acid 4-methylsulphonylbenzyl ester.
The amines of Formula IV are known and include ammonia, methylamine, n-propylamine, isopropylamine, n-butylamine, sec.-butylamine, isobutylamine and β-methoxyethylamine.
The β-ketocarboxylic acid esters of Formula V used as starting materials are also known or can be prepared according to known methods; see e.g., Houben-Weyl, Methoden der Organischen Chemie (Methods of Organic Chemistry), VII/4, 230 et seq. (1968). The following are typical examples: formylacetic acid benzyl ester, acetoacetic acid benzyl ester, n-propionylacetic acid benzyl ester, isopropionylacetic acid benzyl ester, acetoacetic acid 2-phenylethyl ester, acetoacetic acid 1-phenyl-propyl-2 ester, acetoacetic acid 2-phenylpropyl-1 ester, acetoacetic acid 2-phenoxyethyl ester, acetoacetic acid 2-(naphthyloxy-1)-ethyl ester, acetoacetic acid 4-methylbenzyl ester, acetoacetic acid 3-methylbenzyl ester, acetoacetic acid 4-isopropylbenzyl ester, acetoacetic acid 3,4-dimethyl ester, acetoacetic acid 4-methoxybenzyl ester, acetoacetic acid 3-methoxybenzyl ester, acetoacetic acid 3,4-dimethoxybenzyl ester, acetoacetic acid 3,4,5-trimethoxybenzyl ester, acetoacetic acid 4-n-butoxybenzyl ester, acetoacetic acid 4-chlorobenzyl ester, acetoacetic acid 3-chlorobenzyl ester, acetoacetic acid 2-chlorobenzyl ester, acetoacetic acid 3,4-dichlorobenzyl ester, acetoacetic acid 4-fluorobenzyl ester, acetoacetic acid 4-bromobenzyl ester, acetoacetic acid 4-bromo-3-chlorobenzyl ester, acetoacetic acid 3,4,5-trichlorobenzyl ester, acetoacetic acid 3-chloro-4-methylbenzyl ester, acetoacetic acid 3-chloro-4-methoxybenzyl ester, acetoacetic acid 4-trifluoromethylbenzyl ester, acetoacetic acid 3-trifluoromethylbenzyl ester, acetoacetic acid 3-chloro-4-trifluoromethylbenzyl ester, acetoacetic acid 4-trifluoromethoxybenzyl ester, acetoacetic acid 4-hydroxybenzyl ester, acetoacetic acid 4-aminobenzyl ester, acetoacetic acid 4-n-butylaminobenzyl ester, acetoacetic acid 4-dimethylaminobenzyl ester, acetoacetic acid 4-nitrobenzyl ester, acetoacetic acid 4-cyanobenzyl ester, acetoacetic acid 4-carbamoylbenzyl ester, acetoacetic acid 4-sulphamoylbenzyl ester, acetoacetic acid 3-chloro-4-sulphamoylbenzyl ester, acetoacetic acid 4-methylthiobenzyl ester, acetoacetic acid 4-methylsulphinylbenzyl ester and acetoacetic acid 4-methylsulphonylbenzyl ester.
The ylidene-β-ketocarboxylic acid esters of Formula VI are also known or can be prepared according to known methods; see e.g., Org. Reactions XV, 204 et seq. (1967). The following are examples: 2'-nitrobenzylideneacetoacetic acid benzyl ester, 3'-nitrobenzylideneacetoacetic acid benzyl ester, 2'-trifluoromethylbenzylideneacetoacetic acid benzyl ester, 2'- or 3'-cyanobenzylideneacetoacetic acid benzyl ester, 2'-, 3'- or 4'-methoxybenzylideneacetoacetic acid benzyl ester, 2'-, 3'- or 4'-methylbenzylideneacetoacetic acid benzyl ester, 2'-cyclopropylbenzylideneacetoacetic acid benzyl ester, 2'-, 3'- or 4'-chloro/bromo/fluorobenzylideneacetoacetic acid benzyl ester, 2'-trifluoromethoxybenzylideneacetoacetic acid benzyl ester, 4'-carbomethoxybenzylideneacetoacetic acid benzyl ester, 4'-dimethylaminobenzylideneacetoacetic acid benzyl ester, 2'-methylmercaptobenzylideneacetoacetic acid benzyl ester, 2'-methylsulphinylbenzylideneacetoacetic acid benzyl ester, 2'-methyl-sulphonylbenzylideneacetoacetic acid benzyl ester, 1'-naphthylideneacetoacetic acid benzyl ester, 2'-nitrobenzylideneacetoacetic acid 2-phenylethyl ester, 2'-nitrobenzylideneacetoacetic acid 2-phenoxyethyl ester, 2'-nitrobenzylideneacetoacetic acid 4 -methylbenzyl ester, 3'-nitrobenzylideneacetoacetic acid 3,4-dimethylbenzyl ester, 3'-nitrobenzylideneacetoacetic acid 4-methoxybenzyl ester, 2'-nitrobenzylideneacetoacetic acid 3,4-dimethoxybenzyl ester, 2'-nitrobenzylideneacetoacetic acid 3,4,5-trimethoxybenzyl ester, 2'-nitrobenzylideneacetoacetic acid 4-chlorobenzyl ester, 3'-nitrobenzylideneacetoacetic acid 3-chlorobenzyl ester, 2'-nitrobenzylideneacetoacetic acid 3,4-dichlorobenzyl ester, 2'-nitrobenzylideneacetoacetic acid 4-fluorobenzyl ester, 2'-nitrobenzylideneacetoacetic acid 3-chloro-4-methylbenzyl ester, 2'-nitrobenzylideneacetoacetic acid 3-chloro-4-methoxybenzyl ester, 2'-nitrobenzylideneacetoacetic acid 4-trifluoromethylbenzyl ester, 2'-nitrobenzylideneacetoacetic acid 4-trifluoromethoxybenzyl ester, 2'-nitrobenzylideneacetoacetic acid 4-dimethylaminobenzyl ester, 2'-nitrobenzylideneacetoacetic acid 4-cyanobenzyl ester, 2'-nitrobenzylideneacetoacetic acid 4-carbamoylbenzyl ester, 2'-nitrobenzylideneacetoacetic acid 4-sulphamoylbenzyl ester, 2'-nitrobenzylideneacetoacetic acid 3-chloro-4-sulphamoylbenzyl ester, 2'-nitrobenzylideneacetoacetic acid 4-methylsulphonylbenzyl ester, (2'-quinolyl)-methylideneacetoacetic acid benzyl ester, (1'-isoquinolyl)-methylideneacetoacetic acid benzyl ester, α-pyridylmethylideneacetoacetic acid benzyl ester, β-pyridylmethylideneacetoacetic acid benzyl ester, γ-pyridylmethylideneacetoacetic acid benzyl ester, (2'-thenyl)-methylideneacetoacetic acid benzyl ester, (2'-furyl)-methylideneacetoacetic acid benzyl ester and 3'-nitrobenzylidenepropionylacetic acid benzyl ester.
The enamino compounds of Formula VII are known or can be prepared according to known methods; see e.g., A. C. Cope, J. Amer. Chem. Soc, 67, 1017 (1945). The following are examples: 2-aminopent-2-en-4-one, 2-methylaminopent-2-en-4-one, 3-aminohept-3-en-5-one, β-aminocrotonic acid methyl ester, β-methylaminocrotonic acid methyl ester, β-(2-methoxyethylamino)-crotonic acid methyl ester, β-aminocrotonic acid ethyl ester, β-aminocrotonic acid n-butyl ester, β-aminocrotonic acid isopropyl ester, β-aminocrotonic acid cyclopentyl ester, β-aminocrotonic acid allyl ester, β-aminocrotonic acid 2-methoxyethyl ester, β-aminocrotonic acid 2-dimethylaminoethyl ester, β-aminocrotonic acid 2-(N-benzyl-N-methylamino)-ethyl ester, β-aminocrotonic acid 2-(piperidinyl-1)ethyl ester, β-aminocrotonic acid 2-(N-methylpiperazinyl-1)ethyl ester and β-aminocrotonic acid 2-(α-pyridyl)-ethyl ester.
The β-dicarbonyl compounds of Formula VIII are known or can be prepared according to known methods; see e.g., Houben-Weyl, Methoden der Organischen Chemie (Methods of Organic Chemistry), VII/4, 230 et seq. (1968). The following are examples: 2,4-pentanedione, 3,5-heptanedione, 2,6-nonanedione, 2,6-dimethyl-3,5-heptanedione, formylacetic acid ethyl ester, acetoacetic acid methyl ester, acetoacetic acid ethyl ester, acetoacetic acid n-butyl ester, acetoacetic acid isopropyl ester, acetoacetic acid cyclopentyl ester, acetoacetic acid alkyl ester, acetoacetic acid propargyl ester, acetoacetic acid 2-methoxyethyl ester, acetoacetic acid 2-dimethylaminoethyl ester, acetoacetic acid 2-(piperidinyl-1)-ethyl ester, acetoacetic acid 2-(α-pyridyl)-ethyl ester, propionylacetic acid ethyl ester, butyrylacetic acid methyl ester and isobutyrylacetic acid ethyl ester.
The aldehydes of Formula IX are known or can be prepared according to known methods; see e.g., E. Mosettig, Org. Reactions, VIII, 218 et seq. (1954). The following are examples: benzaldehyde, 4-phenylbenzaldehyde, 2-, 3- or 4-methylbenzaldehyde, 2- or 4-n-butylbenzyldehyde, 2-, 3- or 4-isopropylbenzaldehyde, 2- or 4-cyclopropylbenzaldehyde, 2-vinylbenzaldehyde, 2-ethinylbenzaldehyde, 2-, 3- or 4-methoxybenzaldehyde, 2-, 3- or 4-chloro/bromo/fluorobenzaldehyde, 2-, 3- or 4-trifluoromethylbenzaldehyde, 2-, 3- or 4-trifluoromethoxybenzaldehyde, 4-hydroxybenzaldehyde, 2-, 3- or 4-nitrobenzaldehyde, 2-, 3- or 4-cyanobenzaldehyde, 3-azidobenzaldehyde, 2-, 3- or 4-dimethylaminobenzaldehyde, 3-carbethoxybenzaldehyde, 3- or 4-carbamoylbenzaldehyde, 2-, 3- or 4-methylmercaptobenzaldehyde, 2-, 3- or 4-methylsulphinylbenzaldehyde, 2-, 3- or 4-methylsulphonylbenzaldehyde, 3,4,5-trimethoxybenzaldehyde, 2,3- or 2,6-dichlorobenzaldehyde, 2,4-dimethylbenzaldehyde, 2,4- or 2,6-dinitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2-nitro-4-methoxybenzaldehyde, 2-nitro-4-cyanobenzaldehyde, 2-chloro-4-cyano-benzaldehyde, 4-cyano-2-methylbenzaldehyde, 3-methyl-4-trifluoromethylbenzaldehyde, 3-chloro-4-trifluoromethylbenzaldehyde, 4-chloro-3-sulphamoylbenzaldehyde, α-, β- or γ-pyridinaldehyde, 6-methylpyridin-2-aldehyde, furan-2-aldehyde, thiophen-2-aldehyde, pyrrol-2-aldehyde, pyrimidin-4-aldehyde, 5-nitro-6 -methylpyridin-2-aldehyde, quinolin-2-aldehyde, isoquinolin-1-aldehyde and 1- or 2-naphthaldehyde.
Diluents which can be used in the process are water and all inert organic solvents including alcohols, especially alkanols such as ethanol, methanol and isopropanol, ethers such as dioxane, diethyl ether, tetrahydrofuran, glycol monomethyl ether and glycol dimethyl ether, glacial acetic acid, dimethylformamide, dimethylsulfoxide, acetonitrile, pyridine and the like. Reaction temperatures can be varied within a substantial range. In general, the reaction is carried out at temperatures of from about 20° C to about 150° C, but advantageously at the boiling point of the particular solvent. The reaction can be carried out under elevated pressure but in general, normal pressure is employed. The amines of Formula IV are generally used in a 1 to 2 molar excess. All other reactants are generally employed in substantially equimolar amounts.
In addition to the compounds for which typical methods of preparation are presented hereafter, the following compounds of the present invention are specifically noted: 2,6-dimethyl-4-(2-methylphenyl)-1,4-dihydropyridine-3-methoxycarbonyl-5-carboxylic acid benzyl ester, 2,6-dimethyl-4-(3-isopropylphenyl)-1,4-dihydropyridine-3-methoxycarbonyl-5-carboxylic acid benzyl ester, 2,6-dimethyl-4-(2-cyclopropylphenyl)-1,4-dihydropyridine-3-methoxycarbonyl-5-carboxylic acid benzyl ester, 2,6-dimethyl-4-(2-ethinylphenyl)-1,4-dihydropyridine-3-methoxycarbonyl-5-carboxylic acid benzyl ester, 2,6-dimethyl-4-(2-methoxyphenyl)-1,4-dihydropyridine-3-ethoxycarbonyl-5-carboxylic acid benzyl ester, 2,6-dimethyl-4-(3-methoxyphenyl)-1,4-dihydropyridine-3-ethoxycarbonyl-5-carboxylic acid benzyl ester, 2,6-dimethyl-4-(3,4,5-trimethoxyphenyl)-1,4-hydropyridine-3-methoxycarbonyl-5-carboxylic acid benzyl ester, 2,6-dimethyl-4-(2-fluoropheyl)-1,4-dihydropyridine-3-methoxycarbonyl-5-carboxylic acid benzyl ester, 2,6-dimethyl-4-(3-trifluoromethylphenyl)-1,4-dihydropyridine-3-methoxycarbonyl-5-carboxylic acid benzyl ester, 2,6-dimethyl-4-(4-trifluoromethylphenyl)-1,4-dihydropyridine-3-methoxycarbonyl-5-carboxylic acid benzyl ester, 2,6-dimethyl-4-(2-trifluoromethoxyphenyl)-1,4-dihydropyridine-3-methoxycarbonyl-5-carboxylic acid benzyl ester, 2,6-dimethyl-4-(2-cyanophenyl)-1,4-dihydropyridine-3-ethoxycarbonyl-5-carboxylic acid benzyl ester, 2,6-dimethyl-4-(3-cyanophenyl)-1,4-dihydropyridine-3-isopropoxycarbonyl-5-carboxylic acid benzyl ester, 2,6-dimethyl-4-(3-azidiophenyl)-1,4-dihydropyridine-3-methoxycarbonyl-5-carboxylic acid benzyl ester, 2,6-dimethyl-4-(4-dimethylaminophenyl)-1,4-dihydropyridine-3-methoxycarbonyl-5-carboxylic acid benzyl ester, 2,6-dimethyl-4-(3-sulphamoylphenyl)-1,4-dihydropyridine-3-methoxycarbonyl-5-carboxylic acid benzyl ester, 2,6-dimethyl-4-(4-chloro-3-sulphamoylphenyl)-1,4-dihydropyridine-3-ethoxycarbonyl-5-carboxylic acid ester, 2,6-dimethyl-4-(2-methylmercaptophenyl)-1,4-dihydropyridine-3-methoxycarbonyl-5-carboxylic acid benzyl ester, 2,6-dimethyl-4-(2-methylsulphinylphenyl)-1,4-dihydropyridine-3-ethoxycarbonyl-5-carboxylic acid benzyl ester, 2,6-dimethyl-4-(2-methylsulphonylphenyl)-1,4-dihydropyridine-3-ethoxycarbonyl-5-carboxylic acid benzyl ester, 2,6-dimethyl-4-(2-methylphenyl)-1,4-dihydropyridine-3-isoproxycarbonyl-5-carboxylic acid 4-methoxybenzyl ester, 2,6-dimethyl-4(2-cyclopropylphenyl)-1,4-dihydropyridine-3-ethoxycarbonyl-5-carboxylic acid 4-methylbenzyl ester, 2,6-dimethyl-4-(2-methoxyphenyl)-1,4-dihydropyridine-3-(β-methoxyethyl)-carbonyl-5-carboxylic a acid 4-chlorobenzyl ester, 2,6-dimethyl 4-(3-trifluoromethylphenyl)-1,4-dihydropyridine-3-methoxycarbonyl-5-carboxylic acid 3,4-dichlorobenzyl ester, 2,6-dimethyl-4-(2-trifluoromethoxyphenyl)-1,4-dihydropyridine-3-methoxycarbonyl-5-carboxylic acid 2-phenylethyl ester, 2,6-dimethyl-4-(2-trifluoromethoxyphenyl)-1,4-dihydropyridine-3-methoxycarbonyl-5-carboxylic acid 2-phenoxyethyl ester, 2,6-dimethyl-4-(2-cyanophenyl)-1,4-dihydropyridine-3-methoxycarbonyl-5-carboxylic acid 2-phenyl-ether ester, 2,6-dimethyl-4-(2-cyanophenyl)-1,4-dihydropyridine-3-methoxycarbonyl-5-carboxylic acid 3,4,5-trimethoxybenzyl ester, 2,6-dimethyl-4-(isoquinolyl)-1,4-dihydropyridine-3-methoxycarbonyl-5-carboxylic acid benzyl ester and 2,6-dimethyl-4-(quinolyl-2)-1,4-dihydropyridine-3-methoxycarbonyl-5-carboxylic acid 2-phenyl-ethyl ester.
Compound according to the invention which are of particular interest are those of Formula I in which
R is phenyl, unsubstituted or substituted by nitro. cyano, trifluoromethyl or halo, or R is pyridyl;
R 1 is alkyl or alkoxy, each with 1 to 4 carbon atoms, or the group --OR 6 wherein R 6 is alkoxyalkyl of up to 4 carbon atoms or cycloalkyl of 5 or 6 carbon atoms;
R 2 and R 4 are the same or different and are ethyl or methyl;
R 3 is hydrogen or lower alkyl;
X is alkylene of 1 to 4 carbon atoms optionally branched; and
R 5 is phenoxy or phenyl optionally substituted by 1, 2 or 3 identical or different substituents selected from the group consisting of alkyl and alkoxy, each with 1 to 4 carbon atoms, halo, trifluoromethyl and nitro.
When either R or R 5 is polysubstituted, it will be appreciated that the patterns of substitution include only those which are sterically permissible.
The new compounds can be used as medicaments and have a broad and diverse spectrum of pharmacological action. In particular the following main actions are conveniently demonstrable in animal models;
1. On parenteral, oral and perlingual administration, the compounds produce a distinct and long-lasting dilation of th coronary vessels. This action on the coronary vessels is intensified by a simultaneous nitrite-like effect of reducing the load on the heart. Heart metabolism is thus influenced or modified in the sense of an energy saving.
2. The excitability of the stimulus formation and excitation conduction system within the heart is lowered, so that an anti-fibrillation action at therapeutic doses results.
3. The tone of the smooth muscle of the vessels is greatly reduced under the action of the compounds. This vascular-spasmolytic action can take place in the entire vascular system or can manifest itself more or less isolated in circumscribed vascular regions, such as, for example, the central nervous system.
4. The compounds lower and blood pressure of normotonic and hypertonic animals and can thus be used as anti-hypertensive or hypotensive agents.
5. The compounds have strong muscular-spasmolytic actions which manifest themselves on the smooth muscle of the stomach, the intestinal tract, the urogenital tract and the respiratory system.
In general, a satisfactory pharmacological response is observed, in the case of intravenous administration, upon administration of from about 0.0001 to about 1 mg/kg, preferably 0.0005 to 0.1 mg/kg, of body weight daily. In the case of oral administration, the dosage is from 0.005 to 10 mg/kg, preferably 0.05 to 5 mg/kg, of body weight daily.
At times, it may of course be necessary to deviate from these ranges mentioned and in particular to do so as a function of body weight, the route of administration, the species, its response towards the medicine and its overall condition, and the time or interval at which it is administered. In some cases, less than the above-mentioned minimum amount produces an adequate response while in other cases the upper limited mentioned must be exceeded. When large amounts are administered, it is often advisable to divide these into several administrations over the course of the day.
The hypotensive activity of these compounds can be seen from the following in which are presented the limiting doses, in mg/kg, at which various compounds have a discernable hypotensive effect on the hypertonic rat.
______________________________________Compound Dose (mg/kg)______________________________________2,6-dimethyl-3-carbomethoxy-4-(2-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid benzyl ester 0.32,6-dimethyl-3-carbomethoxy-4-(2-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 4-chlorobenzyl ester 1.02,6-dimethyl-3-carbomethoxy-4-(2-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 3,4-dichlorobenzylester 1.02,6-dimethyl-3-carbomethoxy-4-(2-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 4-methylbenzyl ester 1.02,6-dimethyl-3-carbisopropoxy-4-(3-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid benzyl ester 3.12,6-dimethyl-3-carbisopropoxy-4-(3-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 4-chlorobenzyl ester 10.02,6-dimethyl-3-carbisopropoxy-4-(3-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 3,4-dichlorobenzylester 3.12,6-dimethyl-3-carbisopropoxy-4-(3-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 2-chlorobenzyl ester 10.02,6-dimethyl-3-carbo(2-methoxyethoxy)-4-(3-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid benzyl ester 10.02,6-dimethyl-3-carbo(2-methoxyethoxy)-4-(3-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 1-phenylethyl ester 1.02,6-dimethyl-3-carbo(2-methoxyethoxy)-4-(3-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 1-(4-chlorophenyl)-ethyl ester 0.3______________________________________
The compounds of the present invention are administered parenterally or orally in any of the usual pharmaceutical forms. These include solid and liquid oral unit dosage forms such as tablets, capsules, powders, suspensions, solutions, syrups and the like, including sustained release preparations, and fluid injectable forms such as sterile solutions and suspensions. The term unit dosage form as used in this specification and the claims refer to physically discrete units to be administered in single or multiple dosage to animals, each unit containing a predetermined quantity of active material in association with the required diluent, carrier or vehicle. The quantity of active material is that calculated to produce the desired therapeutic effect upon administration of one or more of such units.
Powders are prepared by comminuting the compound to a suitable fine size and mixing with a similarly comminuted diluent pharmaceutical carrier such as an edible carbohydrate material as for example, starch. Sweetening, flavoring, preservative, dispersing and coloring agents can also be present.
Capsules are made by preparing a powder mixture as described above and filling formed gelatin sheaths. A lubricant such as talc, magnesium stearate and calcium stearate can be added to the powder mixture as an adjuvant before the filling operation; a glidant such as colloidal silica may be added to improve flow properties; a disintegrating or solubilizing agent may be added to improve the availability of the medicament when the capsule is ingested.
Tablets are made by preparing a powder mixture, granulating or slugging, adding a lubricant and disintegrant and pressing into tablets. A powder mixture is prepared by mixing the compound, suitably comminuted, with a diluent or base such as starch, sucrose, kaolin, dicalcium phosphate and the like. The powder mixture can be granulated by wetting with a binder such as syrup, starch paste, acacia mucilage or solutions of cellulosic or polymeric materials and forcing through a screen. As an alternative to granulating, the powder mixture can be run through the tablet machine and the resulting imperfectly formed slugs broken into granules. The granules can be lubricated to prevent sticking to the tablet forming dies by means of the addition of stearic acid, a stearate salt, talc or mineral oil. The lubricated mixture is then compressed into tablets. The medicaments can also be combined with free flowing inert carriers and compressed into tablets directly without going through the granulating or slugging steps. A protective coating consisting of a sealing coat of shellac, a coating of sugar or polymeric material and a polish coating of wax can be provided. Dyestuffs can be added to these coatings to distinguish different unit dosages.
Oral fluids such as syrups and elixirs can be prepared in unit dosage form so that a given quantity, e.g. a teaspoonful, contains a predetermined amount of the compound. Syrups can be prepared by dissolving the compound in a suitably flavored aqueous sucrose solution while elixirs are prepared through the use of a nontoxic alcoholic vehicle. Suspensions can be formulated by dispersing the compound in a nontoxic vehicle in which it is insoluble.
Fluid unit dosage forms for parenteral administration can be prepared by suspending or dissolving a measured amount of the compound in a nontoxic liquid vehicle suitable for injection such as an aqueous or oleaginous medium and sterilizing the suspension or solution. Alternatively a measured amount of the compound is placed in a vial amd the vial and its contents are sterilized and sealed. An accompanying vial or vehicle can be provided for mixing prior to administration.
The following examples will serve to further typify the present invention, in particular the manner of synthesizing these compounds, but should not be contrued as a restriction on the scope of the invention, the invention being defined solely by the appended claims.
EXAMPLES 1 TO 6
2,6-Dimethyl-3-methoxycarbonyl-4-(2'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid benzyl ester ##STR10##
EXAMPLE 1
18.7 g (75 mmols) of 2'-nitrobenzylideneacetoacetic acid methyl ester and 14.3 g 75 mmols) of β-aminocrotonic acid benzyl ester in 120 ml of ethanol were together heated for 10 hours under reflux. After the reaction mixture had cooled, the solvent was distilled off in vacuo and 50 ml of a 2:1 mixture of ether and petroleum ether were added to the oily residue. The product crystallised throughout after a short time and was filtered off and recrystallised from ethanol.
Melting point: 136° C. Yield: 22.2 g (70%)
EXAMPLE 2
18.7 g (75 mmols) of 2'-nitrobenzylideneacetoacetic acid methyl ester, 14.4 g (75 mmols) of acetoacetic acid benzyl ester and 9 ml (132 mmols) of a 25 percent strength aqueous solution of ammonia, in 120 ml of ethanol, were together heated for 15 hours under reflux.
Thereafter the solvent was distilled off in vacuo, and the residue was triturated with 30 ml of diethyl ether, filtered off and recrystallised from ethanol.
Melting point: 135°-136° C. Yield: 18.3 g (58%).
EXAMPLE 3
16.3 (50 mmols) of 2'-nitrobenzylideneacetoacetic acid benzyl ester and 5.8 g (50 mmols) of β-aminocrotonic acid methyl ester in 90 ml of ethanol were together heated for 10 hours under reflux. After the reaction mixture had cooled, the solvent was distilled off in vacuo. The oily residue crystallised throughout on cooling with ice and was filtered off and recrystallised from ethanol. Melting point: 136° C. Yield: 14.2 g (67%).
EXAMPLE 4
16.3 g (50 mmols) of 2'-nitrobenzylideneacetoacetic acid benzyl ester, 5.8 g (50 mmols) of acetoacetic acid methyl ester and 6 ml (88 mmols) of a 25 per cent strength aqueous ammonia solution, in 90 ml of methanol, were together heated for 15 hours under reflux. Thereafter the solvent was distilled off in vacuo and the oily residue was mixed with a little ether, whereupon the product soon crystallised. The solid substance was filtered off and recrystallised from ethanol.
Melting point: 136° C. Yield 13 g (62%).
EXAMPLE 5
9.6 g (50 mmols) of β-aminocrotonic acid benzyl ester, 7.5 g (50 mmols) of 2-nitrobenzaldehyde and 5.8 g (50 mmols) of acetoacetic acid methyl ester in 90 ml of methanol were together heated for 15 hours under reflux. After the reaction mixture had cooled the solvent was distilled off and the oily residue was mixed with ether and cooled with ice. Hereupon, the product soon crystallised and was filtered off and recrystallised from ethanol.
Melting point: 136° C. Yield: 10.8 g (51%).
EXAMPLE 6
5.8 g (50 mmols) of β-aminocrotonic acid methyl ester, 7.5 g (50 mmols) of 2-nitrobenzaldehyde and 9.6 g (50 mmols) of acetoacetic acid benzyl ester in 90 ml of ethanol were together heated for 15 hours under reflux. Thereafter the solvent was distilled off in vacuo and the residue was triturated with 30 ml of diethyl ether whilst cooling with ice, filtered off and recrystallised from ethanol. Melting point: 135°-136° C. Yield: 9 g (43%).
EXAMPLES 7 TO 12 ##STR11##
EXAMPLE 7
Analogously to Example 1, heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 4-chlorobenzyl ester in 120 ml of ethanol for 10 hours gave 2,6-dimethyl-3-methyoxycarbonyl-4-(2'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 4-chlorobenzyl ester of melting point 129° C (from ethanol).
Yield: 67%
EXAMPLE 8
The compound of Example 7 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 4-chlorobenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield 55% of theory.
EXAMPLE 9
The compound of Example 7 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 4-chlorobenzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of methanol.
Yield: 62% of theory.
EXAMPLE 10
The compound of Example 7 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 4-chlorobenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of methanol.
Yield: 55% of theory.
EXAMPLE 11
The compound of Example 7 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 4-chlorobenzyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of methanol.
Yield: 60% of theory.
EXAMPLE 12.
The compound of Example 7 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid 4-chlorobenzyl ester in 90 ml of ethanol.
Yield: 45% of theory.
EXAMPLES 13 TO 18 ##STR12##
EXAMPLE 13
Analogously to Example 1 heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 2-chlorobenzyl ester in 120 ml of ethanol also gave 2,6-dimethyl-3-methoxycarbonyl-4-(2'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 2-chloro-benzyl ester of melting point 147° C (from ethanol).
Yield: 55% of theory.
EXAMPLE 14
The compound of Example 13 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 2-chlorobenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 48% of theory.
EXAMPLE 15
The compound of Example 13 was also contained analogously to Example 3 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 2-chlorobenzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of methanol.
Yield: 60% of theory.
EXAMPLE 16
The compound of Example 13 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 2-chlorobenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of methanol.
EXAMPLE 17
The compound of Example 13 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-amino crotonic acid 2-chlorobenzyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of methanol.
Yield: 45% of theory.
EXAMPLE 18
The compound of Example 13 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid 2-chlorobenzyl ester in 90 ml of ethanol.
Yield 42% of theory.
EXAMPLES 19 TO 24 ##STR13##
EXAMPLE 19
Analogously to Example 1 heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 3,4-dichlorobenzyl ester in 120 ml of n-propanol gave 2,6-dimethyl-3-methoxycarbonyl-4-(2'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 3,4-dichlorobenzyl ester of melting point 137° C (from ethanol).
Yield: 75% of theory.
EXAMPLE 20
The compound of Example 19 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 3,4-dichlorobenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 65% of theory.
EXAMPLE 21
The compound of Example 19 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 3,4-dichlorobenzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of n-propanol.
Yield: 72% of theory.
EXAMPLE 22
The compound of Example 19 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 3,4-dichlorobenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 60% of theory.
EXAMPLE 23
The compound of Example 19 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 3,4-dichlorobenzyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of n-propanol.
Yield- 48. of theory.
EXAMPLE 24
The compound of Example 19 was also obtained analogously to Example 6 by heating a solution of 50 mols of β-aminocrotonic acid methyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid 3,4-dichlorobenzyl ester in 90 ml of ethanol.
Yield: 52% of theory.
EXAMPLES 25 TO 30 ##STR14##
EXAMPLE 25
Analogously to Example 1, heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 4 methylbenzyl ester in 120 ml of dimethylformamide for 5 hours gave 2,6-dimethyl-3-methoxycarbon 1-4-(2'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 4-methylbenzyl ester of melting point 126° C (from ethanol).
Yield: 72% of theory.
EXAMPLE 26
The compound of Example 25 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 4-methylbenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield- 64% of theory.
EXAMPLE 27
The compound of Example 25 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 4-methylbenzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of dimethylformamide.
Yield: 65% of theory.
EXAMPLE 28
The compound of Example 25 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 4-methylbenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 59% of theory.
EXAMPLE 29
The compound of Example 25 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 4 methylbenzyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of n-propanol.
Yield- 55% of theory.
EXAMPLE 30
The compound of Example 25 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid 4-methylbenzyl ester in 90 ml of n-propanol.
Yield: 62% of theory.
EXAMPLES 31 TO 36 ##STR15##
EXAMPLE 31
Analogously to Example 1, heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 4-methoxybenzyl ester in 120 ml of n-butanol for 7 hours gave 2,6-dimethyl-3methoxycarbonyl-4-(2'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 4-methoxybenzyl ester of melting point 152° C (from ethanol).
Yield: 75. of theory.
EXAMPLE 32
The compound of Example 31 `was also obtained analogously to Example 2 by heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 4-methoxybenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 61% of theory.
EXAMPLE 33
The compound of Example 31 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 4-methoxybenzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of n-butanol. Yield:
67% of theory.
EXAMPLE 34
The compound of Example 31 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 4-methoxybenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of n-propanol.
Yield: 58. of theory.
EXAMPLE 35
The compound of Example 31 as also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 4-methoxybenzyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of n-propanol.
Yield: 62% of theory.
EXAMPLE 36
The compound of Example 31 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrontic acid methyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid 4-methoxybenzyl ester in 90 ml of n-propanol.
Yield: 67% of theory.
EXAMPLES 37 TO 42 ##STR16##
EXAMPLE 37
Analogously to Example 1 heating a solution of 65 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 3,4-dimethoxybenzyl ester in 120 ml of glycol monomethyl ester for 5 hours gave 2,6-dimethyl-3-methoxycarbonyl-4-(2'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 3,4-dimethoxybenzyl ester of melting point 149° C (from methanol).
Yield: 77% of theory.
EXAMPLE 38
The compound of Example 37 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 3,4-dimethoxybenzyl ester and 9 ml of concentrated ammonia in 120 ml of n-propanol.
Yield: 65% of theory.
EXAMPLE 39
The compound of Example 37 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 3,4-dimethoxybenzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of glycol monomethyl ether.
Yield: 71% of theory. Example 40
The compound of Example 37 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 2'-nitrobenxylideneacetoacetic acid 3,4-dimethoxybenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of n-propanol.
Yield: 62% of theory.
EXAMPLE 41
The compound of Example 37 was also obtained analogously to Example 5 by heating a solution of 50 mmole of β-aminocrotonic acid 3,4-dimethoxybenzyl ester, 50 mmols of 2-nitro benzaldehyde and 50 mmols of acetoacetic methyl ester in 90 ml of n-propanol.
Yield: 73% of theory.
Example 42
The compound of Example 37 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrontonic acid methyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid 3,4-dimethoxybenzyl ester in 90 ml of n-propanol.
Yield: 68% of theory.
EXAMPLES 43 to 48 ##STR17##
EXAMPLE 43
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid benzyl ester in 120 ml of pyridine for 10 hours gave 2,6-dimethyl-3-methoxycarbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid benzyl ester of melting point 133° C (from ethanol).
Yield: 75% of theory.
EXAMPLE 44
The compound of Example 43 was obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid benzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 66% of theory.
EXAMPLE 45
The compound of Example 43 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid benzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of pyridine.
Yield 77% of theory.
EXAMPLE 46
The compound of Example 43 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid benzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of n-propanol. Yield: 70% of theory.
EXAMPLE 47
The compound of Example 43 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid benzyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of n-propanol.
Yield: 64% of theory.
EXAMPLE 48
The compound of Example 43 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid benzyl ester on 90 ml of ethanol.
Yield: 69% of theory.
EXAMPLE 49 to 54 ##STR18##
EXAMPLE 49
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 4-chlorobenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-methoxycarbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 4-chlorobenzyl ester of melting point 169° C (from ethanol).
Yield: 72% of theory.
EXAMPLE 50
The compound of Example 49 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 4-chlorobenzyl ester and 9 ml of concentrated ammonia in 120 ml of n-propanol.
Yield: 59% of theory.
EXAMPLE 51
The compound of Example 49 was also obtained analogously to Example 3 by heating a solution of 500 mmols of 3'-nitrobenzylideneacetoacetic acid 4-chlorobenzyl ester and 50 mmols of β-aminocrontonic acid methyl ester in 90 ml of pyridine.
Yield: 65% of theory.
EXAMPLE 52
The compound of Example 49 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 4-chlorobenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of n-propanol.
Yield: 62% of theory.
EXAMPLE 53
The compound of Example 49 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 4-chlorobenzyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of n-butanol.
Yield: 67% of theory.
EXAMPLE 54
The compound of Example 49 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acidmethyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 4-chlorobenzyl ester in 90 ml of ethanol.
Yield: 73% of theory.
EXAMPLES 55 to 60 ##STR19##
EXAMPLE 55
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 3,4-dichlorobenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-methoxycarbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 3,4-dichlorobenzyl ester of melting point 149° C (from ethanol).
Yield: 75% of theory.
EXAMPLE 56
The compound of Example 55 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 3,4-dichlorobenzyl ester and 9 ml of concentrated ammonia in 120 ml of n-butanol.
Yield: 62% of theory.
EXAMPLE 57
The compound of Example 55 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 3,4-dichlorobenzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of n-propanol.
Yield: 67% of theory.
EXAMPLE 58
The compound of Example 55 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 3,4-dichlorobenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of methanol.
Yield: 60% of theory.
EXAMPLE 59
The compound of Example 55 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 3,4-dichlorobenzyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of methanol.
Yield 59% of theory.
EXAMPLE 60
The compound of Example 55 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 3,4-dichlorobenzyl ester in 90 ml of ethanol.
Yield: 62% of theory.
EXAMPLES 61 to 66 ##STR20##
EXAMPLE 61
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 3-chlorobenzyl ester in 120 ml of pyridine gave 2,6 dimethyl-3-methoxycarbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 3-chlorobenzyl ester of melting point 142° C (from ethanol).
Yield: 70% of theory.
EXAMPLE 62
The compound of Example 61 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 3-chlorobenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 63% of theory.
EXAMPLE 63
The compound of Example 61 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 3-chlorobenzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of n-propanol.
Yield: 60% of theory.
EXAMPLE 64
The compound of Example 61 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 3-chlorobenzyl ester, 50 mmols of acetoacetic acid methyl ester of 6 ml of concentrated ammonia in 90 ml of methanol.
Yield: 55% of theory.
EXAMPLE 65
The compound of Example 61 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 3-chlorobenzyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of methanol.
Yield: 56% of theory.
EXAMPLE 66
The compound of Example 61 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 3-chlorobenzyl ester in 90 ml of ethanol.
Yield: 59% of theory.
EXAMPLES 67 to 72 ##STR21##
EXAMPLE 67
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 4-methylbenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-methoxycarbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 4-methylbenzyl ester of melting point 112° C (from ethanol).
Yield: 65% of theory.
EXAMPLE 68
The compound of Example 67 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzlideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 4-methylbenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 58% of theory.
EXAMPLE 69
The compound of Example 67 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 4-methylbenzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of n-propanol.
Yield: 68% of theory.
EXAMPLE 70
The compound of Example 67 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 4-methylbenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of methanol. Yield: 60% of theory.
EXAMPLE 71
The compound of Example 67 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 4-methylbenzyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of ethanol.
Yield: 65% of theory.
EXAMPLE 72
The compound of Example 67 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 4-methylbenzyl ester in 90 ml of ethanol.
Yield: 61% of theory.
EXAMPLES 73 to 78 ##STR22##
EXAMPLE 73
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 4-methoxybenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-methoxycarbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 4-methoxybenzyl ester of melting point 136° C (from ethanol).
Yield: 75% of theory.
EXAMPLE 74
The compound of Example 73 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylidieneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 4-methoxybenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 60% of theory.
EXAMPLE 75
The compound of Example 73 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 4-methoxybenzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of ethanol.
Yield: 62% of theory.
EXAMPLE 76
The compound of Example 73 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 4-methoxybenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of methanol.
Yield: 59% of theory,
EXAMPLE 77
The compound of Example 73 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 4-methoxybenzyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of ethanol.
Yield: 62% of theory.
EXAMPLE 78
The compound of Example 73 was also obtained analogously to Example 6 by heating a solution of 50 mmols of aminocrotonic acid methyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 4-methoxybenzyl ester in 90 ml of ethanol.
Yield: 58% of theory.
EXAMPLE 79 to 84 ##STR23##
EXAMPLE 79
Analogously to Example 1 heating a solution of 75 mmols of 3'-n1trobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 3,4-dimethoxybenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-methoxycarbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 3,4-dimethoxybenzyl ester of melting point 129° C (from ethanol).
Yield: 75% of theory.
EXAMPLE 80
The compound of Example 79 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 3,4-dimethoxybenzyl ester and 9 ml of concentrated ammonia in 120 mo of ethanol.
Yield: 62% of theory.
EXAMPLE 81
The compound of Example 79 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 3,4-dimethoxybenzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of ethanol.
Yield: 68% of theory.
EXAMPLE 82
The compound of Example 79 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 3,4 -dimethoxybenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of methanol.
Yield: 59% of theory.
EXAMPLE 83
The compound of Example 79 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 3,4-dimethoxybenzyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of ethanol.
Yield: 55% of theory.
Example 84
The compound of Example 79 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-amino crotonic acid methyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 3,4-dimethoxybenzyl ester in 90 ml of ethanol. Yield: 57% of theory.
EXAMPLES 85 to 90 ##STR24##
EXAMPLE 85
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 2-phenylethyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-methoxycarbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 2-phenylethyl ester of melting point 122° C (from ethanol).
Yield: 74% of theory.
EXAMPLE 86
The compound of Example 85 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 2-phenylethyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 61: of theory.
EXAMPLE 87
The compound of Example 85 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 2-phenylethyl ester and 50 mmols oc β-aminocrotonic acid methyl ester in 90 ml of ethanol.
Yield: 69% of theory.
EXAMPLE 88
The compound of Example 85 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 2-phenylethyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of methanol.
Yield: 59% of theory.
EXAMPLE 89
The compound of Example 85 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 2-phenylethyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of ethanol.
Yield: 57% of theory.
EXAMPLE 90
The compound of Example 85 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 2-phenylethyl ester in 90 ml of ethanol.
Yield: 55% of theory.
EXAMPLES 91 to 96 ##STR25##
EXAMPLE 91
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid isoporpyl ester and 75 mmols of β-aminocrotonic acid benzyl ester in 120 ml of isopropanol gave 2,6-dimethyl-3-isopropoxycarbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid benzyl ester of melting point 121° C (from ethanol).
Yield: 71% of theory.
EXAMPLE 92
The compound of Example 91 as also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid isopropyl ester, 75 mmols of acetoacetic acid benzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 63% of theory.
EXAMPLE 93
The compound of Example 91 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid benzyl ester and 50 mmols of β-aminocrotonic acid isoporpyl ester in 90 ml of isopropanol.
Yield: 75% of theory.
EXAMPLE 94
The compound of Example 91 was obtained analogously to example 4 by heating a solution of 50 mmol of 3'-nitrobenzylideneacetoacetic acid benzyl ester, 50 mmols of acetoacetic acid isopropyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 61% of theory.
EXAMPLE 95
The compound of Example 91 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid benzyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid isopropyl ester in 90 ml of isoproanol.
Yield: 58% of theory.
EXAMPLE 96
The compound of Example 91 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid isopropyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid benzyl ester in 90 ml of isopropanol.
Yield: 56% of theory.
EXAMPLES 97 to 102 ##STR26##
EXAMPLE 97
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid isopropyl ester and 75 mmols of β-aminocrotonic acid 4-chlorobenzyl ester in 120 ml of isopropanol gave 2,6-dimethyl-3-isopropoxycarbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 4-chlorobenzyl ester of melting point 137° C (from ethanol).
Yield: 78% of theory.
EXAMPLE 98
The compound of Exaple 97 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid isopropyl ester, 75 mmols of acetoacetic acid 4-chlorobenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 60% of theory.
EXAMPLE 99
The compound of Example 97 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 4-chlorobenzyl ester and 50 mmols of β-aminocrotonic acid isopropyl ester in 90 ml of isopropanol.
Yield: 74% of theory.
EXAMPLE 100
The compound of Example 97 was also obtaned analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetonacetic acid 4-chlorobenzyl ester, 50 mmols of acetoacetic acid isopropyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 62% of theory.
EXAMPLE 101
The compound of Example 97 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 4-chlorobenzyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid isopropyl ester in 90 ml of isopropanol.
Yield: 58% of theory.
EXAMPLE 102
The compound of Example 97 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid isopropyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 4-chlorobenzyl ester in 90 ml of isopropanol.
Yield: 60% of theory.
EXAMPLE 103 to 108 ##STR27##
EXAMPLE 103
Analogously to Example 1 eating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid isopropyl ester and 75 mmols of β-aminocrotonic acid 3,4-dichlorobenzyl ester in 120 ml of isopropanol gave 2,6-dimethyl-3-isopropoxycarbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 3, 4-dichlorobenzyl ester of melting point 155° C (from ethanol).
Yield: 75% of theory.
EXAMPLE 104
The compound of Example 103 was also obtained analogously to Example 2by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid isopropyl ester, 75 mmols of acetoacetic acid 3,4-dichlorobenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 62% of theory.
EXAMPLE 105
The compound of Example 103 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzlideneacetoacetic acid 3,4-dichlorobenzyl ester and 50 mmols of β-aminocrotonic acid isopropyl ester in 90 ml of isopropanol.
Yield: 70% of theory.
EXAMPLE 106
The compound of Example 103 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 3,4-dichlorobenzyl ester, 50 mmols of acetoacetic acid isopropyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 59% of theory.
EXAMPLE 107
The compound of Example 103 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 3,4-dichlorobenzyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid isopropyl ester in 90 ml of isopropanol.
Yield: 55% of theory.
EXAMPLE 108
The compound of Example 103 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid isopropyl ester, 50 mmols of 30-nitrobenzaldehyde and 50 mmols of acetoacetic acid 3,4-dichlorobenzyl ester in 90 ml of isopropanol.
Yield: 58% of theory.
EXAMPLES 109 to 114 ##STR28##
EXAMPLE 109
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoaceic acid isopropyl ester and 75 mmols of β-aminocrotonic acid 3-chlorobenzyl ester in 120 ml of isopropanol gave 2,6-dimethyl-3-isopropoxycarbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 3-chlorobenzyl ester of melting point 104° C (from ethanol).
Yield: 69% of theory.
EXAMPLE 110
The compound of Example 109 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzlideneacetoacetic acid isopropyl ester, 75 mmols of acetoacetic acid 3-chlorobenzyl ester and 9 ml of concentrated ammonia in 120 of ethanol.
Yield: 56% of theory.
EXAMPLE 111
The compound of Example 109 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 3-chlorobenzyl ester and 50 mmols of β-aminocrotonic acid isopropyl ester in 90 ml of isopropanol.
Yield: 65% of theory.
EXAMPLE 112
The compound of Example 109 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 3-chlorobenzyl ester, 50 mmols of acetoacetic acid isopropyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 57% of theory.
EXAMPLE 113
The compound of Example 109 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-amino crotonic acid 3-chlorobenzyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid isopropyl ester in 90 ml of isopropanol.
Yield: 60% of theory.
EXAMPLE 114
The compound of Example 109 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid isopropyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 3-chlorobenzyl ester in 90 ml of isopropanol.
Yield: 57% of theory.
EXAMPLES 115 to 120 ##STR29##
EXAMPLE 115
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid isopropyl ester and 75 mmols of β-aminocrotonic acid 2-chlorobenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-isopropoxycarbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 2-chlorobenzyl ester of melting point 103° C (from ethanol).
Yield: 73% of theory.
EXAMPLE 116
The compound of Example 115 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid isopropyl ester, 75 mmols of acetoacetic acid 2-chlorobenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 61% of theory.
EXAMPLE 117
The compound of Example 115 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 2-chlorobenzyl ester and 50 mmols of β-aminocrotonic acid isopropyl ester in 90 ml of ethanol.
Yield: 68% of theory.
EXAMPLE 118
The compound of Example 115 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 2-chlorobenzyl ester, 50 mmols of acetoacetic acid isopropyl ester of 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 55% of theory.
EXAMPLE 119
The compound of Example 115 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 2-chlorobenzyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid isopropyl ester in 90 ml of isopropanol.
Yield: 58% of theory.
EXAMPLE 120 The compound of Example 115 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-amino-crotonic acid isopropyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 2-chlorobenzyl ester in 90 ml of isopropanol.
Yield 54% of theory.
EXAMPLES 121 to 126 ##STR30##
EXAMPLE 121
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid isopropyl ester and 75 mmols of β-aminocrotonic acid 4-methylbenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-isopropoxycarbonyl-4-(3'-nitrophenyl)1,4-dihydropyridine-5-carboxylic acid 4-methylbenzyl ester of melting point 106° C (from ethanol).
Yield: 75% of theory.
EXAMPLE 122
The compound of Example 121 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid isopropyl ester, 75 mmols of acetoacetic acid 4-methylbenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 63% of theory.
EXAMPLE 123
The compound of Example 121 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 4-methylbenzyl ester and 50 mmols of β-aminocrotonic acid isopropyl ester in 90 ml of ethanol.
Yield 71% of theory.
EXAMPLE 124
The compound of Example 121 was also obtained analogously to Example 4 by heating a solution of 50 mmols 3'-nitrobenzylideneacetoacetic acid 4-methylbenzyl ester, 50 mmols of acetoacetic acid isopropyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 59% of theory.
EXAMPLE 125
The compound of Example 121 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 4-methylbenzyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid isopropyl ester in 90 ml of isopropanol.
Yield: 61% of theory.
EXAMPLE 126
The compound of Example 121 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-amino crotonic acid isopropyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 4-methylbenzyl ester in 90 ml of isopropanol.
Yield: 56% of theory.
EXAMPLES 127 to 132 ##STR31##
EXAMPLE 127
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid isopropyl ester and 75 mmols of β-aminocrotonic acid 3,4-dimethoxybenzyl ester in 120 ml of isopropanol gave 2,6-dimethyl-3-isopropoxycarbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 3,4-dimethoxybenzyl ester of melting point 154° C (from ethanol).
Yield: 77% of theory.
EXAMPLE 128
The compound of Example 127 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid isopropyl ester, 75 mmols of acetoacetic acid 3,4-dimethoxybenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 61% of theory.
EXAMPLE 129
The compound of Example 127 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 3,4-dimethoxybenzyl ester and 50 mmols of β-aminocrotonic acid isopropyl ester in 90 ml of ethanol.
Yield: 75% of theory.
EXAMPLE 130
The compound of Example 127 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 3,4-dimethoxybenzyl ester, 50 mmols of acetoacetic acid isopropyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 62% of theory.
EXAMPLE 131
The compound of Example 127 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrontonic acid 3,4-dimethoxybenzyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid isopropyl ester in 90 ml of isopropanol.
Yield: 59% of theory.
EXAMPLE 132
The compound of Example 127 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid isopropyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 3,4-dimethoxybenzyl ester in 90 ml of ethanol. Yield: 55% of theory.
EXAMPLES 133 to 138 ##STR32##
EXAMPLE 133
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid 2-methoxyethyl ester and 75 mmols of β-aminocrotonic acid benzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-(2-methoxyethyloxy)-carbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid benzyl ester of melting point 152° C (from ethanol).
Yield: 79% of theory.
EXAMPLE 134
The compound of Example 133 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid 2-methoxyethyl ester, 75 mmols of acetoacetic acid benzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 68% of theory.
EXAMPLE 135
The compound of Example 133 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid benzyl ester and 50 mmols of β-aminocrotonic acid 2-methoxyethyl ester in 90 ml of ethanol.
Yield: 72% of theory.
EXAMPLE 136
The compound of Exalime 133 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid benzyl ester, 50 mmols of acetoacetic acid 2-methoxyethyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 64% of theory.
EXAMPLE 137
The compound of Example 133 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid benzyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 2-methoxyethyl ester in 90 ml of ethanol.
Yield: 64% of theory.
EXAMPLE 138
The compound of Example 133 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid 2-methoxyethyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid benzyl ester in 90 ml of ethanol.
Yield: 57% of theory.
EXAMPLE 139 to 144 ##STR33##
EXAMPLE 139
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid 2-methoxyethyl ester and 75 mmols of β-aminocrotonic acid 1-phenylethyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-(2-methoxyethyloxy)-carbonyl-4-(3'-nitroethyl) 5 carboxylic acid 1-phenyl ethyl ester of melting point 122° C (from ethanol).
Yield: 68% of theory.
EXAMPLE 140
The compound of Example 139 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid 2-methoxyethyl ester, 75 mmols of acetoacetic acid 1-phenylethyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 59% of theory.
EXAMPLE 141
The compound of Example 139 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 1-phenylethyl ester and 50 mmols of β-aminocrotonic acid 2-methoxyethyl ester in 90 ml of ethanol.
Yield: 61% of theory.
EXAMPLE 142
The compound of Example 139 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 1-phenylethyl ester, 50 mmols of acetoacetic acid 2-methoxyethyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 54% of theory.
EXAMPLE 143
The compound of Example 139 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 1-phenylethyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 2-methoxyethyl ester in 90 ml of ethanol.
Yield: 57% of theory.
EXAMPLE 144
The compound of Example 139 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid 2-methoxyethyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 1-phenylethyl ester in 90 ml of ethanol.
Yield: 52% of theory.
EXAMPLES 145 to 150 ##STR34##
EXAMPLE 145
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid 2-methoxyethyl ester and 75 mmols of β-aminocrotonic acid 1-(4-chlorophenyl)-ethyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-(2-methoxyethyloxy)-carbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 1-(4-chlorophenyl)-ethyl ester of melting point 106° C (from ethanol).
Yield: 72% of theory.
EXAMPLE 146
The compound of Example 145 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid 2-methoxyethyl ester, 75 mmols of acetoacetic acid (1-(4-chlorophenyl)-ethyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 60% of theory.
EXAMPLE 147
The compound of Example 145 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 1-(4-chlorophenyl)-ethyl ester and 50 mmols of β-aminocrotonic acid 2-methoxyethyl ester in 90 ml of ethanol.
Yield: 66% of theory.
EXAMPLE 148
The compound of Example 145 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 1-(4-chlorophenyl)-ethyl ester, 50 mmols of acetoacetic acid 2-methoxyethyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 58% of theory.
EXAMPLE 149
The compound of Example 145 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonicacid 1-(4-chlorophenyl)-ethyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 2-methoxyethyl ester in 90 ml of ethanol.
Yield: 59% of theory.
EXAMPLE 150
The compound of Example 145 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid 2-methoxyethyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 1-(4-chlorophenyl)-ethyl ester in 90 ml of ethanol.
Yield: 54% of theory.
EXAMPLES 151 to 156 ##STR35##
EXAMPLE 151
Analogously to Example 1 heating a solution of 75 mmols of 2'-trifluoromethylbenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid benzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-methoxycarbonyl-4-'2'-trifluoromethylphenyl)-1,4-dihydropyridine-5-carboxylic acid benzyl ester of melting point 136° C (from ethanol).
Yield: 75% of theory.
EXAMPLE 152
The compound of Example 151 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 2'-trifluoromethylbenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid benzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 66% of theory.
EXAMPLE 153
The compound of Example 151 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 2'-trifluoromethylbenzylideneacetoacetic acid benzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of ethanol.
Yield: 71% of theory.
EXAMPLE 154
The compound of Example 151 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 2'-trifluoromethylbenzylideneacetoacetic acid benzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol. Yield: 60% of theory.
EXAMPLE 155
The compound of Example 151 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid benzyl ester, 50 mmols of 2-trifluoromethylbenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of ethanol.
Yield: 52% of theory.
EXAMPLE 156
The compound of Example 151 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of 2-trifluoromethylbenzaldehyde and 50 mmols of acetoacetic acid benzyl ester in 90 ml of ethanol.
Yield: 54% of theory.
EXAMPLES 157 to 162 ##STR36##
EXAMPLE 157
Analogously to Example 1 heating a solution of 75 mmols of 2'-chlorobenzylideneacetoacetic acid ethyl ester and 75 mmols of β-aminocrotonic acid 2-chlorobenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-ethoxycarbonyl-4-(2'-chlorophenyl)-1,4-dihydropyridine-5-carboxylic acid 2-chlorobenzyl ester of melting point 120° C (from ethanol).
Yield: 63% of theory.
EXAMPLE 158
The compound of Example 157 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 2'-chlorobenzylideneacetoacetic acid ethyl ester, 75 mmols of acetoacetic acid 2-chlorobenzyl ester and 9 ml of concentrated ammonia in 120 ml of methanol.
Yield: 54% of theory.
EXAMPLE 159
The compound of Example 157 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 2'-chlorobenzylideneacetoacetic acid 2-chlorobenzyl ester and 50 mmols of β-aminocrotonic acid ethyl ester in 90 ml of ethanol.
Yield: 59% of theory.
EXAMPLE 160
The compound of Example 157 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 2'-chlorobenzylideneacetoacetic acid 2-chlorobenzyl ester, 50 mmols of acetoacetic acid ethyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 52% of theory.
EXAMPLE 161
The compound of Example 157 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 2-chlorobenzyl ester, 50 mmols of 2-chlorobenzaldehyde and 50 mmols of acetoacetic acid ethyl ester in 90 ml of ethanol.
Yield: 53% of theory.
EXAMPLE 162
The compound of Example 157 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid ethyl ester, 50 mmols of 2-chlorobenzaldehyde and 50 mmols of acetoacetic acid 2-chlorobenzyl ester in 90 ml of ethanol.
Yield: 50% of theory.
EXAMPLES 163 to 168 ##STR37##
EXAMPLE 163
Analogously to Example 1 heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 4-fluorobenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-methoxycarbonyl-4-(2'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 4-fluorobenyzl ester of melting point 117° C (from ethanol).
Yield: 75% of theory.
EXAMPLE 164
The compound of Example 163 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 4-fluorobenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 63% of theory.
EXAMPLE 165
The compound of Example 163 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 4-fluorobenzyl ester, and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of methanol.
Yield: 71% of theory.
EXAMPLE 166
The compound of Example 163 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 4-fluorobenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6ml of concentrated ammonia in 90 ml of ethanol.
Yield: 62% of theory.
EXAMPLE 167
The compound of Example 163 was also obtained anaogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 4-fluorobenzyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of ethanol.
Yield: 56% of theory.
EXAMPLE 168
The compound of Example 163 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid 4-fluorobenzyl ester in 90 ml of ethanol.
Yield: 52% of theory.
EXAMPLES 169 to 174 ##STR38##
EXAMPLE 169
Analogously to Example 1 heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid isobutyl ester and 75 mmols of β-aminocrotonic acid benzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-isobutoxycarbonyl-4-(2'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid benzyl ester of melting point 154° C (from ethanol).
Yield: 71% of theory.
EXAMPLE 170
The compound of Example 169 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid isobutyl ester, 75 mmols of acetoacetic acid benzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 59% of theory.
EXAMPLE 171
The compound of Example 169 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid benzyl ester and 50 mmols of β-aminocrotonic acid isobutyl ester in 90 ml of ethanol.
Yield: 73% of theory.
EXAMPLE 172
The compound of Example 169 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid benzyl ester, 50 mmols of acetoacetic acid isobutyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 62% of theory.
EXAMPLE 173
The compound of Example 169 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid benzyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid isobutyl ester in 90 ml of ethanol.
Yield: 59% of theory.
EXAMPLE 174
The compound of Example 169 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid isobutyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid benzyl ester in 90 ml of ethanol.
Yield: 56% of theory.
EXAMPLES 175 to 180 ##STR39##
EXAMPLE 175
Analogously to Example 1 heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid cyclopentyl ester and 75 mmols of β-aminocrotonic acid benzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-cyclopentyloxycarbonyl-4-(2'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid benzyl ester of melting point 111° C (from ethanol).
Yield: 73% of theory.
EXAMPLE 176
The compound of Example 175 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid cyclopentyl ester, 75 mmols of acetoacetic acid benzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 61% of theory.
EXAMPLE 177
The compound of Example 175 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid benzyl ester and 50 mmols of β-aminocrotonic acid cyclopentyl ester in 90 ml of ethanol.
Yield: 68% of theory.
EXAMPLE 178
The compound of Example 175 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid benzyl ester, 50 mmols of acetoacetic acid cyclopentyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 57% of theory.
EXAMPLE 179
The compound of Example 175 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid benzyl ester, 50 mmols of 2-nitrobenzaldehye and 50 mmols of acetoacetic acid cyclopentyl ester in 90 ml of ethanol.
Yield: 55% of theory.
EXAMPLE 180
The compound of Example 175 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid cyclopentyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid benzyl ester in 90 ml of ethanol.
Yield: 52% of theory.
EXAMPLE 181 to 186 ##STR40##
EXAMPLE 181
Analogously to Example 1 heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid cyclohexyl ester and 75 mmols of β-aminocrotonic acid benzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-cyclohexyloxycarbonyl-4-(2'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid benzyl ester of melting point 134° C (from ethanol).
Yield: 68% of theory.
EXAMPLE 182
The compound of Example 181 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid cyclohexyl ester, 75 mmols of acetoacetic acid benzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield:59% of theory.
EXAMPLE 183
The compound of Example 181 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid benzyl ester and 50 mmols of β-aminocrotonic acid cyclohexyl ester in 90 ml of ethanol.
Yield: 63% of theory.
EXAMPLE 184
The compound of Example 181 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid benzyl ester, 50 mmols of acetoacetic acid cyclohexyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 58% of theory.
EXAMPLE 185
The compound of Example 181 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid benzyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid cyclohexyl ester in 90 ml of ethanol.
Yield: 57% of theory.
EXAMPLE 186
The compound of Example 181 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid cyclohexyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid benzyl ester in 90 ml of ethanol.
Yield: 52% of theory.
EXAMPLES 187 to 192 ##STR41##
EXAMPLE 187
Analogously to Example 1 heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 3-chloro-4-methylbenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-methoxycarbonyl-4-(2'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 3-chloro-4-methylbenzyl ester of melting point 132° C (from ethanol).
Yield: 72% of theory.
EXAMPLE 188
The compound of Example 187 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 3-chloro- 4-methylbenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 61% of theory.
EXAMPLE 189
The compound of Example 187 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 3-chloro-4-methylbenzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of ethanol.
Yield: 62% of theory.
EXAMPLE 190
The compound of Example 187 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 3-chloro-4-methylbenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 53% of theory.
EXAMPLE 191
The compound of Example 187 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 3-chloro-4-methylbenzyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of ethanol.
Yield: 51% of theory.
EXAMPLE 192
The compound of Example 187 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of 2-nitro-benzaldehyde and 50 mmols of acetoacetic acid 3-chloro- 4-methylbenzyl ester in 90 ml of ethanol.
Yield: 54% of theory.
EXAMPLES 193 to 198 ##STR42##
EXAMPLE 193
Analogously to Example 1 heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 4-tert.-butylbenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-methoxycarbonyl-4-(2'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 4-tert.-butylbenzyl ester of melting point 146° C (from ethanol).
Yield: 75% of theory.
EXAMPLE 194
The compound of Example 193 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetic acid 4-tert.-butyl benzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 60% of theory.
EXAMPLE 195
The compound of Example 193 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 4-tert.-butylbenzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of ethanol.
Yield: 64% of theory.
EXAMPLE 196
The compound of Example 194 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 4 -tert.-butylbenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 55% of theory.
EXAMPLE 197
The compound of Example 193 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 4-tert.-butylbenzyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of ethanol.
Yield: 51% of theory.
EXAMPLE 198
The compound of Example 193 was also obtained analogously to Example 6 by heating a soluton of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mols of acetoacetic acid 4-tert.-butylbenzyl ester in 90 ml of ethanol.
Yield: 54% of theory.
EXAMPLES 199 TO 204 ##STR43##
EXAMPLE 199
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 4-tert.-butylbenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-methoxycarbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 4-tert.-butylbenzyl ester of melting point 161° C (from ethanol).
Yield: 78% of theory.
EXAMPLE 200
The compound of Example 199 was also obtained analogously to Example 12 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 4-tert.-butylbenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 65% of theory.
EXAMPLE 201
The compound of Example 199 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 4-tert.-butylbenzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of ethanol.
Yield: 67% of theory.
EXAMPLE 202
The compound of Example 199 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 4-tert.-butylbenzyl ester, 50 mmols of acetoacetic acid methyl ester and 7 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 59% of theory.
EXAMPLE 203
The compound of Example 199 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 4-tert.-butylbenzyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of ethanol.
Yield: 55% of theory.
EXAMPLE 204
The compound of Example 199 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 4-tert.-butylbenzyl ester in 90 ml of ethanol.
Yield: 51% of theory.
EXAMPLES 205 TO 210 ##STR44##
EXAMPLE 205
Analogously to Example 1 heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-methylaminocrotonic acid benzyl ester in 120 ml of ethanol gave 1,2,6-trimethyl-3-methoxycarbonyl-4-(2'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid benzyl ester of melting point 182° C (from ethanol/dimethylformamide).
Yield: 67% of theory.
EXAMPLE 206
The compound of Example 205 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid benzyl ester and 9 ml of a 30% strength aqueous methylamine solution in 120 ml of ethanol.
Yield: 52% of theory.
EXAMPLE 207
The compound of Example 205 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid benzyl ester and 50 mmols of β-methylaminocrotonic acid methyl ester in 90 ml of ethanol.
Yield: 61% of theory.
EXAMPLE 208
The compound of Example 205 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid benzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of a 30% strength methylamine solution in 90 ml of ethanol.
Yield: 50% of theory.
EXAMPLE 209
The compound of Example 205 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-methylaminocrotonic acid benzyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of ethanol.
Yield: 52% of theory.
EXAMPLE 210
The compound of Example 205 was also obtained analogously to Example 6 by heating a solution of 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid benzyl ester in 90 ml of ethanol.
Yield: 49% of theory.
EXAMPLE 211 TO 216 ##STR45##
EXAMPLE 211
Analogously to Example 1 heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 4-trifluoromethylbenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-methoxycarbonyl-4-(2'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 4-trifluoromethylbenzyl ester of melting point 130° C (from ethanol).
Yield: 72% of theory.
EXAMPLE 212
The compound of Example 211 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 4-trifluoromethylbenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 61% of theory.
EXAMPLE 213
The compound of Example 211 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 4-trifluoromethylbenzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of ethanol.
Yield: 63% of theory.
EXAMPLE 214
The compound of Example 211 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 4-trifluoromethylbenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 52% of theory.
EXAMPLE 215
The compound of Example 211 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 4-trifluoromethylbenzyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of ethanol.
Yield: 54% of theory.
EXAMPLE 216
The compound of Example 211 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid 4-trifluoromethylbenzyl ester in 90 ml of ethanol.
Yield: 50% of theory.
EXAMPLE 217 TO 222 ##STR46##
EXAMPLE 217
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 4-trifluoromethylbenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-methoxycarbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 4-trifluoromethylbenzyl ester of melting point 163° C (from ethanol).
Yield: 75% of theory.
EXAMPLE 218
The compound of Example 217 was also obtained nalogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 4-trifluoromethylbenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 63% of theory.
EXAMPLE 219
The compound of Example 217 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 4-trifluoromethylbenzyl ester and 50 mmol of β-aminocrotonic acid methyl ester in 90 ml of ethanol. Yield: 64% of theory.
EXAMPLE 220
The compound of Example 217 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 4-trifluoromethylbenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 55% of theory.
EXAMPLE 221
The compound of Example 217 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 4-trifluoromethylbenzyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of ethanol.
Yield: 51% of theory.
EXAMPLE 222
The compound of Example 217 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 4-trifluoromethylbenzyl ester in 90 ml of ethanol.
Yield: 48% of theory.
EXAMPLES 223 TO 228 ##STR47##
EXAMPLE 223
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid isopropyl ester and 75 mmols of β-aminocrotonic acid 4-trifluoromethylbenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-isopropoxycarbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 4-trifluoromethylbenzyl ester of melting point 139° C (from ethanol).
Yield: 76% of theory.
EXAMPLE 224
The compound of Example 223 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid isopropyl ester, 75 mmols of acetoacetic acid 4-trifluoromethylbenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 62% of theory.
EXAMPLE 225
The compound of Example 223 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 4-trifluoromethylbenzyl ester and 50 mmols of β-aminocrotonic acid isopropyl ester in 90 ml of ethanol.
Yield: 68% of theory.
EXAMPLE 226
The compound of Example 223 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 4-trifluoromethylbenzyl ester, 50 mmols of acetoacetic acid isopropyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 53% of theory.
EXAMPLE 227
The compound of Example 223 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 4-trifluoromethylbenzyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid isopropyl ester in 90 ml of ethanol.
Yield: 51% of theory.
EXAMPLE 228
The compound of Example 223 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid isopropyl ester, 50 mmols of 3-nitrobenzaldehyde and 5 mmols of acetoacetic acid 4-trifluoromethylbenzyl ester in 90 ml of ethanol.
Yield: 47% of theory.
EXAMPLES 229 TO 234 ##STR48##
EXAMPLE 229
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 4-fluorobenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-methoxycarbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 4-fluorobenzyl ester of melting point 168° C (from ethanol).
Yield: 74% of theory.
EXAMPLE 230
The compound of Example 229 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 4-fluorobenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 65% of theory.
EXAMPLE 231
The compound of Example 229 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 4-fluorobenzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of ethanol.
Yield: 70% of theory.
EXAMPLE 232
The compound of Example 229 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 4-fluorobenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 59% of theory.
EXAMPLE 233
The compound of Example 229 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 4-fluorobenzyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of ethanol.
Yield: 54% of theory.
Example 234
The compound of Example 229 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 4-fluorobenzyl ester in 90 ml of ethanol.
Yield: 50% of theory.
EXAMPLE 235 TO 240 ##STR49##
EXAMPLE 235
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 2-phenoxyethyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-methoxycarbonyl-4-(3'-nitrophenyl)-5-carboxylic acid 2-phenoxyalkyl ester of melting point 13° C (from ethanol).
Yield: 70% of theory.
EXAMPLE 236
The compound of Example 235 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 2-phenoxyethyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 58% of theory.
EXAMPLE 237
The compound of Example 235 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 2-phenoxyethyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of ethanol. Yield: 61% of theory.
EXAMPLE 238
The compound of Example 235 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 2-phenoxyethyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol. Yield: 54% of theory.
EXAMPLE 239
The compound of Example 235 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 2-phenoxyethyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of ethanol.
Yield: 50% of theory.
EXAMPLE 240
The compound of Example 235 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 2-phenoxyethyl ester in 90 ml of ethanol.
Yield: 45% of theory.
EXAMPLES 241 to 246 ##STR50##
EXAMPLE 241
Analogously to Example 1 heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester and 75 ml of β-aminocrotonic acid 3,4,5-trimethoxybenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-methoxycarbonyl-4-(2'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 3,4,5-trimethoxybenzyl ester of melting point 125° C (from ethanol).
Yield: 78% of theory.
EXAMPLE 242
The compound of Example 241 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 3,4,5-trimethoxybenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 65% of theory.
EXAMPLE 243
The compound of Example 241 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 3,4,5-trimethoxybenzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of ethanol.
Yield: 69% of theory.
EXAMPLE 244
The compound of Example 241 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 3,4,5-trimethoxybenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 55% of theory.
EXAMPLE 245
The compound of Example 241 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 3,4,5-trimethoxybenzyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of ethanol.
Yield: 52% of theory.
EXAMPLE 246
The compound of Example 241 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid 3,4,5-trimethoxybenzyl ester in 90 ml of ethanol.
Yield: 49% of theory.
EXAMPLES 247 TO 252 ##STR51##
EXAMPLE 247
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid 2-methoxyethyl ester and 75 mmols of β-aminocrotonic acid 3,4,5-trimethoxybenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-(2-methoxyethoxy)-carbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 3,4,5-trimethoxybenzyl ester of melting point 160° C (from ethanol).
Yield: 71% of theory.
EXAMPLE 248
The compound of Example 247 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid 2-methoxyethyl ester, 75 mmols of acetoacetic acid 3,4,5-trimethoxybenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 60% of theory.
EXAMPLE 249
The compound of Example 247 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 3,4,5-trimethoxybenzyl ester and 50 mmols of β-aminocrotonic acid 2-methoxyethyl ester in 90 ml of ethanol.
Yield: 66% of theory.
EXAMPLE 250
The compound of Example 247 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 3,4,5-trimethoxybenzyl ester, 50 mmols of acetoacetic acid 2-methoxyethyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 57% of theory.
EXAMPLE 251
The compound of Example 247 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 3,4,5-trimethoxybenzyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 2-methoxyethyl ester in 90 ml of ethanol.
Yield: 53% of theory.
EXAMPLE 252
The compound of Example 247 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid 2-methoxyethyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 3,4,5-trimethoxybenzyl ester in 90 ml of ethanol.
Yield: 49% of theory.
EXAMPLES 253 TO 258 ##STR52##
EXAMPLE 253
Analogously to Example 1 heating a solution of 75 mmols of 2'-cyanobenzylideneacetoacetic acid ethyl ester and 75 mmols of β-aminocrotonic acid benzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-ethoxycarbonyl-4-(2'-cyanophenyl)-1,4-dihydropyridine-5-carboxylic acid benzyl ester of melting point 136° C (from ethanol).
Yield: 65% of theory.
EXAMPLE 254
The compound of Example 253 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 2'-cyanobenzlideneacetoacetic acid ethyl ester, 75 mmols of acetoacetic acid benzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 54% of theory.
EXAMPLE 255
The compound of Example 253 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 2'-cyanobenzylideneacetoacetic acid benzyl ester and 50 mmols of β-aminocrotonic acid ethyl ester in 90 ml of ethanol.
Yield: 59% of theory.
EXAMPLE 256
The compound of Example 253 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 2'-cyanobenzylideneacetoacetic acid benzyl ester, 50 mmols of acetoacetic acid ethyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 49% of theory.
EXAMPLE 257
The compound of Example 253 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid benzyl ester, 50 mmols of 2-cyanobenzaldehyde and 50 mmols of acetoacetic acid ethyl ester in 90 ml of ethanol.
Yield: 45% of theory.
EXAMPLE 258
The compound of Example 253 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid ethyl ester, 50 mmols of 2-cyanobenzaldehyde and 50 mmols of acetoacetic acid benzyl ester and 90 ml of ethanol.
Yield: 42% of theory.
EXAMPLES 259 TO 264 ##STR53##
EXAMPLE 259
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetylacetone and 75 mmols of β-aminocrotonic acid benzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-acetyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid benzyl ester of melting point 152° C (from ethanol).
Yield: 67% of theory.
EXAMPLE 260
The compound of Example 259 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetylacetone, 75 mmols of acetoacetic acid benzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 55% of theory.
EXAMPLE 261
The compound of Example 259 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid benzyl ester and 50 mmols of 2-aminopent-2-en-4-one in 90 ml of ethanol.
Yield: 51% of theory.
EXAMPLE 262
The compound of Example 259 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid benzyl ester, 50 mmols of acetylacetone and 66 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 46% of theory.
EXAMPLE 264
The compound of Example 259 was also obtained analogously to Example 6 by heating a solution of 50 mmols of 2-aminopent-2-en-4-one, 50 mmols of 3-nirobenzaldehyde and 50 mmols of acetoacetic acid benzyl ester in 90 ml of ethanol.
Yield: 40% of theory.
EXAMPLES 265 to 270 ##STR54##
EXAMPLE 265
Analogously to Example 1 heating a solution of 75 mmols of pyridyl-3-methylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 4-methylbenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-methoxycarbonyl-4-(pyridyl-3)-1,4-dihydropyridine-5-carboxylic acid 4-methylbenzyl ester of melting point 175° C (from ethanol).
Yield: 65% of theory.
EXAMPLE 266
The compound of Example 265 was also obtained analogously to Example 2 by heating a solution of 75 mmols of pyridyl-3-methylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 4-methylbenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 58% of theory.
EXAMPLE 267
The compound of Example 265 was also obtained analogously to Example 3 by heating of solution of 50 mmols of pyridyl-3-methylideneacetoacetic acid 4-methylbenzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of ethanol.
Yield: 60% of theory.
EXAMPLE 268
The compound of Example 265 was also obtained analogously to Example 4 by heating a solution of 50 mmols of pyridyl-3-methylideneacetoacetic acid 4-methylbenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 52% of theory.
EXAMPLE 269
The compound of Example 265 was also obtained anaologously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 4-methylbenzyl ester, 50 mmols of pyridin-3-aldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of ethanol.
Yield: 53% of theory.
EXAMPLE 270
The compound of Example 265 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of pyridin-3-aldehyde and 50 mmols of acetoacetic acid 4-methylbenzyl ester in 90 ml of ethanol.
Yield: 48% of theory.
EXAMPLES 271 TO 276 ##STR55##
EXAMPLE 271
Analogously to Example 1 heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid 4-nitrobenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-methoxycarbonyl-4-(2'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 4-nitrobenzyl ester of melting point 156° C (from ethanol).
Yield: 75% of theory.
EXAMPLE 272
The compound of Example 271 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid 4-nitrobenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 62% of theory.
EXAMPLE 273
The compound of Example 271 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 4-nitrobenzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of ethanol.
Yield: 64% of theory.
EXAMPLE 274
The compound of Example 271 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid 4-nitrobenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 58% of theory.
EXAMPLE 275
The compound of Example 271 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 4-nitrobenzyl ester, 50 mmols of acetoacetic acid methyl ester and 50 mmols of 2-nitrobenzyldehyde in 90 ml of ethanol.
Yield: 55% of theory.
EXAMPLE 276
The compound of Example 271 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid 4-nitrobenzyl ester in 90 ml of ethanol.
Yield: 51% of theory.
EXAMPLES 277 TO 282 ##STR56##
EXAMPLE 277
Analogously to Example 1 heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid isopropyl ester and 75 mmols of β-aminocrotonic acid 2-phenoxyethyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-isopropoxycarbonyl-4-(3'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid 2-phenoxyethyl ester of melting point 110° C (from ethanol).
Yield: 70% of theory.
EXAMPLE 278
The compound of Example 277 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 3'-nitrobenzylideneacetoacetic acid isopropyl ester, 75 mmols of acetoacetic acid 2-phenoxyethyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 61% of theory.
EXAMPLE 279
The compound of Example 277 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 2-phenoxyethyl ester and 50 mmols of β-aminocrotonic acid isopropyl ester in 90 ml of ethanol.
Yield: 68% of theory.
EXAMPLE 280
The compound of Example 277 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 3'-nitrobenzylideneacetoacetic acid 2-phenoxyethyl ester, 50 mmols of acetoacetic acid isopropyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 55% of theory.
EXAMPLE 281
The compound of Example 277 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid 2-phenoxyethyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid isopropyl ester in 90 ml of ethanol.
Yield: 51% of theory.
EXAMPLE 282
The compound of Example 277 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid isopropyl ester, 50 mmols of 3-nitrobenzaldehyde and 50 mmols of acetoacetic acid 2-phenoxyethyl ester in 90 ml of ethanol.
Yield: 48% of theory.
EXAMPLES 283 to 288 ##STR57##
EXAMPLE 283
Analogously to Example 1 heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid α-methylbenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-methoxycarbonyl-4- (2'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid α-methylbenzyl ester of melting point 154° C (from ethanol).
Yield: 60% of theory.
EXAMPLE 284
The compound of Example 283 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid α-methylbenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 49% of theory.
EXAMPLE 285
The compound of Example 283 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid α-methylbenzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of ethanol.
Yield: 52% of theory.
EXAMPLE 286
The compound of Example 283 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid α-methylbenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield 44% of theory.
EXAMPLE 287
The compound of Example 283 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid α-methylbenzyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ml of ethanol.
Yield: 40% of theory.
EXAMPLE 288
The compound of Example 283 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid α-methylbenzyl ester in 90 ml of ethanol.
Yield: 33% of theory.
EXAMPLES 289 to 294 ##STR58##
EXAMPLE 289
Analogously to Example 1 heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester and 75 mmols of β-aminocrotonic acid α-methyl-4-chlorobenzyl ester in 120 ml of ethanol gave 2,6-dimethyl-3-methoxycarbonyl-4-(2'-nitrophenyl)-1,4-dihydropyridine-5-carboxylic acid α-methyl-4-chlorobenzyl ester of melting point 206° C (from ethanol).
Yield: 56% of theory.
EXAMPLE 290
The compound of Example 289 was also obtained analogously to Example 2 by heating a solution of 75 mmols of 2'-nitrobenzylideneacetoacetic acid methyl ester, 75 mmols of acetoacetic acid α-methyl-4-chlorobenzyl ester and 9 ml of concentrated ammonia in 120 ml of ethanol.
Yield: 48% of theory.
EXAMPLE 291
The compound of Example 289 was also obtained analogously to Example 3 by heating a solution of 50 mmols of 2'-nitrobenzylideneacetoacetic acid α-methyl-4-chlorobenzyl ester and 50 mmols of β-aminocrotonic acid methyl ester in 90 ml of ethanol.
Yield: 45% of theory.
EXAMPLE 292
The compound of Example 289 was also obtained analogously to Example 4 by heating a solution of 50 mmols of 2'-nitrobenzylideneactoacetic acid α-methyl-4-chlorobenzyl ester, 50 mmols of acetoacetic acid methyl ester and 6 ml of concentrated ammonia in 90 ml of ethanol.
Yield: 38% of theory.
EXAMPLE 293
The compound of Example 289 was also obtained analogously to Example 5 by heating a solution of 50 mmols of β-aminocrotonic acid α-methyl-4-chlorobenzyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid methyl ester in 90 ethanol.
Yield: 35% of theory.
EXAMPLE 294
The compound of Example 289 was also obtained analogously to Example 6 by heating a solution of 50 mmols of β-aminocrotonic acid methyl ester, 50 mmols of 2-nitrobenzaldehyde and 50 mmols of acetoacetic acid α-methyl-4-chlorobenzyl ester in 90 ml of ethanol.
Yield: 31% of theory.
|
1,4-Dihydropyridines characterized by a carbo(arylalkoxy) group in the 5-position, an aryl group in the 4-position and a alkanoyl or carbalkoxy group in the 3-position and further optionally substituted in the 1,2 and 6-positions are coronary dilating, spasmolytic and hypotensive agents. The compounds, of which 2,6-dimethyl-3-carbomethoxy-4-(2-nitrophenyl)-5-carbobenzoxy-1,4-dihydropyridine is a representative embodiment, are prepared through the reaction of an ylidene-β-dicarbonyl compound, which may be generated in situ from the corresponding β-dicarbonyl compound and an aldehyde, and an enaminocarboxylic acid ester, which may also be generated in situ from a β-dicarbonyl compound and an amine.
| 2
|
BACKGROUND OF THE INVENTION
The present invention relates in general to a cooling fan for rotating electrical machinery such as motors and alternators, and more specifically to fan blade structures which result in reduced fan noise.
Dynamoelectric machines, such as generators, alternators, and motors, are types of rotating machinery which convert mechanical energy into electrical energy and vice versa. Such machines include a stator and a rotor. The rotor is coupled to a shaft for rotation adjacent the stator. Either the rotor or stator, or both, include windings which conduct current and thus produce heat. Other electrical components such as rectifier diodes and mechanical components such as bearings also produce heat and are often located inside the housing of the rotating machine.
In order to provide cooling of such machines, the housing is typically ventilated to allow airflow through the machine. In addition, fans may be included on the rotor or the shaft for drawing air through the housing.
An automotive alternator is known having a structure wherein a fan is attached to each end of the rotor interior of the housing. A front fan draws air in through the front end of the housing and out through the side of the housing. A rear fan draws air through the rear end of the housing and out through the side of the housing. Thus, cooling airflow can be directed to all interior parts, including electrical components, bearings, and windings.
The main disadvantage connected with the use of cooling fans is the noise generated. Since most fans, such as air conditioning fans and automobile alternators, are operated in the vicinity of people, it is desirable to minimize noise generation. Prior art attempts to solve the noise problem have failed to achieve sufficiently reduced noise with a structure which is suitable for inexpensive, large volume production. Prior art solutions typically assume a constant fan speed. That is not a valid assumption for an automobile alternator, which is required to operate over a wide speed range.
U.S. Pat. No. 4,162,419 granted to DeAngelis, discloses an automotive alternator having airflow through the alternator as a result of an internal fan rotating within the housing. Such airflow is directed over semiconductor elements within the alternator. An exterior fan is also provided on the opposite end of the alternator. The fans described in this patent provide efficient cooling of all components, but it would be desirable to decrease the noise levels produced.
U.S. Pat. No. 4,684,324, issued to Perosino, teaches a radiator fan for motor vehicles with a central hub and an outer ring which are joined by curved blades. In an attempt to provide quiet operation of the fan, a particular curvature is provided for the fan blades as viewed in the axial direction. Manipulating the blade curvature has made some beneficial impact on noise generation.
German Offenlegungsschrift 2617029 discloses a fan intended for the electrical generator of an internal combustion engine. The fan is made from a stamped metal plate such that axially projecting fan blades are produced. In addition to curved blades defining a curved flow path, the blades are given no sharp edges so as to achieve some improvement in noise performance.
In the publications Raj et al. (I), Noise Generation In FC Centrifigual Fan Rotors, Fluid Transients and Acoustics in the Power Industry, ASME Annual Winter Meeting, San Francisco, Calif. (1978), pages 289--300, and Raj et al. (II), Measurements of the Mean Flow Velocity and Velocity Fluctuations at the Exit of an FC Centrifugal Fan Rotor, Journal of Engineering for Power, Transactions of ASME, Vol. 103 (April 1981), pages 393-399, flow separation in the air flow through the fan is identified as the major source of noise. These publications propose a two-dimensional aerofoil blade shape with a convergent blade passage to reduce the flow separation and thus reduce noise. Such blade shapes cannot be produced by simple manufacturing techniques such as stamping of sheet metal parts. Furthermore, thickening of the blades undesirably adds mass to the fan which reduces the efficiency of the machine and raises the requirements for mechanical strength of the fan.
SUMMARY OF THE INVENTION
It is a principal object of the present invention to provide a fan for rotating electrical machinery which is not subject to the foregoing disadvantages.
It is a further object of the present invention to provide fan cooled rotating electrical machinery which operates quietly and with a large cooling fluid flow.
It is another object of the present invention to provide a method for reducing noise generated by a variable speed rotating centrifugal fan rotor.
It is still another object to provide a fan plate and fan blade structure which operates with reduced noise but is manufacturable by simple and inexpensive techniques.
These and other objects are achieved by a fan comprising a support plate and a plurality of blades. The support plate is adapted to be coupled to a shaft of a rotating electrical machine and rotates about a central axis. The plurality of blades are supported by the supporting plate to extend substantially normal thereto and have substantially constant thickness. Each blade extends radially from the central axis and a flow channel is defined between each adjacent blade. At least a portion of each blade has a height profile with respect to the supporting plate which is tapered to reduce flow separation of fluid passing through the flow channels. The reduction of flow separation is obtained over a range of rotational speeds of the fan because of the substantially constant cross-sectional area of the flow channels resulting from the tapered profile. More specifically, each blade has a height profile which is a function of radial distance from the central axis. The height profile preferably includes a tapered segment in which the height profile is substantially inversely proportional to radial distance from the fan center in order to maintain a corresponding portion of the defined channel at a constant cross-sectional area.
The invention further includes a method for reducing noise generated by a variable speed rotating centrifugal fan and rotor. A plurality of fan blades are provided for defining a plurality of flow channels and for creating a pressure difference during rotation to cause a fluid flow. The blades are provided with a tapered portion in which blade height decreases in proportion to increasing radius from the fan center. This relationship reduces the size of regions in the flow channels with a positive derivative of pressure with respect to radial distance from the central axis.
BRIEF DESCRIPTION OF THE DRAWINGS
The novel features of the invention are set forth with particularity in the appended claims. The invention itself, however, both as to its organization and method of operation, together with further objects and advantages thereof, may best be understood by reference to the following description taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a cross-sectional view of an alternator according to the present invention.
FIG. 2A is a top view of a centrifugal fan showing a condition resulting in excessive noise.
FIG. 2B is a side view of a prior art fan blade having a constant height.
FIG. 3A is a top view of a fan improvement according to the present invention.
FIG. 3B is a side view of a fan blade height profile according to the improvement of FIG. 3A.
FIG. 4 is a perspective view of one embodiment of the fan of the invention.
FIG. 5 is a top view of the fan of FIG. 4.
FIG. 6 is a side view of a fan blade as indicated in FIG. 5.
FIG. 7 is a perspective view of another embodiment of the fan of the invention.
FIG. 8 is a top view of the fan of FIG. 7.
FIG. 9 is a side view of a fan blade as indicated in FIG. 8.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Turning now to FIG. 1, an alternator 10 illustrates one preferred use of the fan of the invention. A housing 11 includes a front casting 12 and a rear casting 13. Each casting preferrably includes cooling fins such as fins 14 on rear casting 13 to provide conductive cooling. The castings further include a plurality of air passages 15, 16, 17, and 18 to allow convective cooling of the machine.
A stator member 23 is supported in housing 11 and is wound with armature coils such as coil 24. Stator member 23 can, for example, support three armature coils to provide three-phase voltage generation.
A shaft 20 is supported in housing 11 by a front bearing 21 and a rear bearing 22. Shaft 20 extends through front casting 12 to receive pulley apparatus (not shown) for driving rotation of shaft 20 from a source of power such as an internal combustion engine (not shown). A through-bolt boss 29 may receive a bolt in order to secure alternator 10 together.
A rotor member 25 is secured to shaft 20 and includes pole pieces 26. Rotor member 25 rotates adjacent to the stationary stator member 23. A rotor winding 27 is secured to rotor member 25 and receives a DC excitation current through a brush assembly 28.
Stator coils 24 are connected to rectifying electronics (not shown) such as diodes for converting the generated AC voltage to a DC voltage. The electronics are secured to a heat sink 30 within housing 11 to receive a cooling air flow.
A front fan 31 and a rear fan 32 located within the housing are also secured to rotor member 25, as by projection welds (not shown) made using a well known resistance-welding process. In the presently described embodiment, front fan 31 includes backward bending blades (with respect to the direction of rotation--see FIGS. 4-6) and rear fan 32 includes forward bending blades (see FIGS. 7-9) such that rotation of the fans draws air in through the ends of the housing and out the sides of the housing, for example, along paths 33 and 34, respectively, The rotating fan blades create a static pressure which drops with increasing radial distance from the center of rotation. The dropping static pressure causes a dynamic air flow along the negative pressure gradient.
A major contribution to noise generation in prior art fan configurations arises from flow separation within the channels between adjacent blades. With reference to FIGS. 2A and 2B, a prior art centrifugal fan 35 is shown which supports a plurality of fan blades each having a constant height h. Blades 36 and 37 define a channel between the concave surface of blade 36 and the convex surface of blade 37. Upon rotation of fan 35, e.g., in the direction indicated by arrow 38, an air flow is created in the channel along a path 40. Due to the parameters of the flow channels in the prior art fan, a region 41 of flow separation develops adjacent the concave surface of blade 36. For rotation in the direction opposite arrow 38, flow separation region 41 would develop adjacent the convex surface of blade 37 and air flow would be radially inward (i.e., opposite to the direction of path 40). Region 41 has a pressure gradient such that the derivative of pressure with respect to radial position is positive, i.e., pressure increases with increasing distance from the center of rotation. An air flow results in region 41 which is in a direction opposite to the primary flow direction. This results in a circulating air flow having high turbulence and creating excessive noise.
FIGS. 3A and 3B illustrate an improved fan blade of the present invention which reduces flow separation and the resultant noise. A support plate 45 has an aperture 48 for receiving a shaft along a defined central axis 49. A plurality of fan blades including blades 46 and 47 are supported by support plate 45. The fan blades all have substantially constant and equal thicknesses to facilitate the manufacture of the fan by a stamping process. Each of the fan blades in FIG. 3A has a substantially identical arcuate shape and define flow channels, e.g., channel 51, between adjacent blades discharging within the housing. Upon rotation of the fan, an air flow develops between blades 46 and 47 which has a flow direction shown by arrow 50 either radially inward or radially outward depending on the direction of fan rotation. The present invention provides improved noise performance independently of the direction of fan rotation.
According to the present invention, each flow channel 51 maintains a substantially constant cross-sectional area measured at each radial position r 1 , r 2 , r 3 , etc. by virtue of fan blades 46 and 47 having a predetermined height profile with respect to support plate 45, as shown in FIG. 3B. In general, the fan blade is tapered to reduce flow separation of fluid passing through its flow channel. This reduction is accomplished over a range of rotational speeds of the fan because of the constant cross-sectional area of channel 51. In this example, a taper portion 55 extends from a radially inner end 56 of blade 46 to a radially outer end 57. The tapered portion 55 can include substantially all of the radial extent of blade 46 as is shown in FIG. 3B, or can be employed in conjunction with a constant height inner blade portion, such as is shown in FIGS. 1, 6, and 9, to maintain a high suction pressure, for example.
Each cross section of a flow channel taken at radial positions along the flow channel is coincident with an arc portion of a circle having a circumference determined by that radial position. Since the circumference of a circle increases in direct proportion to the radius (2πr), then the cross-sectional area of a channel between a pair of blades is maintained constant by decreasing the blade height in inverse proportion to radius. For example, in FIGS. 3A and 3B, the cross-sectional area of the channel at radius r 1 is proportional to r 1 times the height h 1 . At a radius r 2 , the cross-sectional area is proportional to r 2 times the height h 2 . To maintain the cross-sectional area of the channel constant, r 1 times h 1 is set equal to r 2 times h 2 . Solving for h 2 gives:
h.sub.2 =(r.sub.1 ×h.sub.1)/r.sub.2.
Therefore, a tapered segment is included in the height profile of each fan blade in which blade height is substantially inversely proportional to radius from the central axis of the fan.
A further improvement in noise performance is obtained by the addition of a bevel or chamfer 60 at the outermost edge of blade 46. Bevel 60 avoids sharp corners and helps to reduce any additional flow separation caused at the blade termination by the relatively high linear speed of outer end 57.
A preferred embodiment of front fan 31 (FIG. 1) is shown in FIGS. 4--6. A support plate 61 has an aperture 62 for receiving a shaft of the rotating machine. The fan is a one-piece metal stamping having a plurality of raised blades 63 each with reinforcing gussets 65 and 66. A plurality of dimples 64 are provided on support plate 61 in order to attach the fan to a rotor member by means of a projection weld.
As shown in FIG. 6, blade 63 has a height profile rising from support plate 61 which includes a constant height segment 70, a tapered segment 71, and a beveled segment 72. Tapered segment 71 is inclined toward plate 61 such that blade height decreases from the height of constant height segment 70 in proportion to increasing radial distance from the center of the fan, e.g., at a point where radial position is 10 percent greater than the radius at the intersection of segments 70 and 71, the blade height is decreased by 10 percent. Beveled segment 72 has an even greater incline.
Blades 63 are straight and thus define flow channels with straight sides. However, the inclined segments of the blades result in a channel volume between blades having a constant cross-sectional area, and a substantial reduction in noise generation is achieved.
A preferred embodiment of rear fan 32 (FIG. 1) is shown in FIGS. 7-9. A support plate 75 has an aperture 76 for receiving a shaft of the rotating machine. The fan is a one-piece metal stamping having a plurality of raised blades 77 each with a reinforcing gusset 79. A plurality of dimples 78 are provided on support plate 75 in order to attach the fan to a rotor member by means of a projection weld.
As shown in FIG. 9, blade 77 has a height profile rising from support plate 75 which includes a constant height segment 80, a tapered segment 81, an outer beveled segment 82, and an inner beveled segment 83. Tapered segment 81 is inclined toward plate 75 in the manner previously described. Beveled segment 82 has an even greater incline.
Blades 77 are curved and thus define flow channels with curved sides. However, the incline of the tapered segments provides a channel having a constant cross-sectional area. Inner bevel 83 further reduces noise by avoiding a sharp corner at the inner end of blade 77.
Alternators using the fan blade profiles of the present invention have been found to have decreased noise levels of up to 3 dBa (adjusted dB) over similar alternators with similar blades having substantially rectangular blade height profiles. Blade shapes have been investigated having a constant height inner segment comprising of from about 43 to 50 percent of the total radial extent of the blade and having a tapered portion comprising from about 50 to 57 percent of the radial blade extent. This range provides the best trade-off between reducing noise sound pressure and maintaining thermal performance (i.e., adequate air flow). Bevels at either end of the blade can preferably be provided which may include about 5 to 10 percent of the blade radial extent.
The fans of the invention maintained their effectiveness in providing reduced noise levels and a large cooling air flow over a large speed range, e.g., 0 to 23,000 rpm. They are further capable of being manufactured by inexpensive fabrication techniques such as by metal stamping.
While preferred embodiments of the invention have been shown and described herein, it will be understood that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions will occur to those skilled in the art without departing from the spirit of the invention. Accordingly, it is intended that the appended claims cover all such variations as fall within the spirit and scope of the invention.
|
A centrifugal fan for ventilated rotating machinery is provided having tapered fan blades to reduce sound pressure levels generated by fan operation over a wide speed range. The tapering of the fan blades keeps the cross-sectional area of each flow channel substantially constant as the air flows radially through the fan, resulting in a less turbulent flow. Each fan blade may include a height profile having a tapered segment in which blade height decreases in proportion to increasing radial distance from the central axis of the fan.
| 5
|
BACKGROUND OF THE INVENTION
1. The Field of the Invention
The invention disclosed herein relates to connectors having conductive contact units which are movably mounted such that they are permitted a certain degree of movement and are accordingly able to receive misaligned terminals.
2. The Prior Art
U.S. Pat. No. 3,444,504 discloses one form of an electrical connector wherein the contact section has limited movement independent of the housing in which it is positioned. The contact section is attached to a blade section having weak flexural strength which provides the contact section with a certain degree of movement so that it may effectively mate with a misaligned terminal.
SUMMARY OF THE INVENTION
The invention disclosed herein may be characterised as consisting of a contact unit positioned in an insulating housing having access slots to tab terminal receiving openings at either end of the unit. The unit itself consists of a pair of elongated, identical blades held together in parallel relation by spring members which permit limited blade separation in both the horizontal and vertical planes.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an isometric view of the connector of the present view with the housing thereof separated;
FIG. 2 is an isometric view showing the connector of FIG. 1 in one contemplated manner of usage;
FIG. 3 is a cross-sectional view of one contact unit, the view being taken along line 3--3 in FIG. 1;
FIG. 4 is an isometric view of a contact unit shown in exploded fashion;
FIG. 5 is a view taken along line 5--5 of FIG. 2, partially in cross-section, showing a contact unit in the housing; and
FIG. 6 is the view of FIG. 5 showing misaligned tab terminals received in the contact unit.
DESCRIPTION OF THE INVENTION
Connector 10 of FIG. 2 is shown in FIG. 1 with components housing 12 in two sections and contact units 14 (two being diagrammatically represented) between the two housing sections. The connector illustrated in the drawings show a housing adapted to contain three contact units. The connector can be made to contain any number of units, however, from one on up.
The disassembled housing 12 of FIG. 1 suggests one and the preferred way of molding it; i.e., molding a first section 12-A containing substantially the full width of compartments 16 and a second section 12-B comprising substantially a cover plate. Pins 18 on section 12-A are received in holes 20 in section 12-B and hold the two sections together.
Slots 22 provide access to the compartments and are located in both front face 24 and back end 26 of the housing. The slot walls are beveled to facilitate tab terminal entry.
Contact units 14 are positioned loosely in the compartments with unit ends 28 facing slots 22 such as shown in FIGS. 5 and 6.
FIG. 2 shows a connector 10 in one type of usage. To the left of the connector is a high current-carrying bus bar 30 having three tab terminals 32 (only two are visible) extending laterally therefrom. This type bar may be found mounted in a computer cabinet or the like and connector 10 is secured to the bar by machine screws 34, with tab terminals 32 inserted into compartments 16 through slots 22 and into contact units 14 as shown in FIG. 6.
A drawer 36, shown to the right of the connector in FIG. 2 is the type in which several printed circuit boards (not shown) are mounted for use in a computer. Each board is connected to one of the tab terminals 38 shown extending rearwardly from the drawer. Drawer 36 is movable towards and away from connector 10 mounted on bus bar 30. The boards in the drawer are energized by sliding the drawer rearwardly so that tab terminals 38 thereon enter connector 10 and more particularly, contact units 14 therein. FIG. 6 shows connector 10 providing the electrical connection between bus bar 30 (only tab terminals 32 shown) and drawer 36 (only tab terminals 38 shown). Alternatively, connector 10 can be secured to the back of drawer 36 for movement onto the tab terminals on bus bar 30.
As is well known, manufacturing tolerances on main frames and drawers 36 used thereon are not close. Accordingly, the insertion match between contact units 14 in connector 10 and tab terminals 38 on the drawer may be and often is less than perfect. It becomes necessary then that some forgiveness is available somewhere between the drawer and bus bar; i.e., connector 10 and more particularly, contact units 14 therein.
FIGS. 3 and 4 will now be referred to in describing the novel features of contact units 14 which permit the aforementioned misalignment while at the same time providing an extremely good electrical connection required for high currents.
A contact unit 14 is shown in FIG. 4 in an exploded manner. Each unit includes a pair of identical blades 40 and a pair of identical spring members 42.
Ends 44 on blades 40 are turned or bent obliquely out of the plane of the blade with the degree of bending, relative to intermediate section 46; i.e., the portion of the blade between ends 44, being about forty-five degrees. The side towards which the ends are bent is hereinafter referred to as the outer side 48 of each blade. The opposite side then is referred to as the inner side 50.
With respect to the intermediate section 46 of the blade, a pair of raised contact surfaces 52 are provided on inner side 50 with one contact surface adjacent each end 44. The raised contact surfaces preferrably extend across most of the width of the blade.
The raised contact surfaces are stamped so that corresponding depressions 54 are in outer side 48.
Blades 40 are preferrably made from half-hard copper and plated with silver.
Spring members 42 may be characterised as being elongated and narrow with a set of two parallel arms 56 extending from each side of center section 58. Fingers 60 extend down from the side of the free end 62 of each arm. The free ends 64 of each finger is a concavo-convex shape with the convex surface 66 facing in towards the convex surface on the adjacent finger.
The edges of center section 58 curve in to reduce the size of the section so that it functions more easily as a pivot point for arms 56. Spring members 42 are preferrably made from stainless steel.
Contact unit 14 is assembled by holding the two blades 40 together, inner sides 50 facing each other, and clipping spring members 42 over the edges of the blades. The convex surfaces 66 on fingers 60 are received in depressions 54 in the outer sides 48 of the blades. FIG. 3 shows this.
As assembled, the raised contact surfaces 52 on one blade abutt surfaces 52 on the parallel blade. Further, the turned out ends 44 provide a beveled entrance to guide tab terminals in between the blades and particularly between the raised contact surfaces.
FIG. 5 shows a contact unit 14 positioned in compartment 16 in housing 12. Further, connector 10 which the aforementioned components form, is between tab terminals 32 of bar 30 and tab terminals 38 of drawer 36. As illustrated in the drawing of that figure, the tab terminals are offset relative to each other, with connector 10 and with contact unit ends 28. Normally the connector would be in alignment with bus bar 30 to which it is mounted. For purposes of illustration, however, it is assumed that the holes in bus bar 30 receiving machine screws 34 on connector 10 are out of alignment with tab terminals 32. Accordingly, as shown in FIG. 6, tab terminals 32 has been inserted into unit end 28 off-center in a direction towards the top of the drawing sheet. Similarly, tab terminal 38 enters the opposite unit end off-center towards the bottom of the drawing sheet. Contact unit 14 absorbs this misalignment in two ways. First, it has room within compartment 16 to move. Thus, the left end moves up and of course, the right end must move down. Secondly, the blades move apart differentially; i.e., the blade ends spread apart non-symmetrically relative to the center line (not shown) of the particular compartment.
As the tab terminals enter in between contact surfaces 52 the blades are able to spread apart by arms 56 pivoting outwardly about center section 58 such as shown in an exaggerated scale in FIG. 6. The result of the arms pivoting about is that a significant force is continuously pressed against the tab terminals so that the contact surfaces transfer high current between the tab terminals and blades very effectively without significant heat rise. Further, the raised contact surfaces 52 serve to concentrate the force to enhance even more the current transfer.
The foregoing detailed description has been given for clearness of understanding only, and no unnecessary limitations should be understood therefrom, as some modifications will be obvious to those skilled in the art.
|
The present invention relates to a connector for joining high current-carrying devices, such as bus bars, used in computers and the like. More particularly, the connector includes one or more contact units each consisting of two elongated contact blades held loosely together by spring members. Tab terminals are received into the units from either end. The contact blades are able to move, as a unit or separately, to accept misaligned tab terminals.
| 7
|
BACKGROUND OF THE INVENTION
The present invention relates to a device for cleaning an oil dipstick and has particular application for use with dipsticks as incorporated in internal combustion engines of motor vehicles.
In internal combustion engines and particularly those employed in motor vehicles, and also in certain central heating oil tanks or the like, an oil dipstick extends through a bore formed in the crankcase or tank for emersion in the oil as contained therein. In the usual practice of measuring the oil level in the crankcase or tank, the dipstick is removed from the bore and wiped clean prior to reinsertion thereof for an oil level reading. This cleaning operation of the dipstick before the measurement is usually accomplished by wiping the dipstick with a cloth or suitable absorbent material. Because there is some risk of becoming soiled in removing the dipstick and observing the oil level, this operation is normally carried out by an attendant or workshop personnel; and since maintenance of a predetermined oil level is of critical importance to the life of an internal combustion engine, measurement of the oil levels at periodic intervals is necessary.
Prior to the instant invention, some efforts have been made to incorporate a wiping device as part of the bore through which the dipstick extends, and although some of these prior known devices have accomplished the purpose intended, the materials from which they were constructed, such as felt, fabric, or similar absorbent materials, resulted in relatively short-term use thereof that required replacement parts. Other more complicated self-wiping devices have also been utilized, but have been costly in the construction and maintenance thereof. Some prior known devices are represented in the following patents: U.S. Pat. Nos. 1,747,100; 2,029,672; 2,634,445; 3,686,702 and 3,703,038 and German Pat. No. 1,023,599.
SUMMARY OF THE INVENTION
The present invention relates to an oil dipstick for use in measuring oil level in an oil receiving chamber as formed in a housing and includes an elongated rod on the outermost end of which a handle is formed. A wiping member is removably received in a bore as formed in the casing, the rod slidably extending through the wiping member in frictional contact therewith and being movable outwardly of said casing relative to the wiping member, wherein oil is removed therefrom by contact with the wiping member. A locking member is secured to the rod and is engageable with the wiping member for selectively locking the wiping member to the rod, so that the wiping member and the rod are removable from the bore as a unit for a reading of the oil level on the rod. The locking member includes a lever on which a hook elememt is formed, the wiping member having means for receiving the hook element in locking engagement for securing the wiping member to the rod, the lever being pivotally movable to release the rod from said wiping member for movement relative thereto.
Accordingly, it is an object of the invention to provide a device for cleaning oil dipsticks which enables the measurement of oil level within a casing to be carried out without the use of an auxilliary cleaning medium and without the danger of the user soiling his hands or clothing in the oil level reading operation.
DESCRIPTION OF THE DRAWINGS
In the drawings which illustrate the best mode presently contemplated for carrying out the present invention;
FIG. 1 is a perspective view of the oil dipstick as embodied in the present invention;
FIG. 2 is a sectional view of the oil dipstick embodied herein as normally located in a bore formed in a casing in which oil is located;
FIG. 3 is a view similar to FIG. 2 illustrating the dipstick rod after disengagement thereof from the wiping member during the retracting movement of the rod in carrying out the wiping operation; and
FIG. 4 is a sectional view taken along line 4--4 in FIG. 1.
DESCRIPTION OF THE INVENTION
Referring now to drawing, the oil dipstick as embodied in the present invention is generally indicated at 10 and as shown is intended for use in the measurement of oil level in the chamber or crankcase of an automotive vehicle or in an oil tank of a central heating unit or the like. As shown in FIGS. 2 and 3, a casing 12 is partially shown and comprises a part of the casing or crankcase of an automotive vehicle or an oil tank. Projecting inwardly from the casing 12 is a tubular extension 14 in which a bore 16 is formed for receiving the dipstick 10 as will be described.
The dipstick 10 includes an elongated rod 18 having a semispherical configuration which as shown in FIG. 4 defines a flat face 20. Formed on the uppermost end of the elongated rod 18 is a curved handle 22 that is conventional in configuration and provides a finger grip for removing and handling the dipstick 10 during an oil reading operation. The lowermost end of the rod 18 is offset as indicated at 24, the offset portion 24 defining a stop, which prevents removal of the rod 18 from a wiping member which will hereinafter be described. As further indicated in FIG. 1, markings 26 are formed on the flat face 20 of the rod 18 adjacent to the stop 24 and indicate the level of oil in the casing or crankcase in which the dipstick 10 is located.
The primary purpose of the dipstick as embodied in the present invention is to enable a reading of an oil level to be carried out without using a cleaning medium such as a rag or absorbent paper for initially cleaning the lowermost end of the dipstick after it has been extracted from the casing 12. In order to accomplish this purpose, a wiping member generally indicated at 28 is provided. As shown more clearly in FIG. 1, the wiping member 28 includes an upper portion 30 to which a lower portion 32 is joined. The upper and lower portions 30 and 32 of the wiping member 28 are individually formed as illustrated in the drawing, although it is understood that these two portions can be formed in a one-piece construction. The upper portion 30 has a spool-like appearance and includes an upper flange 34 and a lower flange 36 between which a central portion 38 is integrally joined, vertical ribs being spaced around the central portion 38 and extending from the top flange 34 to the bottom flange 36. Integrally joined to the upper flange 34 is a head portion 42 that is generally circular in configuration and that has a diameter somewhat less than the diameter of the flange 34. As shown in FIG. 3, a slot 44 is formed in the head portion 42 and includes a tapered or inclined wall 46 beneath which an undercut recess portion 48 is located that defines a shoulder 50 therewith, the purpose of which will be described hereinafter. Projecting below the lower flange 36 in coaxial relation therewith is a reduced extension 52 that provides for the joining of the upper portion 30 to the lower portion 32. As more clearly illustrated in FIGS. 2 and 3, the lower portion 32 includes a tubular shank 54 having spaced annular ribs 56 formed thereon. Joined to the tubular shank 54 is an enlarged neck portion 58 to which an upper flange 60 is integrally connected. Formed interiorly of the enlarged neck portion 58 is an annular recess that receives an annular rib 62 located on the extension 52 for connecting the upper portion 30 to the lower portion 32. A suitable adhesive may also be used to firmly fix the extension 52 within the tubular shank 54 for joining the upper portion 30 to the lower portion 32. Formed as part of the lower tubular member 54 is a lower end wall 64 in which an opening is located for receiving the rod therethrough. As further illustrated in FIGS. 2 and 3, the rod 18 also slidably extends through an appropriately formed bore that extends axially through the upper portion 30 and the extension 52 projecting therebelow.
As described hereinabove, the lower portion 32 is formed of a deformable or elastic material, such as rubber that will resist deterioration when subject to oil. The elastic material may also be formed of any suitable plastic material that is insoluable in oil and that is sufficiently rigid so as to enable the spaced ribs 56 to firmly locate the wiping member 28 in the bore 16 of the oil crankcase. Although the upper and lower portions 30 and 32 of the wiping member 28 are shown and described hereinabove as being formed separately and joined together, it is contemplated that the wiping member may be formed of a suitable plastic material for molding in a one-piece construction. It is understood that the material will be sufficiently resilient to enable the lower portion to be frictionally received within the bore 16 of the oil crankcase, but the upper portion 30 will also be sufficiently rigid for securement thereof to a locking member, which will be described hereinbelow.
In order to secure the wiping member 28 to the rod 18, a locking member generally indicated at 66 is provided. As shown in the drawing, the locking member 66 includes a U-shaped bracket generally indicated at 68 defined by walls 70 and 72 to which is joined a curved end wall 74. Joined to the side walls 70 and 72 and molded as an integral part thereof, is an interior wall 76 that cooperates with the curved end wall 74 to form a longitudinally extending recess 78. As shown in FIG. 4, the recess 78 has a configuration corresponding to the cross-section of the rod 18 and receives the rod therein. The bracket 68 is preferably molded around the rod 18, and a plurality of small deformations are formed on the rod in the area around which the bracket is molded to fix the bracket on the rod against axial movement.
Located between the side walls 70 and 72 of the bracket 68 is a lever generally indicated at 80 that is formed with a tapered handle portion 82 and a locking portion 84 that terminates in a hook 86. Formed intermediate the handle portion 82 and the locking portion 84 is an enlarged portion 88 that receives a pin 90 for pivotally mounting the lever 80 between the side walls 70 and 72 of the bracket 68. As shown more clearly in FIG. 3, the lever 80 has a spring member 92 formed as an integral part thereof and that extends upwardly from the enlarged portion 88 adjacent to the pivot axis of the lever as represented by the pin 90. The spring member 92 bears against the interior wall 76 and normally urges the hook element 86 into engagement with the shoulder 50 of the upper portion 30 of the wiping member 28, when the rod 18 is moved downwardly relative to the wiping member 28. This relative movement of the rod 18 with respect to the wiping member 28 is facilitated by formation of the upper portion 30 of a plastic material that enables the rod to freely slide within the bore as formed therein.
In use of the oil dipstick embodied in the present invention, the wiping member 28 is normally mounted in the bore 16 of the casing 12, the rod 18 being located in the position illustrated in FIGS. 1 and 2, wherein the hook 86 is urged into engagement with the shoulder 50 by the spring 92. When an oil reading in the casing 12 is to be taken, the lever 80 is depressed at the handle portion 82 to release the hook 86 from the shoulder 50 of the head portion 30. Simultaneously, the rod 18 is lifted outwardly relative to the wiping member 28, the annular ribs 56 of the lower portion 32 of the wiping member frictionally retaining the wiping member in the bore 16. As the rod 18 moves outwardly relative to the wiping member, the lower surfaces of the rod 18 wipe against the portion of the lower wall 64 immediately adjacent to the opening therein, thereby removing the residual oil located on the lower end of the rod. The rod 18 reaches the upper limit of travel relative to the wiping member 28 when the stop 24 engages the lower end wall 64. At this point, the lower end of the rod 18 has been wiped clean of the oil. The rod 18 is then reinserted into the casing 12 by moving it downwardly relative to the wiping member 28, the hook 86 riding on the inclined wall 46 in the slot 44. When the hook 86 slides off of the inclined wall 46, the spring 92 urges it inwardly into the recess portion 48 for engagement with the shoulder 50. In this position, the rod 18 is now located to the wiping member 28. The entire assembly is then lifted outwardly by the handle 22, the wiping member 28 being forced outwardly of the bore 16 with the rod 18 for a reading of the oil level on the lower end thereof. After the oil level has been determined, the rod 18 and wiping member 28 are reinserted into the bore 16 and pushed downwardly until the flexible lower portion 32 of the wiping member 28 is snugly received within the bore 16.
It is seen that the oil level measurement can be performed with one hand, and there is little danger of soiling hands or clothing of the user, particularly since the oil dipstick is moved essentially in a straight line motion.
Although the rod 18 is illustrated in the drawing as having a semispherical configuration, it is understood that the rod can be formed with a circular cross-sectional configuration. In this event, it is contemplated that the head portion 42 would be formed with an annular shoulder for accommodating the hook 86 regardless of the radial position of the locking member 66 relative to wiping member 28. A straight line movement of the rod 18 would still accomplish the intended purpose as described hereinabove.
While there is shown and described herein certain specific structure embodying the invention, it will be manifest to those skilled in the art that various modifications and rearrangements of the parts may be made without departing from the spirit and scope of the underlying inventive concept and that the same is not limited to the particular forms herein shown and described except insofar as indicated by the scope of the appended claims.
|
An oil dipstick for use in measuring the oil level in an oil receptacle such as the crankcase of an automotive vehicle, including an elongated rod that is received in a wiping member in frictional contact therewith and is movable outwardly of the crankcase relative to the wiping member, wherein oil is removed therefrom by contact with the wiping member. A locking member is secured to the rod and is engageable with the wiping member for selectively locking the wiping member to the rod, so that the wiping member and rod are removable from the crankcase as a unit for a reading of the oil level on the rod.
| 6
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to printed circuit boards having improved fire resistance and improved environmental stability. More particularly, the invention relates to halogen-free fire retardant printed circuit boards incorporating potentially flammable polymers.
2. Description of the Related Art
Printed circuit boards are employed in a wide variety of applications. For example, they can be found inside radio and television sets, telephone systems, automobile dashboards and computers. They also play an important role in the operation of airborne electronic equipment and guided missiles. In forming insulating dielectric materials for printed circuit boards, it is common to employ organic polymer films that may be flammable under certain circumstances.
To combat this problem, fire retardant halogen additives are commonly employed. The purpose of the halogens is to attain an acceptable flammability rating as determined by Underwriters Laboratory (UL) 94V0 or 94V1 flammability tests, for most standard resins. For example, Japanese abstract JP6240214 provides a copper-clad laminate having a copper foil coated with a flame-retardant adhesive. The flame-retardant adhesive comprises a poly(vinyl acetal) resin, epoxy resin, polyisocyanate resin, and brominated polyester resin. U.S. Pat. No. 6,071,836 discloses polybutadiene and polyisoprene thermosetting compositions having a bromine-containing fire retardant. However, these additives are very expensive and interfere with the physical and electrical properties of the polymer. Also, decomposition of dielectric materials having halogen additives produces carcinogenic materials such as furan and dioxins.
In order to minimize the impact on the environment of electronic materials, many countries are requiring the substrates used in circuit boards to be halogen-free. For example, Japanese abstract JP11343398 provides a laminate and metal foil utilizing a flame retardant epoxy resin composition. This flame retardant composition comprises an epoxy resin, a hardener and an additive, wherein at least one incorporated hardener comprises a polycondensate of phenols, a compound having a triazine ring and aldehydes, and an inorganic filler as an additive. Also, Japanese abstract JP10195178 discloses a halogen-free flame-retardant composition comprising a bisphenol A epoxy resin, a novolac epoxy resin, a phenolic resin curing agent, a cure accelerator and an inorganic filler. U.S. Pat. No. 5,082,727 teaches a flameproof product wherein the flameproofing agents are a combination of organic borates, salts of phosphoric acids and oxide hydrates of magnesium and/or of aluminum. However, these alternatives are also very expensive and do not have good peel strengths to foil conductors.
It has therefore been desirable to provide an affordable, non-flammable, halogen-free dielectric composition for printed circuit boards having good properties and performance. The present invention offers a solution to this problem, providing a method by which copper foils are coated with non-halogenated thermoplastic dielectric layers and thermosetting polymer layers.
In particular, a printed circuit board is provided comprising a substrate having opposite surfaces, a thermosetting polymer layer on each of the opposite substrate surfaces, a thermoplastic dielectric layer on each of the thermosetting polymer layers, and an electrically conductive layer on each of the thermoplastic dielectric layers. The thermosetting layers may have various degrees of flammability, but the thermoplastic layers are inherently flame resistant and prevent combustion of the thermosetting polymers. The thermoplastic dielectric also adds strength to the laminate, resulting in a less brittle thin core than the prior art. The result is a cost efficient, environmentally safe and flame resistant laminate having excellent properties, including a decreased probability of shorting, good dielectric breakdown voltage, a smooth surface and good electrical/thermal performance.
SUMMARY OF THE INVENTION
The invention provides a circuit board comprising in order:
a) a planar substrate having opposite surfaces;
b) a thermosetting polymer layer on each of the opposite substrate surfaces;
c) a thermoplastic dielectric layer on each of the thermosetting polymer layers; and
d) an electrically conductive layer on each of the thermoplastic dielectric layers.
The invention also provides a process for manufacturing a printed circuit board comprising:
a) depositing a thermosetting polymer layer onto opposite surfaces of a substrate;
b) depositing a thermoplastic dielectric layer onto each of the thermosetting polymer layers; and
c) depositing an electrically conductive layer onto each of the thermoplastic dielectric layers.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention provides a halogen-free, fire retardant printed circuit board.
The first step in the process of the invention is to deposit a thermosetting polymer layer onto opposite surfaces of a planar substrate. Typical substrates are those suitable to be processed into an integrated circuit or other microelectronic device. Suitable substrates for the present invention non-exclusively include non-halogenated materials such as fiberglass, aramid (Kevlar), aramid paper (Thermount), polybenzoxolate paper or combinations thereof. Of these, fiberglass is the most preferred substrate. Also suitable are semiconductor materials such as gallium arsenide (GaAs), silicon and compositions containing silicon such as crystalline silicon, polysilicon, amorphous silicon, epitaxial silicon, and silicon dioxide (SiO 2 ) and mixtures thereof. The preferred thickness of the substrate is of from about 10 to about 200 microns, more preferably from about 10 to about 100 microns. In a preferred embodiment of this invention, the substrate of the printed circuit board may comprise a plurality of adjacent strata including the strata of the above substrate materials, forming a complex multilayered article. In this embodiment, each stratum is attached to an adjacent stratum by a thermosetting polymer layer.
The thermosetting polymer layers are preferably deposited onto the substrate as liquids by coating, evaporation or vapor deposition to allow for control and uniformity of the polymer thickness. The liquid layers may subsequently be partially or fully cured on the substrate, thus forming a prepreg. For the purposes of this invention, an A-staged prepreg comprises a substrate having uncured thermosetting polymer thereon, a B-staged prepreg incorporates a partially cured thermosetting polymer, and a C-staged prepreg has a fully cured polymer. The most preferred prepreg for use in this invention is a B-staged, partially cured prepreg. Curing is conducted by placing the prepreg into an oven to evaporate any solvent from the polymer and either partially or fully cure the layers. Such may be done by subjecting the prepreg to a temperature of from about 100° F. to about 600° F., for about 1 to about 10 minutes. After curing is completed, the prepreg is removed from the oven and cooled.
The thermosetting polymer layers may also be deposited in the form of liquids or sheets that are laminated onto opposite sides of the substrate. Lamination is preferably conducted in a press at a minimum of about 275° C., for about 30 minutes. Preferably, the press is under a vacuum of at least 28 inches of mercury, and maintained at a pressure of about 150 psi. The thermosetting polymer layers preferably comprise non-halogenated materials such as epoxies, bis-malimide triazine epoxies, thermosetting polyimides, cyanate esters, allylated polyphenylene ethers, benzocyclobutenes, phenolics and combinations thereof. Of these epoxies and polyimides are preferred. Preferably, the thermosetting polymer layers have a thickness of from about 5 to about 200 microns, more preferably from about 2 to about 100 microns.
Next, thermoplastic dielectric layers are deposited onto each of the thermosetting polymer layers or onto the conductive layers. The thermoplastic dielectric layers may be deposited in the form of liquids or sheets that are laminated onto each thermosetting polymer layer, under conditions similar to those for lamination of the thermosetting layers. Preferably, the thermoplastic dielectric layers are deposited onto the thermosetting layers as liquids by coating, evaporation or vapor deposition, allowing for control and uniformity of the polymer thickness. The thermoplastic dielectric layers preferably comprise a substantially non-flammable material as determined by the UL94V0 test. These materials preferably include polyimides, polyesters, polyester containing co-polymers, polyarylene ethers, liquid crystal polymers, polyphenylene ethers, amines, and combinations thereof. Of these, polyimides are the most preferred. Polyimides are preferred because they have high electrical strengths, good insulating properties, a high softening point and are inert to many chemicals. Preferred are polyimides having a glass transition temperature (Tg) of from about 160° C. to about 320° C., with a glass transition temperature of from about 190° C. to about 270° C. being preferred. Preferably, the thermoplastic dielectric layers have a thickness of from about 5 to about 200 microns, more preferably from about 2 to about 100 microns.
The thermoplastic dielectric liquids will typically have a viscosity ranging from about 5,000 to about 35,000 centipoise with a preferred viscosity in the range of 15,000 to 27,000 centipoise. The polymer liquids will each comprise a solution including from about 10 to about 60% and preferably 15 to 30 wt % polymer with the remaining portion of the solution comprising one or more solvents. It is preferred that a single solvent be used in each polymer solution. Useful solvents include acetone, methyl-ethyl ketone, N-methyl pyrrolidone, and mixtures thereof. A most preferred single solvent is N-methyl pyrrolidone.
Either one or both of the thermosetting and thermoplastic polymers may also optionally comprise a filler material. Preferred fillers non-exclusively include ceramics, boron nitride, silica, barium titanate, strontium titanate, barium strontium titanate, quartz, glass beads (micro-spheres), aluminum oxide, nonceramic fillers and combinations thereof. If incorporated, a filler is preferably present in the thermoplastic dielectric polymer or thermosetting polymer in an amount of from about 5% to about 80% by weight of the each polymer, more preferably from about 10% to about 50% by weight of the each polymer. The percent of total polymer to the substrate material and to fillers may have a strong effect on flammability of the circuit board. Generally, the less the amount of thermosetting polymer present in the circuit board, the less flammable the circuit board will be.
The ratio of the thermoplastic dielectric to the thermosetting dielectric is important to obtain a fire resistant circuit board having good properties. Preferably, the weight ratio of the thermoplastic dielectric to the thermosetting dielectric is from about 1:0.5 to about 1:15, and more preferably from about 1:1 to about 1:8.
After the thermoplastic dielectric layers have been deposited onto the thermosetting polymer layers and/or the electrically conductive layers the materials are laminated together to form a metallic clad substrate. Each conductive layer may comprise either the same metal or may comprise different metals. The conductive layers preferably comprise foils and preferably comprise a material such as copper, zinc, brass, chrome, nickel, aluminum, stainless steel, iron, gold, silver, titanium and combinations and alloys thereof. Most preferably, the conductive layers comprise a copper foil. At least one of the electrically conductive foils may also comprise a part of an electrical circuit.
The conductive layers preferably have a thickness of from about 0.5 to about 200 microns, more preferably from about 9 to about 70 microns. The conductive materials used in the flexible composites of this invention may be manufactured with a shiny side surface and a matte surface. Examples of such conductive materials are disclosed in U.S. Pat. No. 5,679,230, which is incorporated herein by reference. The conductive layers may be applied using any well known method of metal deposition such as electrolytic or electroless deposition, coating, sputtering, evaporation or by lamination onto the thermoplastic layer.
After the circuit board is formed, it may then be selectively etched using well known photolithographic techniques using a photoresist composition. First, a photoresist is deposited directly onto the conductive layer. The photoresist composition may be positive working or negative working and is generally commercially available. Suitable positive working photoresists are well known in the art and may comprise an o-quinone diazide radiation sensitizer. The oquinone diazide sensitizers include the o-quinone-4-or-5-sulfonyl-diazides disclosed in U.S. Pat. Nos. 2,797,213; 3,106,465; 3,148,983; 3,130,047; 3,201,329; 3,785,825; and 3,802,885. When o-quinone diazides are used, preferred binding resins include a water insoluble, aqueous alkaline soluble or swellable binding resin, which is preferably a novolac. Suitable positive photodielectric resins may be obtained commercially, for example, under the trade name of AZ-P4620 from Clariant Corporation of Somerville, N.J. as well as Shipley I-line photoresist. Negative photoresists are also widely commercially available.
The photoresist is then imagewise exposed to actinic radiation such as light in the visible, ultraviolet or infrared regions of the spectrum through a mask, or scanned by an electron beam, ion or neutron beam or X-ray radiation. Actinic radiation may be in the form of incoherent light or coherent light, for example, light from a laser. The photoresist is then imagewise developed using a suitable solvent. Subsequently, the conductive layer is etched by well known etching techniques. The circuit board may then be rinsed and dried. After the circuit lines and spaces are etched through the metal layer and the conductive layer, the remaining photoresist may be removed from the metal layer surface either by stripping with a suitable solvent or by ashing by well known ashing techniques.
It is preferred that each of the substrate, thermosetting polymer layers, thermoplastic dielectric layers and electrically conductive layers are absent, i.e. free of halogen containing fire retardant additives. More particularly, it is preferred that each of these constituents are absent, i.e. free of bromine containing fire retardant additives. As a result, the fire resistant printed circuits formed by this invention are more environmentally safe than those of the prior art.
The following non-limiting examples serve to illustrate the invention.
EXAMPLE 1
An electrodeposited copper foil of about 12 to about 35 microns is coated with about 12 microns of a crosslinked thermoplastic polyimide. A fiberglass cloth is impregnated with a non-halogenated thermosetting polyimide (such as Keramid 601), forming a prepreg. The polymer is then partially cured. The thickness of this prepreg is about 68 microns. A copper foil is then laminated to the prepreg with the polymer coating facing the prepreg. The lamination is done under a vacuum (28 inches of Hg) at 275° C., with 200 psi of pressure for 90 minutes. The resulting laminate has a dielectric thickness of approximately 90 microns and passes the UL94V0 test for flammability.
EXAMPLE 2
Example 1 is repeated except a non-halogenated epoxy replaces the thermosetting polyimide. The lamination temperature is reduced to 185° C. and the time is reduced to 60 minutes. The resulting laminate passes the UL94V0 test for flammability.
EXAMPLE 3
Example 1 is repeated except the substrate is another fiberglass and the prepreg thickness is about 115 microns. The resulting product has a dielectric thickness of about 135 microns and a rating of UL94V1.
EXAMPLE 4
Example 3 is repeated except boron nitride is incorporated into the thermosetting resin to the level of 30% by volume. The resulting product has a rating of UL94V0.
EXAMPLE 5
Example 4 is repeated except an epoxy resin is substituted for the thermosetting polyimide and lamination parameters adjusted as per Example 2. The resulting product has a rating of UL94V0.
While the present invention has been particularly shown and described with reference to preferred embodiments, it will be readily appreciated by those of ordinary skill in the art that various changes and modifications may be made without departing from the spirit and scope of the invention. It is intended that the claims be to interpreted to cover the disclosed embodiment, those alternatives which have been discussed above and all equivalents thereto.
|
This invention relates to printed circuit boards having improved fire resistance and improved environmental stability. The invention provides halogen-free fire retardant printed circuit boards incorporating potentially flammable polymers. Flame resistant thermoplastic layers prevent combustion of thermosetting polymers, as well as adding strength to the laminate, resulting in a less brittle thin core than the prior art. The flame resistant circuit board is cost efficient, environmentally safe and has excellent properties, including a decreased probability of shorting, good dielectric breakdown voltage, a smooth surface and good electrical/thermal performance.
| 8
|
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a 35 U.S.C. §371 national stage application of PCT/US2009/040665 filed Apr. 15, 2009, which claims the benefit of U.S. Provisional Patent Application No. 61/045,133 filed Apr. 15, 2008, both of which are incorporated herein by reference in their entireties for all purposes.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not Applicable.
BACKGROUND
A well capable of producing oil or gas that is deep enough will typically have a well structure to provide support for the borehole and isolation capabilities for different formations. Typically, the well structure includes an outer structure, such as a conductor housing at the surface, that is secured to conductor pipe that extends a short depth into the well. A wellhead housing is landed in the conductor housing with an outer or first string of casing extending from the wellhead and through the conductor to a deeper depth into the well. Depending on the particular conditions of the geological strata above the target zone (typically, either an oil or gas producing zone or a fluid injection zone), one or more additional casing strings (e.g., production casing, casing, tubing, production tubing, etc.) will extend through the outer string of casing to increasing depths until the well is cased to its final depth. Each string of casing is supported at the upper end by a casing hanger that lands in and is supported by the wellhead housing, each set above the previous one. Between each casing hanger and the wellhead housing, a casing hanger seal assembly is set to isolate each annular space between strings of casing. The last, and innermost, string of casing extends into the well to the final depth and is referred to as the production casing. The strings of casing between the outer casing and the production casing are typically referred to as intermediate casing strings.
When drilling and running strings of casing in the well, it is critical that the operator maintain pressure control of the well. This is accomplished by establishing a column of fluid with predetermined fluid density inside the well that is circulated down into the well through the inside of the drill string and back up the annulus around the drill string to the surface, for example. This column of density-controlled fluid balances the downhole pressure in the well. A blowout preventer system (BOP) is also used to as a safety system to ensure that the operator maintains pressure control of the well. The BOP is located above the wellhead housing and is capable of shutting in the pressure of the well, such as in an emergency pressure control situation.
After drilling and installation of the casing strings, the well is completed for production by installing a string of production tubing that extends to the producing zone within the production casing, for example. Perforations are made in the production casing to allow fluids to flow from the formation into the productions casing at the producing zone. At some point above the producing zone, a packer seals the space between the production casing and the production tubing to ensure that the well fluids flow through the production tubing to the surface. The tubing is supported by a tubing hanger assembly that lands and locks above the production casing hanger.
Various arrangements of production control valves are arranged at the wellhead in an assembly generally known as a tree, which is generally either a vertical tree or a horizontal tree. With a vertical tree, after the production hanger and production tubing are installed in the wellhead housing, the BOP is removed and the vertical tree is locked and sealed onto the wellhead. The vertical tree has one or more production bores containing actuated valves that extend vertically to the respective lateral production fluid outlets in the vertical tree. The production bores and production valves are thus in-line with the production tubing.
With a vertical tree, the tree may be removed while leaving the completion (the production tubing and hanger) in place. However, if it is necessary to pull the completion, the vertical tree must be removed and replaced by a BOP, which involves setting and testing plugs or relying on downhole valves, which may be unreliable by not having been used or tested for a long time. Moreover, removal and installation of the tree and BOP assembly generally requires robust lifting equipment, such as a rig, that have high daily rental rates, for instance. The well is also in a vulnerable condition while the vertical tree and BOP are being exchanged and neither of these pressure-control devices is in position, which is a lengthy operation that usually involves plugging and/or killing the well.
Instead of vertical trees, trees with the arrangement of production control valves offset from the production tubing, generally called horizontal trees, can be used. One type of horizontal tree is a Spool Tree™ which is shown and described in U.S. Pat. No. 5,544,707, hereby incorporated herein by reference for all purposes. A horizontal tree also locks and seals onto the wellhead housing; but the tubing hanger, instead of being located in the wellhead, locks and seals in the tree bore. After the tree is installed, the tubing string and tubing hanger are run into the tree using a tubing hanger running tool. The production port extends through the tubing hanger and seals prevent fluid leakage and production fluid flows into the corresponding production port in the tree. A locking mechanism above the production seals locks the tubing hanger in place in the tree. With the production valves offset from the production tubing, the production tubing hanger and production tubing may be removed from the tree without having to remove the horizontal tree from the wellhead housing. A problem with horizontal trees, however, is that if the tree needs to be removed, the entire completion must also be removed, which takes considerable time and also involves setting and testing plugs or relying on downhole valves, which may be unreliable by not having been used or tested for a long time. Additionally, because the locking mechanism on the tubing hanger is above and blocks access to the production port seals, the entire completion must be pulled, should the seals requiring servicing.
To manage expected maintenance costs, which are especially high for an offshore well, an operator typically selects equipment best suited for the type of maintenance he or she expects will be required. For example, a well operator must predict whether there will be a greater need in the future to pull the tree from the well for repair, or pull the completion, either for repair or for additional work in the well. Depending on the predicted maintenance events, an operator must decide whether the horizontal or vertical tree, each with its own advantages and disadvantages, is best suited for his or her purpose. For instance, with a vertical tree, it is more efficient to pull the tree and leave the completion in place. However, if the completion needs to be pulled, the tree must be pulled as well, increasing the time and expense of pulling the completion. Just the opposite is true for a horizontal tree, where it is more efficient to pull the completion, leaving the tree in place. However, if the tree needs to be pulled, the entire completion must be pulled as well, increasing the time and expense of pulling the tree. The life of the well could easily span 20 years and it is difficult to predict at the outset which capabilities are more desirable for maintenance over the life of the well. Thus, an incorrect prediction could greatly increase the cost of production over the life of the well.
BRIEF DESCRIPTION OF THE DRAWINGS
For a more detailed description of the embodiments, reference will now be made to the following accompanying drawings:
FIG. 1 is a cross section of a subsea wellhead for installation of the multi-section tree;
FIG. 2 is a cross section of the subsea wellhead and the landing section of the multi-section tree installed;
FIG. 3 is a cross-section of the multi-section tree with both tree sections installed without the completion;
FIG. 4 is a cross-section of a multi-section tree with the landing section and the valve section and the completion installed on the subsea wellhead;
FIG. 5 is a cross-section of the multi-section tree with the tree cap and production seal assembly removed;
FIG. 6 is a cross section of the multi-section tree of FIG. 5 with a protector installed on the completion;
FIG. 7 is a cross section of the multi-section tree with the valve section removed and the completion left installed with the protector; and
FIG. 8 is a cross section of the multi-section tree with the valve section removed and the completion left installed with a low profile protector.
DETAILED DESCRIPTION OF THE EMBODIMENTS
In the drawings and description that follows, like parts are marked throughout the specification and drawings with the same reference numerals, respectively. The drawing figures are not necessarily to scale. Certain features of the invention may be shown exaggerated in scale or in somewhat schematic form and some details of conventional elements may not be shown in the interest of clarity and conciseness. The present invention is susceptible to embodiments of different forms. Specific embodiments are described in detail and are shown in the drawings, with the understanding that the present disclosure is to be considered an exemplification of the principles of the invention, and is not intended to limit the invention to that illustrated and described herein. It is to be fully recognized that the different teachings of the embodiments discussed below may be employed separately or in any suitable combination to produce desired results. Any use of any form of the terms “connect”, form of the terms “connect”, “engage,” “couple,” “attach,” or any other term describing an interaction between elements is not meant to limit the interaction to direct interaction between the elements and may also include indirect interaction between the elements described. The various characteristics mentioned above, as well as other features and characteristics described in more detail below, will be readily apparent to those skilled in the art upon reading the following detailed description of the embodiments, and by referring to the accompanying drawings.
FIG. 1 illustrates a subsea wellhead 12 for installation of a multi-section tree 10 as shown in FIGS. 2-4 , that includes a landing section 14 and a valve section 16 . When the well is ready for completion, the landing section 14 and valve section 16 are lowered and installed onto the wellhead 12 using hydraulically operated collet connectors 18 , with seals being formed by appropriate gaskets. Although not shown, appropriate valves for controlling fluid production from the multi-section tree 10 are located in or attached to the valve section 16 . Also, though shown in FIGS. 2 and 3 as being installed separately, the landing section 14 and the valve section 16 may be connected on the surface and installed on the wellhead 12 at the same time.
As shown in FIG. 5 , the multi-section tree 10 is used for installing a completion that includes a tubing hanger 20 attached to and supporting the weight of a string of production tubing 22 extending below the tubing hanger 20 and into the well. The tubing hanger 20 includes an internal bore 24 aligned on one end with the bore of the production tubing 22 . The other end of the internal bore 24 exits the tubing hanger 20 in alignment with a master production port 26 in the valve section 16 for producing well fluids to the surface.
When the well is ready for completion, appropriate plugs are set downhole from the wellhead 12 to maintain fluid pressure. The blowout preventer (BOP) and riser are then removed from the wellhead 12 and the multi-section tree 10 is installed either in separate sections or both sections at the same time. The BOP and riser are then reattached to the multi-section tree 10 and the plugs removed from the well using an appropriate tool run in through the riser. When installed, the multi-section tree 10 may be pressure tested to confirm the pressure integrity of the multi-section tree 10 . A tubing hanger running tool (THRT) is then used to lower the completion, including the tubing hanger 20 and the production tubing 22 , through the riser and land the tubing hanger 20 in the multi-section tree 10 .
As shown in FIG. 4 , there are fluid connections between the tubing hanger 20 and the multi-section tree 10 . To align the tubing hanger 20 with the multi-section tree 10 , and thus align the connections, a passive vertical orientation sleeve 28 is installed to the bottom of the tubing hanger 20 . The orientation sleeve 28 also includes a ramp surface 30 that engages a key 32 on the inner surface of the landing section 14 to orient the tubing hanger 20 . As the tubing hanger 20 lands in the multi-section tree 10 , the engagement between the ramp surface 30 and the key 34 causes the tubing hanger 20 to rotate into position via a camming relationship therebetween. The tubing hanger 20 is thus aligned to its set position with the production tubing 22 extending through the orientation sleeve 28 .
As shown in FIGS. 2-4 , the multi-section tree 10 includes a fluid line connection adapter 34 between the landing section 14 and the valve section 16 . Also, extending through the orientation sleeve 28 is a fluid line 36 that extends downhole to a surface-controlled subsurface safety valve (SCSSV) (not shown), which controls the flow of fluid through the production tubing 22 from the producing zone. The fluid line 36 extends from the SCSSV and into the tubing hanger 20 and routes into a passive coupler 40 that forms a fluid tight connection with an inlet fluid connector 38 in the adapter 34 when the tubing hanger 20 lands in the multi-section tree 10 . Fluid may then route through the adapter 34 to an outlet connector 42 that is connected to a tree fluid line connector 44 . From the tree fluid line connector 44 , the fluid line routes through the valve section 16 . Extending through the valve section 16 , the tree fluid line is accessible from outside the multi-section tree 10 by a hydraulic control line 46 that extends to the surface. When connected, the hydraulic control line 46 enables surface control of the SCSSV for well operations as discussed further below. The adapter 38 may alternatively be separated into two units that make the inlet connection in the landing section 14 and the outlet connection between the landing section 14 and the valve section 16 with a fluid line being routed in between through the landing section 14 .
With the completion set in position, a lockdown actuator (not shown) actuates a locking mechanism 48 that engages a corresponding lock groove on the tubing hanger 20 . The locking mechanism thus locks the tubing hanger 20 and the production tubing 22 in place within the multi-section tree 10 . The lockdown actuator is located externally, internally, or a combination thereof in the multi-section tree 10 and may include an unlock override to unlock the locking mechanism 48 . In the set position, the tubing hanger 20 seals against the inside wall of the multi-section tree 10 at various positions, including above and below the production port 26 .
The seals above and below the production port 26 seal the interface between the internal bore 24 of the tubing hanger 20 and the production port 26 . However, not all of the seals are necessary for every application. They may be located in different locations, not included at all, or have additional secondary barriers. Alternatively, the port 26 may be sealed to the port 24 directly, for example with a face seal, seal sub, or coupler. Additionally, these seals may be made from metal and/or non-metal composition depending on the performance characteristics needed.
With the completion set and locked, the well is ready for production. To create a barrier to fluid from escaping the internal bore 24 through the top of the tubing hanger 20 , plugs 50 are run into the internal bore 24 and set above the side outlet. Alternatively, a valve located in the internal bore 24 above the side outlet may be operated to the closed position. In the exemplary embodiment, the internal profile of the tubing hanger 20 may include features that allow setting of the plug 50 either above or below the master production port 26 . A tree cap 84 may now be installed through the drilling riser or by means of a remotely operated vehicle (ROV). The BOP and riser may then be removed from the multi-section tree 10 and retrieved. Using the hydraulic control line 46 , hydraulic fluid may be used to open the downhole SCSSV and allow fluid production to flow from the production tubing 22 , through the tubing hanger 20 , and into the production port 26 for flow to the surface or any other desired location. Additionally, as shown in FIGS. 3 and 4 , the multi-section tree 10 allows for fluid communication from the production tubing 22 annulus below the tubing hanger 20 to the bore of the multi-section tree 10 above the tubing hanger 20 . Communication with the production tubing 22 annulus allows for pressure control downhole should pressure in the annulus need to be relieved during production. The fluid communication is controlled using an externally mounted annulus valve 54 that is in fluid communication on one side with a valve section bleed port 52 . On the other end, the annulus valve 54 communicates with the annulus below the tubing hanger 20 by connection with a landing section bleed port 60 . Also, the multi-section tree 10 includes a back up annulus valve 58 that further connects with an extra, manual connects with an extra, manual annulus block off (not shown). The annulus valve 54 and back up annulus valve 58 may be any appropriate standard API valve. The annulus valve 54 and the back up annulus valve 58 do not need to be externally connected. Instead, as shown in FIG. 4 , the annulus valve 54 and back up annulus valve 58 may be connected through an additional port 62 within the valve section 16 and port 64 within the landing section 14 .
Also shown in FIGS. 3 and 4 , the multi-section tree 10 includes an isolation sleeve 66 that includes seals on its outer surface to form an environment barrier between the inside wall of the landing section 14 and the wellhead 12 . Although the isolation sleeve 66 is located in the bore, the annulus surrounding the production tubing 22 is not blocked and fluid is allowed to pass around the orientation tool 28 . Another isolation sleeve (not shown) may also be included between the valve section 16 and landing section 14 .
At some point in the life of the well, the well may need to be accessed for additional drilling, maintenance, or other reasons. As shown in FIG. 3 , to access the well the completion may be pulled from the multi-section tree 10 so that drilling equipment and/or tools may be run into the well. To pull the completion, both the BOP and the riser are installed to the top of the multi-section tree 10 . A THRT is run through to the multi-section tree 10 through the riser and engaged with the tubing hanger 20 . The lockdown actuator then releases the locking mechanism 48 so that the THRT may retrieve the completion from the multi-section tree 10 . Because the passive coupler 40 is a vertical connection, the removal of the tubing hanger 20 disconnects the hydraulic fluid line 36 from the inlet fluid connector 38 of the adapter 34 as the completion is pulled from the multi-section tree 10 . With the completion pulled and the well now accessible, work in the well may be performed without also having to pull the multi-section tree 10 from the well. Leaving the multi-section tree 10 in place thus saves considerable time and money for the well operator who does not have to go through the extra steps of removing and then reinstalling the multi-section tree 10 on the wellhead 12 . Moreover, the multi-section tree 10 , when bifurcated, is lighter than conventional trees, allowing installation with less robust equipment that is generally less expensive.
The same can also be said that at some point in the life of the well, the valves of the multi-section tree 10 may need to be serviced or replaced. As shown in FIGS. 5-8 , the valve section 16 may be pulled by itself, leaving the landing section 14 and the completion in place on the wellhead 12 . Before the valve section 16 is removed, a second environmental barrier 15 is established in addition to closing the SCSSV in the production bore below the side outlet. The second barrier may be established by ROV interface and/or by access through a completion riser. A preferred method is to close an additional valve located in the production bore below the side outlet using ROV interface to inject hydraulic fluid to the ITC which in turn injects fluid through the tubing hanger and consequently to operate the valve located in the production bore, Alternatively, the ITC may be operated open water by an ROV or by a tool run through a riser and BOP to re-position the plug 50 from above the outlet to below the outlet ( FIGS. 4 and 5 ). If a riser and BOP are attached, plug 50 may be removed and another plug then installed below the side outlet. Unlike when removing the completion, however, the locking mechanism 48 is left in the engaged position. As discussed more fully below, the seals in the tubing hanger 20 on either side of the production port 26 may be included on a removable seal assembly 80 that surrounds the tubing hanger 20 . Although not necessary, typically the seal assembly is removed as shown in FIG. 5 and a protector 86 that may be temporary is threaded onto the exposed tubing hanger 20 as shown in FIG. 6 .
The hydraulically controlled upper collet connector 18 is then disengaged, and the valve section 16 may then be removed and lifted by attaching an ROV assisted Mechanical Tree Handling Tool coupled to a soft line extending down from a floating vessel, or by the riser and BOP if attached. The design of the coupler 40 allows the vertical separation of the valve section 16 from the landing section 14 . The landing section 14 and the completion are left in place on the wellhead 12 . With the valve section 16 now retrieved, the service and/or replacement work may be performed without having to pull the landing section 14 and the completion from the well. When the well is not being accessed, the protector 86 may remain in place on the tubing hanger 20 . Alternatively, a lower profile protector 88 shown in FIG. 8 may be placed over the tubing hanger 20 and locked into the landing section 14 using any suitable locking engagement. Leaving the landing section 14 and completion in place thus saves considerable time and money for the well operator who does not have to go through the extra steps of removing and then reinstalling the completion just to be able to service the valve section 16 .
As previously mentioned and as shown in FIGS. 4-8 , the seals in the tubing hanger 20 on either side of the production port 26 may be included on a replaceable seal assembly 80 that surrounds the tubing hanger 20 . The seal assembly 80 may also be pulled from the tubing hanger 20 either by itself or in conjunction with pulling the valve section 16 or pulling the tubing hanger 20 . The seal assembly 80 includes the seals installed on a retrievable body 82 that slides down over the tubing hanger 20 and is held in place using a tree cap 84 as shown or it's own retention device. The tree cap 84 can be installed above the tubing hanger 20 as a second barrier and/or a second lockdown for the tubing hanger 20 . The tree cap 84 can lock to the tree profile and/or the tubing hanger profile and seal to the tree profile, the tubing hanger profile, or both. The tree cap 84 could be ROV installable and retrievable or deployed and removed inside a riser or a combination thereof. The tree cap 84 could also be used to install or retrieve the hanger seal assembly 80 or to shift the seal assembly 80 to another position, e.g., rotate the seal assembly 80 to close off fluid flow into the production port 26 . It should also be appreciated that the tree cap 84 may be replaced with any suitable engagement mechanism, such as a threaded connection or lockable dogs engaging a profile on the tubing hanger 20 .
Because the locking mechanism 48 is located below the production port 26 , the top of the tubing hanger 20 is accessible from the bore of the multi-section tree 10 above the tubing hanger 20 . Thus, should the seal assembly 80 need repair or replacement, an appropriate tool or a subsea remote operated vehicle (ROV) may be used to replace the seal assembly 80 without having to pull the entire completion. The ROV may be used to engage the top of the multi-section tree 10 and with the SCSSV set in the closed position, the ROV may remove the seal assembly 80 for repair or replacement.
When the operation is compete, the ROV disengages the multi-section tree 10 and the SCSSV is set to the open position to resume production. With the seal assembly 80 being retrievable from the top of the tubing hanger 20 , the service and/or replacement work may be performed without having to pull the completion from the well. Leaving the completion in place thus saves considerable time and money for the well operator who does not have to go through the extra steps of removing and then reinstalling the completion just to be able to service the production production port 26 seals. The seal assembly 80 may be retrieved and re-installed with the tree valve section 16 or with the tubing hanger 20 as they are each individually retrieved or installed as discussed above. The seal assembly 80 may also be retrieved or installed using ROV interface or using a separate tool run through the riser. The seal assembly 80 may also be retrieved or installed by means or assistance of the tree cap 84 as shown, in conjunction with the additional methods just described.
While specific embodiments have been shown and described, modifications can be made by one skilled in the art without departing from the spirit or teaching of this invention. The embodiments as described are exemplary only and are not limiting. Many variations and modifications are possible and are within the scope of the invention. Accordingly, the scope of protection is not limited to the embodiments described, but is only limited by the claims that follow, the scope of which shall include all equivalents of the subject matter of the claims.
|
A subsea well production system for a well including a subsea wellhead. The system includes a multi-section production tree that includes a landing section engageable with the subsea wellhead and including a landing section bore. The tree also includes a valve section separate from and engageable with the landing section, the valve section including a lateral production port extending through a valve section wall and in communication with a valve section bore. A production tubing supported by a tubing hanger is installed and supported in the landing section bore such that the tubing hanger extends into the valve section bore. The tubing hanger and production tubing are retrievable through the section bores without disengaging the valve section from the landing section. The valve section is also disengageable from the landing section with the tubing hanger remaining in the landing section.
| 4
|
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation of U.S. patent application Ser. No. 11/580,335, filed Oct. 13, 2006 now U.S. Pat. No. 7,382,959, entitled “OPTICALLY ORIENTED THREE-DIMENSIONAL POLYMER MICROSTRUCTURES,” the entire content of which are incorporated herein by reference.
FIELD OF THE INVENTION
The present invention relates to patterning one or more polymer waveguides to form an ordered three-dimensional (3D) microstructure and/or a system and method to fabricate the one or more polymer waveguides.
BACKGROUND OF THE INVENTION
An ordered three-dimensional (3D) microstructure is an ordered 3D structure at the micrometer scale. Currently, polymer cellular materials that are mass produced are created through various foaming processes, which all yield random (not ordered) 3D microstructures. Techniques do exist to create polymer materials with ordered 3D microstructures, such as stereolithography techniques; however, these techniques rely on a bottom-up, layer-by-layer approach which prohibits scalability.
A stereolithography technique is a technique that builds a 3D structure in a layer-by-layer process. This process usually involves a platform (substrate) that is lowered into a photo-monomer (photopolymer) bath in discrete steps. At each step, a laser is scanned over the area of the photo-monomer that is to be cured (polymerized) for that particular layer. Once the layer is cured, the platform is lowered a specific amount (determined by the processing parameters and desired feature/surface resolution) and the process is repeated until the full 3D structure is created. One example of such a stereolithography technique is disclosed in Hull et al., “Apparatus For Production Of Three-Dimensional Objects By Stereolithography,” U.S. Pat. No. 4,575,330, Mar. 11, 1986, which is incorporated by reference herein in its entirety.
Modifications to the above described stereolithography technique have been developed to improve the resolution with laser optics and special resin formulations, as well as modifications to decreasing the fabrication time of the 3D structure by using a dynamic pattern generator to cure an entire layer at once. One example of such a modification is disclosed in Bertsch et al., “Microstereolithography: A Review,” Materials Research Society Symposium Proceedings, Vol. 758, 2003, which is incorporated by reference herein in its entirety. A fairly recent advancement to the standard stereolithography technique includes a two-photon polymerization process as disclosed in Sun et al., “Two-Photon Polymerization And 3D Lithographic Microfabrication,” APS, Vol. 170, 2004, which is incorporated by reference herein in its entirety. However, this advance process still relies on a complicated and time consuming layer-by-layer approach.
3D ordered polymer cellular structures have also been created using optical interference pattern techniques, also called holographic lithography; however, structures made using these techniques have an ordered structure at the nanometer scale and the structures are limited to the possible interference patterns, as described in Campbell et al., “Fabrication Of Photonic Crystals For The Visible Spectrum By Holographic Lithography,” NATURE, Vol. 404, Mar. 2, 2000, which is incorporated by reference herein in its entirety.
Previous work has also been done on creating polymer optical waveguides. A polymer optical waveguide can be formed in certain photopolymers that undergo a refractive index change during the polymerization process. If a monomer that is photo-sensitive is exposed to light (typically UV) under the right conditions, the initial area of polymerization, such as a small circular area, will “trap” the light and guide it to the tip of the polymerized region due to this index of refraction change, further advancing that polymerized region. This process will continue, leading to the formation of a waveguide structure with approximately the same cross-sectional dimensions along its entire length. The existing techniques to create polymer optical waveguides have only allowed one or a few waveguides to be formed and these techniques have not been used to create a self-supporting three-dimensional structure by patterning polymer optical waveguides.
As such, there continues to be a need to create polymer cellular materials with ordered microstructures on a large and useful scale using a simple technique.
SUMMARY OF THE INVENTION
An aspect of the present invention provides a method and system of fabricating polymer cellular (porous) materials with an ordered three-dimensional (3D) microstructure using a simple technique. These cellular materials are created from a pattern of self-propagating polymer waveguides, which are formed in an appropriate photopolymer. This method and system can create truly 3D microstructures without building the structures layer-by-layer as with stereolithography and other prototyping techniques.
Another aspect of the present invention creates polymer cellular materials with ordered microstructures on a large and useful scale.
In an embodiment of the present invention, a system for forming at least one polymer waveguide is provided. The system includes at least one light source selected to produce a light beam; a reservoir having a photo-monomer adapted to polymerize by the light beam; and a patterning apparatus adapted to guide a portion of the light beam into the photo-monomer to form the at least one polymer waveguide through a portion of a volume of the photo-monomer.
In one embodiment of the system, the at least one light source includes at least one collimated light source, the light beam is a collimated light beam, the patterning apparatus includes a mask having at least one aperture and positioned between the at least one collimated light source and the reservoir, and the at least one aperture is adapted to guide the portion of the collimated light beam into the photo-monomer to form the at least one polymer waveguide through the portion of the volume of the photo-monomer.
In one embodiment of the system, the at least one polymer waveguide includes a plurality of waveguides, and the at least one aperture is a single aperture adapted to form the plurality of waveguides.
In one embodiment of the system, the at least one collimated light source is a single collimated light source, the plurality of waveguides are formed from a plurality of exposures of the collimated light beam of the single collimated light source with the mask having the single aperture, and the single collimated light source is adapted to move with respect to the mask between each of the exposures.
In one embodiment of the system, the at least one collimated light source includes a plurality of collimated light sources adapted to produce and direct a plurality of collimated light beams at different angles with respect to a point of the mask, and the plurality of waveguides are formed from a single exposure of the plurality of collimated light beams of the plurality of collimated light sources with the mask having the single aperture.
In one embodiment of the system, the at least one polymer waveguide includes a plurality of waveguides, and the at least one aperture includes a plurality of apertures adapted to form the plurality of waveguides. Here, the plurality of polymer waveguides may be a three-dimensional (3D) ordered polymer microstructure. Also, a spacing between the plurality of waveguides in the 3D ordered polymer microstructure may correspond with a pattern of the plurality of apertures.
In one embodiment of the system, the mask is in contact with at least one surface of the monomer.
In one embodiment of the system, the system further includes a substrate substantially transparent to the collimated light beam interposed between the mask and the photo-monomer.
In another embodiment of the present invention, a method for forming at least one polymer waveguide is provided. The method includes: securing a volume of a photo-monomer; securing a mask having at least one aperture between at least one collimated light source and the volume of the photo-monomer; and directing a collimated light beam from the at least one collimated light source to the mask for a period of exposure time so that a portion of the collimated beam passes through the mask and is guided by the at least one aperture into the photo-monomer to form at least one waveguide through a portion of the volume of the photo-monomer.
In one embodiment of the method, the at least one waveguide has a cross sectional geometry substantially matching the designed aperture geometry on the mask.
In one embodiment of the method, the collimated light source has an incident power, and the period of exposure time is determined to base on the incident power and a desired length of the at least one waveguide.
In one embodiment of the method, the at least one polymer waveguide includes a plurality of waveguides, and the at least one aperture is a single aperture adapted to form the plurality of waveguides.
In one embodiment of the method, the at least one collimated light source is a single collimated light source, the plurality of waveguides are formed from a plurality of exposures of the collimated light beam of the single collimated light source with the mask having the single aperture, and the single collimated light source is adapted to move with respect to the mask between each of the exposures.
In one embodiment of the method, the at least one collimated light source includes a plurality of collimated light sources adapted to produce and direct a plurality of collimated light beams at different angles with respect to a point of the mask, and the plurality of waveguides are formed from a single exposure of the plurality of collimated light beams of a single collimated light source or of the plurality of collimated light sources with the mask having the single aperture.
In one embodiment of the method, the at least one polymer waveguide includes a plurality of waveguides, and the at least one aperture includes a plurality of apertures adapted to form the plurality of waveguides. Here, the method may further include removing any uncured photo-monomer to leave behind a three-dimensional (3D) ordered polymer microstructure. Here, the plurality of polymer waveguides may be a three-dimensional (3D) ordered polymer microstructure. Also, a spacing between the plurality of waveguides in the 3D ordered polymer microstructure may correspond with a pattern of the plurality of apertures.
In yet another embodiment of the present invention, a three-dimensional (3D) ordered polymer microstructure is provided. The 3D ordered polymer microstructure includes: a plurality of waveguides having a first waveguide extended along a first direction, a second waveguide extended along a second direction and patterned with the first waveguide, and a third waveguide extended along a third direction and patterned with the first waveguide and the second waveguide. Here, the plurality of waveguides are formed by polymers and patterned to form the 3D ordered microstructure.
In one embodiment of the 3D ordered polymer microstructure, the waveguides are patterned and formed by securing a volume of a photo-monomer, securing a mask having a plurality of apertures between at least one collimated light source and the volume of the photo-monomer, and directing a collimated light beam from the at least one collimated light source to the mask for a period of exposure time so that a portion of the collimated beam passes through the mask and is guided by the apertures into the photo-monomer to form the plurality of waveguides through a portion of the volume of the photo-monomer.
In yet a further embodiment of the present invention, a method for forming a plurality of patterned polymer waveguides is provided. The method includes: securing a volume of a photo-monomer; and patterning light from at least one light source for a period of exposure time in the photo-monomer to form the plurality of patterned polymer waveguides through a portion of the volume of the photo-monomer.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, together with the specification, illustrate exemplary embodiments of the present invention, and, together with the description, serve to explain the principles of the present invention.
FIG. 1 is a schematic diagram of a system to form a single waveguide from a single collimated beam through a single aperture pursuant to aspects of the present invention;
FIG. 2 illustrates examples of different aperture shapes pursuant to aspects of the present invention;
FIG. 3 is a schematic diagram of a system to form multiple waveguides from a single collimated beam or multiple collimated beams through a single aperture pursuant to aspects of the present invention;
FIG. 4 is a schematic diagram of a system to form a 3D structure (e.g., a 3D ordered polymer microstructure) formed from multiple waveguides created using a single collimated beam or multiple collimated beams through multiple apertures pursuant to aspects of the present invention;
FIG. 5 a illustrates an example of a square mask pattern (or a square mask aperture pattern) pursuant to aspects of the present invention;
FIG. 5 b illustrates an example of a hexagonal mask pattern (or a hexagonal mask aperture pattern) pursuant to aspects of the present invention;
FIG. 6 is a process flow diagram for forming one or more polymer waveguides pursuant to aspects of the present invention;
FIGS. 7 a , 7 b , 7 c , and 7 d are SEM micrographs of a sample 3D polymer microstructure pursuant to aspects of the present invention;
FIG. 8 is a 3D diagram for illustrating a formation of a 3D ordered polymer microstructure pursuant to aspects of the present invention; and
FIG. 9 is another 3D diagram for illustrating a formation of a 3D ordered polymer microstructure pursuant to aspects of the present invention.
DETAILED DESCRIPTION
In the following detailed description, only certain exemplary embodiments of the present invention are shown and described, by way of illustration. As those skilled in the art would recognize, the described exemplary embodiments may be modified in various ways, all without departing from the spirit or scope of the present invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not restrictive.
According to one embodiment of the present invention, a fixed light input (collimated UV light) is used to cure (polymerize) polymer optical waveguides, which can self-propagate in a 3D pattern. The propagated polymer optical waveguides form an ordered 3D microstructure that can be polymerized without anything moving during the formation process to provide a path to large scale, inexpensive production.
The formed polymer cellular materials (3D microstructures) can be used as is, or as templates to form other materials with ordered 3D microstructures, such as metals or ceramics. Because of the simplicity in the processing, as well as the versatility in end material options, embodiments of the present invention have a wide range of applications, such as in lightweight structural materials; energy absorbing materials; heat transfer applications; deployable structures (space structures); conformable core structures; acoustic damping; hook and loop attachments; compliant structures; optics for sub-micron waveguide formation; single body casting/net shape manufacturing; alternate shapes for waveguide members (3D honeycomb); functionally graded structures; heat exchanger/insulator structures; 3D battery/fuel cell structures; thermal switch structures; catalyst support structures; filtration/separation structures; wicking materials/moisture control structures; directional optical coupler/flexible display structures; distributed lighting structures; electrical interconnects; sensor supports with high surface areas; biological growth templates; flexible body/reactive armors; stealth coatings; high friction/high wear surfaces; waveguides for other energy sources; flame retardant foams; etc.
As disclosed in Monro et al. “Topical Review Catching Light In Its Own Trap,” Journal Of Modern Optics, 2001, Vol. 48, No. 2, 191-238, which is incorporated by reference herein in its entirety, some liquid polymers, referred to as photopolymers, undergo a refractive index change during the polymerization process. The refractive index change can lead to a formation of polymer optical waveguides. If a monomer that is photo-sensitive is exposed to light (typically UV) under the right conditions, the initial area of polymerization, such as a small circular area, will “trap” the light and guide it to the tip of the polymerized region, further advancing that polymerized region. This process will continue, leading to the formation of a waveguide structure with approximately the same cross-sectional dimensions along its entire length.
One embodiment of the present invention creates a polymer cellular material with an ordered 3D microstructure by creating a pattern of self-propagating optical waveguides in an appropriate photopolymer. A formation of a single polymer waveguide will be described in more detail below, followed by a more detailed description on how to pattern these polymer waveguides to form an ordered 3D microstructure.
Formation of Single Polymer Waveguide with Single Aperture
Referring to FIG. 1 , a system to form a single optical waveguide according to an embodiment of the present invention includes a collimated light source 100 , a reservoir (mold) 110 having a volume of monomer 120 that will polymerize at a wavelength of a collimated light beam provided by the light source 100 , and a patterning apparatus, such as a mask 130 with a single aperture (open area) 140 of a given shape and dimension. For example, as shown FIG. 2 , the aperture 140 may be in a shape of a triangle, a pentagon, a hexagon, a polygon, an oval, a star, etc.
Referring back to FIG. 1 , a single collimated beam is directed through the aperture 140 in the mask 130 to the monomer 120 . Between the mask 130 and the monomer 120 , there may be a substrate 150 . The substrate can be composed of a material, such as glass, Mylar, and other suitable materials that will transmit the incident light beam to the monomer 120 . That is, in one embodiment of the present invention, the substrate 150 is substantially transparent to the incident light beam. On the surface of the monomer 120 , in the area exposed to a portion of the light beam, an optical waveguide 160 will begin to polymerize.
In one embodiment, the index of refraction change between the polymer and monomer will “trap” and “focus” the light in the polymer and guide the polymerization process. Due to this self-guiding/self-focusing effect, the polymerized waveguide 160 will form with an approximately constant cross-section and a length much greater than the cross-sectional dimensions. The direction in which this polymer waveguide 160 will grow is dependent on the direction of the incident beam. The cross-section of the polymer waveguide 160 is dependent on the shape and dimensions of the incident collimated beam, which in turn is dependent on the shape and dimensions of the aperture 140 in the mask 130 . The length to which the polymer waveguide 160 can “grow” is dependent on a number of parameters including the size, intensity, and exposure time of the incident beam, as well as the light absorption/transmission properties of the photopolymer. The time in which it takes to form a polymer waveguide depends on the kinetics of the polymerization process.
To put it another way, in one embodiment, when the portion of the collimated light beam passes through the mask 130 and first hits the liquid photo-monomer 120 , a polymer “tip” is formed. There is a large enough difference between the refractive index of the monomer and the polymer to cause internal reflection of the light in the polymer—this is the same principle as when light travels through fiber optics. Because of this internal reflection effect, the light is essentially focused to the tip of the polymer, causing the monomer at the tip to cure (i.e. polymerize). This will also propagate the tip of the polymer through the liquid monomer 120 , forming the self-propagating polymer optical waveguide 160 . In addition, because of this internal reflection affect, the waveguide 160 can be “very” long with respect to the cross-sectional dimensions, all while maintaining a constant cross-section through its length. Eventually the formation of the polymer waveguide 160 will stop at the end of the monomer reservoir 110 , or it will stop prior to that if there is not enough energy to polymerize the monomer 120 . This happens because the polymer itself will absorb some of the portion of the collimated light beam passing through the mask 130 .
Formation of Multiple Polymer Waveguides with Single Aperture
As mentioned above, the direction in which the polymer waveguide will form is dependent on the angle of the incident collimated beam. If the collimated beam is perpendicular to a flat monomer surface (as shown in FIG. 1 ), the polymer waveguide will propagate, or grow perpendicular to the monomer surface. By contrast, referring to FIG. 3 , if the incident collimated beam is directed at an angle, the polymer waveguide will grow at an angle relative to the monomer surface. Note this angle will be affected by the change in refractive index between the air and/or substrate and the monomer due to refraction.
That is, as shown in FIG. 3 , a system to form multiple optical waveguides 260 according to an embodiment of the present invention includes one or more collimated light sources 200 , a reservoir (mold) 210 having a volume of monomer 220 that will polymerize at a wavelength of collimated light beams provided by the light sources 200 , and a patterning apparatus, such as a mask 230 with a single aperture (open area) 240 of a given shape and dimension. Between the mask 230 and the monomer 220 , there may be a substrate 250 .
Through the single aperture 240 as described above, the multiple waveguides 260 can be formed by directing multiple collimated beams at different angles through the aperture 240 . That is, in one embodiment of the invention, a single collimated light source is used. Multiple waveguides are formed from a plurality of exposures of the collimated light beam of the single collimated light source with a mask having a single aperture, and the single collimated light source is adapted to move with respect to the mask between each of the exposures.
Alternatively, the multiple waveguides 240 can be formed one at a time through the single aperture 240 by simply changing the incident angle of a single collimated beam after the formation of each of the waveguides 240 . That is, in another embodiment of the present invention, multiple collimated light sources are adapted to produce and direct multiple collimated light beams at different angles with respect to a point of a mask having a single aperture. Multiple waveguides are formed from a single exposure of the multiple light beams of the multiple collimated light sources with the mask having the single aperture.
Formation of 3D Microstructure Using Patterned Optical Waveguides
The technique to create a 3D polymer microstructure is based on the above described approach for forming multiple optical waveguides with a single aperture. However, instead of using a mask with a single aperture, a mask with a two-dimensional pattern of apertures is used to create a three-dimensional polymer microstructure as is shown in FIG. 4 .
Referring to FIG. 4 , a system to form a 3D polymer microstructure according to an embodiment of the present invention includes one or more collimated light sources 300 , a reservoir (mold) 310 having a volume of monomer 320 that will polymerize at a wavelength of collimated light beams provided by the light sources 300 , and a patterning apparatus, such as a mask 330 with multiple apertures (open areas) 340 . Each of the apertures 340 has a given shape and dimension substantially matching a cross section geometry of a waveguide (e.g., waveguide 360 a ). Between the mask 330 and the monomer 320 , there may be a substrate 350 . Here, in FIG. 4 , a truly 3D network can be formed because the intersecting polymer waveguides 360 will simply polymerize together, but will not interfere with waveguide propagation. Also, the spacing between the plurality of waveguides 360 corresponds with the pattern of the plurality of apertures 340 . The pattern of the apertures 340 may, for example, be in a square pattern as shown in FIG. 5 a and/or in a hexagonal pattern as shown in FIG. 5 b . The hole (aperture) spacing, i.e., distance between apertures 340 in the mask 330 , and the number of waveguides 360 formed from each of the apertures 340 will determine the open volume fraction (i.e. open space) of the formed 3D microstructure.
As such, through the embodiment of FIG. 4 , a 3D microstructure (or a 3D ordered polymer microstructure) can be designed for a given application. The design parameters include: 1) the angle and pattern of the polymer waveguides with respect to one another, 2) the packing, or relative density of the resulting cellular structure (or the open volume fraction), and 3) the cross-sectional shape and dimensions of the polymer waveguides.
FIG. 8 is a 3D diagram for illustrating a formation of a 3D ordered polymer microstructure pursuant to aspects of the present invention, and FIG. 9 is another 3D diagram for illustrating a formation of a 3D ordered polymer microstructure pursuant to aspects of the present invention.
In more detail, FIG. 6 shows a method of forming a 3D ordered microstructure according to an embodiment of the present invention. As illustrated in FIG. 6 , a photo-monomer is selected in block 1000 . In block 1010 , a volume of the selected photo-monomer is secured (e.g., in a reservoir). A mask geometry is designed based on a desired 3D structure in block 1020 . A patterning apparatus, such as a mask having the designed geometry, is secured in block 1030 . Here, the secured mask has at least one aperture between at least one collimated light source and the volume of the selected photo-monomer. In addition, the mask may be in contact with the monomer or separated by a substrate (e.g., by a UV transparent substrate).
In block 1040 , an appropriate exposure time is determined based on incident power of a collimated light beam from the at least one collimated light source (e.g., an incident power of an UV light) and a desired length of one or more waveguides. The collimated light beam from the at least one collimated light source is directed to the mask for a period of exposure time so that a portion of the collimated beam passes through the mask and is guided by the at least one aperture into the photo-monomer to form at least one waveguide through a portion of the volume of the photo-monomer. Here, the at least one waveguide has a cross sectional geometry substantially matching the designed aperture geometry on the mask.
In one embodiment as shown in block 1050 , multiple collimated beams at different incident directions and/or angles are directed through the mask for a given amount of time.
Alternatively, as shown in blocks 1050 a , a single collimated beam at a given direction and angle is directed through the mask for a given amount of time. Then, at block 1050 b , the collimated light beam is moved with respect to the mask and the exposure is repeated.
Then, at block 1060 , any uncured photo-monomer is removed to leave behind a 3D ordered polymer microstructure. Here, in one embodiment, the plurality of polymer waveguides are used to form the 3D ordered polymer microstructure, and the 3D ordered polymer microstructure corresponds with the pattern of the plurality of apertures.
Patterning Large Area Microstructures
The resulting 3D polymer microstructure can be formed in seconds in the area where exposed to the incident collimated beam. Since the incident light and the monomer remain fixed with respect to one another during the formation of a polymer waveguide, the exposure area of the collimated beam(s) can be scanned over a larger surface area of monomer, leading to the formation of large-area structures. Alternatively, in one embodiment, a volume of monomer can continuously be fed under a fixed incident light pattern (created from a mask and collimated light) leading to a path for mass production.
Removing Monomer
As described, once the polymer cellular structure is formed in the volume of monomer, the remaining un-polymerized material (monomer) is removed leaving an open cellular polymer material that is the ordered 3D microstructure.
Hereafter, an embodiment of the present invention will be described with reference to the following example. In the following example, a solvent that will dissolve the monomer (but not the polymer) is used to aid in the monomer removal.
EXAMPLE
In forming a 3D polymer structure, a mold with an open top is filled with a monomer that will polymerize in the UV regime. The depth of this mold cavity is approximately 6 mm and was filled with a commercial photo-monomer. This commercial photo-monomer polymerizes via free-radical polymerization when exposed to UV light (wavelength between 250-400 nm), and is highly transmissive to light in this wavelength range—a property required for the formation of polymer waveguides. Non-limiting examples of the photo-monomer include any suitable free-radical photopolymer materials, such as urethanes (polyurethanes), acrylates, methacrylates, cationic polymers, such photo-cured epoxies, etc.
A glass substrate that is substantially transparent to UV light is placed on the top surface of the monomer and a Mylar mask is placed on top of the substrate (e.g., see FIG. 4 ). For this embodiment, the substrate is used to provide space between the mask and the monomer so the polymerized cellular structure does not attach to the mask. In addition to acting as a spacer, the glass substrate helps to hold existing waveguides in place during subsequent waveguide formation.
The Mylar mask used in this embodiment has an array of 150 μm diameter holes arranged in a square pattern (e.g., see FIG. 5 a ). A single collimated UV beam from a Mercury arc lamp was directed through the mask at an angle approximately 45° with respect to the substrate. The power of the incident beam was approximately 3 mW/cm 2 and the exposure time was 100 s. Holding the incident angle with respect to the substrate fixed, the collimated beam was rotated 90° around the substrate normal and exposed for another 100 s. This rotate and exposure step was repeated two more times, giving four total exposures. The 2D schematic of the resulting 3D microstructure from this particular embodiment is substantially the same as the embodiment of FIG. 4 , and the 3D schematics of the resulting 3D microstructures from this particular embodiment are substantially the same as the embodiments of FIGS. 8 and 9 .
SEM micrographs of a sample 3D polymer microstructure that can be formed by the above described exemplary technique are shown in FIGS. 7 a , 7 b , 7 c , and 7 d.
RECAP OF CERTAIN EMBODIMENTS OF THE PRESENT INVENTION
A single polymer waveguide can be created from a single collimated beam and a mask with a single aperture.
Multiple polymer waveguides can be created from multiple exposure time using a single collimated beam and a mask with a single aperture and moving the collimated beam with respect to the mask between each exposure.
Multiple polymer waveguides can be created from a single exposure time using multiple collimated beams at different incident angles and a mask with a single aperture.
A three-dimensional ordered polymer microstructure can be made from multiple polymer waveguides that are created from a mask with multiple apertures.
The shape and dimensions of the polymer waveguides is dependent on the shape and dimensions of the aperture(s) in the mask.
The relative angle(s) of the waveguides in the 3D structure is dependent on the incident angle of the collimated beam.
The length of the individual polymer waveguides that include the 3D structure is dependent on the photopolymer and the light source.
Any photopolymer that can be used to create optical waveguides can be used to create a 3D ordered polymer microstructure.
The area of exposure of the collimated beam(s) and the monomer can be moved with respect to each other to create a structure that is larger than the available exposure area. (This leads to mass/continuous production.)
In view of the foregoing, certain embodiments of the present invention provide methods and systems of creating one or more waveguides and/or patterning these waveguides to form a 3D microstructure. The systems and methods include the use of mask and collimated light.
While the invention has been described in connection with certain exemplary embodiments, it is to be understood by those skilled in the art that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications included within the spirit and scope of the appended claims and equivalents thereof.
|
A three-dimensional (3D) ordered polymer microstructure having a length, a width and a height and including a plurality of waveguides that can be formed utilizing a mask and collimated light. The plurality of waveguides includes a first waveguide having a first finite propagation distance extended along a first direction, a second waveguide having a second finite propagation distance extended along a second direction and a third waveguide having a third finite propagation distance extended along a third direction. Here, only one of the length, width and height of the 3D ordered polymer microstructure is limited by the first finite propagation distance of the first waveguide, the second finite propagation distance of the second waveguide and the third finite propagation distance of the third waveguide.
| 6
|
This invention relates to combustion turbine power plant and more particularly, to method of operating a combustion turbine power plant so as to restore a loss of power which may occur when the combustion turbine assembly is operating at high ambient temperature or with low air density and/or to generate power which exceeds a power production of a conventional combustion turbine assembly by use of complimentary air flow from a compressed air storage.
BACKGROUND OF THE INVENTION
A combustion turbine power plant is the power plant of choice for supplying peak power. For an overwhelming majority of electric power customers (in the U.S. and abroad) power consumption reaches its peak during the summertime, the time when the power production of combustion turbines is at its lowest, due to high ambient temperature. The simplified explanation of the reduced power production is that the high ambient temperature with associated lower inlet air density, reduces mass flow through a combustion turbine assembly with a respective reduction of the power produced. FIGS. 1a, 1b, and 1c present simplified heat and mass balances of a conventional General Electric Frame 7 EA combustion turbine assembly 12 operating at three ambient temperatures: 59 F. (FIG. 1a), 0 F. (FIG. 1b) 90 F. (FIG. 1c). The combustion turbine 12 includes a compressor 14, an expansion turbine 16, a combustor 18 which feeds heated combustion product gas to the expansion turbine 16. The expansion turbine 16 is coupled to drive the compressor 14 and an electric generator 20, which is coupled to the electric grid 17.
FIGS. 1a-1c demonstrate that the conventional General Electric combustion turbine assembly, rated at 84.5 MW at ISO conditions (59 F. with 60% relative humidity), will produce maximum power of approximately 102.5 MW when the ambient temperature is 0 F., and will drop power to approximately 76.4 MW at 90 F. The significant power loss by a combustion turbine assembly during high ambient temperature periods requires a utility to purchase additional peak capacities to meet summer peak demands. Power loses for a combined cycle power plant operating at high ambient temperatures are similar to those of combustion turbine assemblies.
There are conventional methods to partially restore the loss power of combustion turbines/combined cycle plants during high ambient temperature periods: evaporative cooling and various combustion turbine inlet air chillers (mechanical or absorption type). These methods result only in partial restoration of combustion turbine power while significantly increasing capital costs, which is not always justified for an operation limited to time periods with high ambient temperatures.
Accordingly, there is a need to develop a method which will allow a combustion turbine assembly to operate at maximum power, regardless of ambient temperature.
Similar power loss problems exist in the case of a combustion turbine assembly installed at high elevation. The problem in these applications is associated with lower air density and a corresponding loss of consumption turbine power. There are currently no methods to restore power loss associated with high elevation applications.
Accordingly, a need exists to develop a method which will allow a combustion turbine assembly to maintain maximum power even when operating at high elevations.
SUMMARY OF THE INVENTION
An object of the invention is to fulfill the needs referred to above. In accordance with the principles of the present invention, these objectives are obtained by a method of ensuring that a combustion turbine power generation system may operate at maximum allowable power at elevated ambient temperature and/or at low air density and/or operate at a power which exceeds that of a conventional combustion turbine assembly by providing complimentary air from an air storage. The method includes providing at least one combustion turbine assembly including a compressor, an expansion turbine operatively associated with the compressor, a generator coupled with the expansion turbine; a combustor feeding the expansion turbine; flow path structure fluidly connecting an outlet of the compressor to an inlet of the combustor; a compressed air storage; a charging compressor for charging the air storage; charging structure fluidly connecting and outlet of the charging compressor with an inlet to the air storage; connection structure fluidly connecting an outlet of the air storage to an inlet of the combustor; and valve structure associated with the connection structure and the charging structure to control flow through the connection structure and the charging structure, respectively.
The valve structure is controlled to selectively permit one of the following modes of operation: (1) a combustion turbine mode of operation wherein air compressed from the compressor moves through the flow path structure to the combustor feeding the expansion turbine such that the expansion turbine drives the generator, (2) a compressed air augmentation mode of operation wherein compressed air from the air storage is supplied through the connection structure to the combustor in addition to the compressed air passing through the flow path structure to the combustor, which increases mass flow of compressed air and gas to the expansion turbine and thus permits the generator to provide an increased power due to the additional compressed air being suppled to the expansion turbine, and (3) an air storage charging mode of operation wherein compressed air from the charging compressor moves through the charging structure to charge the air storage.
The above and other objects of the present invention will become apparent during the course of the following detailed description and appended claims.
The invention may be best understood with reference to the accompanying drawings wherein illustrative embodiments are shown, and like parts are given like reference numerals.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1a is a schematic diagram of a conventional GE 7 EA combustion turbine operating at 59 F.:
FIG. 1b is a schematic diagram of a conventional GE 7 EA combustion turbine operating at 0 F.;
FIG. 1c is a schematic diagram of a conventional GE 7 EA combustion turbine operating at 90 F.;
FIG. 2. is an embodiment of a combustion turbine power generation system provided in accordance with the principles of the present invention;
FIG. 3 is another embodiment of a combustion turbine power generation system of the invention;
FIG. 4 is yet another embodiment of a combustion turbine power generation system of the invention having a bottom steam cycle;
FIG. 5 is a schematic diagram of operating parameters applicable to the embodiments illustrated in FIGS. 2 and 3 wherein a combustion turbine assembly operates in an air augmentation mode of operation at 90 F. ambient temperature.
DETAILED DESCRIPTION OF THE INVENTION
With reference to FIG. 2, a combustion turbine power generating system provided in accordance with the principles of the present invention is shown, generally indicated at 10. It will be appreciated that the physics and mechanics of the inventive system 10 are identical for operation at high ambient temperature and at high elevations. Therefore, all explanations herein will describe the method and its effectiveness for the high ambient temperature application only. Further, it is to be understood that the invention applies equally to a combined cycle plant, where a combustion turbine is a main component.
Referring to FIG. 2, one embodiment of a combustion turbine power generation system 10 is schematically illustrated and includes a conventional combustion turbine assembly 12 which may be, for example, a GE 7 EA combustion turbine assembly. The combustion turbine assembly 12 includes a shaft assembly having a compressor 14, an expansion turbine 16, and a combustor 18 which feeds heated combustion product gas to the expansion turbine 16. The expansion turbine 16 is coupled to drive the compressor 14 and is coupled with an electric generator 20. The generator 20 is coupled to an electric grid 17. In a combustion turbine mode of operation, air is compressed in the compressor 14 and via a flow path structure 21, the compressed air is sent to the combustor 18, and thereafter heated combustion product gas is expanded in the expansion turbine 16 to produce power.
In accordance with the invention, the combustion turbine assembly 12 is provided so as to inject previously stored compressed air to an inlet of the combustor 18 feeding the expansion turbine 16. If power is to be provided which exceeds power generated by the combustion turbine assembly 12, a capacity of the generator may be upgraded, the function of which will be explained more fully below.
An additional compressed air compression storage and retrieval system (CACSRS) is provided and, in the embodiment illustrated in FIG. 2, includes a compressor train 32 to supply compressed air to a compressed air storage 28 via charging structure 34 in the form of piping. In the illustrated embodiment, the compressor train 32 includes first and second compressors 36 and 38, respectively, driven by an electric motor 40. An intercooler 42 may be provided between the first compressor 36 an the second compressor 38. In addition, an aftercooler 44 may be provided between outlet of the second compressor 38 and an inlet to the compressed air storage 28. A valve 46 is provided between the outlet of the second compressor 38 and an inlet to the aftercooler 44. A valve 48 is provided between an outlet of the aftercooler and an inlet to the compressed air storage 28. Valves 46 and 48 define a first valve system.
An outlet of the compressed air storage 28 is fluidly coupled to an inlet of the combustor 18 via connection structure 50. In the illustrated embodiment, a recuperator 52 is provided between an outlet of the air storage 28 and an inlet to the combustor 18. A valve 54 is provided between an outlet of the recuperator 52 and an inlet of the combustor 18 and a valve 55 is provided in the connection structure 50 between the outlet of the air storage 28 and the inlet to the recuperator 52. Valves 54 and 55 define a second valve system. In addition, an optional valve 56 is provided downstream of a juncture between the charging structure 34 and the connection structure 50 leading to the air storage 28. It can be appreciated that if the recuperator 52 is not provided, then valve 54 is not necessary. Similarly, if the aftercooler 44 is not provided, valve 46 is not necessary.
The electric motor 40 is coupled to the electric grid 17 such that during off-peak hours, the electric motor 40 may drive the compressor train 32 to charge the air storage 28.
The compressed air storage may be a underground geological formation such as a salt dome, a salt deposition, an aquifier, or may be made from hard rock. Alternatively, the air storage 28 may be a man-made pressure vessel which can be provided above-ground.
The method of the present invention includes an integration of the combustion turbine assembly 12 and the additional compressed air charging storage and retrieval system to provide for three modes of operation:
(1) a compressed air storage system charging mode of operation, with a flow path going through the compressor train 32, aftercooler 44, charging structure 34 to the compressed air storage 28; wherein valves 46 and 48 in the charging structure 34 are open and valves 54 and 55 in connection structure 50 are closed; and the motor-driven compressor train 32, using off-peak energy from the grid 17, compresses the ambient air to the specified pressure in the air storage 28.
(2) an air augmentation mode of operation, wherein the conventional combustion turbine assembly 12 operation is integrated with the compressed air flow from the air storage 28; air from the air storage 28 is preheated in the recuperator 52 and is injected upstream of the combustors 18; and wherein the compressed air from the air storage 28 goes through the connection structure 50, through the recuperator 52 to a point upstream of the combustor 18; during this operation valves 46 and 48 in the charging structure 34 are closed and valves 54 and 55 in the connection structure 50 are open and control the additional flow from the air storage 28; this mode of operation results in power production significantly exceeding that of the combustion turbine assembly 12 because the power produced by the expansion turbine 16 results from the expansion of the total flow, which is a sum of the flow compressed by the compressor 14 and an additional flow from the compressed air storage 28; inlet guide vanes of compressor 14 may be closed to reduce power consumption by the compressor 14 to increase the electric power by the electric generator 20 to the electric grid 17; and
(3) a conventional combustion turbine mode of operation, where CACSRS is disconnected from the combustion turbine assembly 12, and valves 46 and 48 in the charging structure 34 and valves 54 and 55 in the connection structure 50 are closed, permitting compressed air to move from the compressor 14 through the flow path structure 21 to the combustor 18 feeding the expansion turbine 16.
Although only one combustion turbine assembly 12 is shown in the embodiments herein, it can be appreciated that numerous combustion turbine assemblies may be provided and coupled with a common air storage to provide the desired augmented air flow and thus, the desired power output.
FIG. 3 is a schematic illustration of a second embodiment of the invention and includes the combustion turbine assembly 12. As above, there is a provision to inject previously stored compressed air upstream of combustor 18 and a provision to extract the compressed air downstream of the compressor 14 for a further intercooling in an intercooler 58 and compression in a boost compressor 60. Also, the capacity of the electric generator 20 may be upgraded, if required.
The method also provides a CACSRS having an electric motor 40 driving the charging boost compressor 60 fed by the intercooler 58. An aftercooler 44 is provided downstream of the boost compressor 60 and valves 46 and 48 are provided before and after the aftercooler, respectively, and are disposed in the charging structure 34. Thus, a flow path is provided from an outlet of the compressor 14 through the intercooler 58, disposed in integrating structure 62, to an inlet of the boost compressor 60, through the aftercooler 44 to the compressed air storage 28. In addition, compressed air may flow from an outlet of the compressor 14 to an inlet of the combustor 18 via the flow path structure 21. The compressed air storage fluidly communicates via connection structure 50 to a point upstream of combustor 18. Valve 64 in the integrating structure 62, together with valve 66 in the flow path structure 21, valves 44 and 46 in the charging structure 34, and valves 54 and 55 in the connection structure 50, selectively control flow through the flow path structure 21, the connection structure 50, the charging structure 34 and the integrating structure 62.
As in the first embodiment, the combustion turbine assembly 12 and the CACSRS are integrated to provide three modes of operation:
(1) a compressed air storage system charging mode of operation, wherein a flow path exists from the compressor 14, through the integrating structure 62 containing the intercooler 58, to the boost compressor 60, through the charging structure 34 containing the aftercooler 44, to the compressed air storage 28; a expansion turbine cooling flow of approximately 5-10% of the nominal flow is flowing from the compressed air storage 28 via the connection structure 50, to the recuperator 52 and to the expansion turbine 16 via unfired combustor 18 and to the exhaust stack;
valves 46 and 48 in the charging structure 34 are open, valves 54 and 55 in the connection structure 50 are partially open to provide the cooling flow via unfired combustor 18 to the expansion turbine 16; valve 64 in integrating structure 62 is open and valve 66 is closed; the combustion turbine electric generator 20, fed by off-peak power from the grid 17, drives the combustion turbine shaft and the boost compressor 60 is driven by the electric motor 40, also fed by off-peak energy from the grid 17;
(2) an air augmentation mode of operation, wherein a conventional combustion turbine operation is integrated with the additional compressed air flow from the air storage 28, which is preheated in the recuperator 52 and injected upstream of the combustor 18; thus, the compressed air from the air storage 28 goes through the connection structure 50, through the recuperator 52 to a point upstream of the combustor 18; valves 46 and 48 in the charging structure 34 are closed, valves 55 and 54 in the connection structure 50 are open and control the additional flow from the air storage 28; valve 64 in the integrating structure 62 is closed and the valve 66 is open; this mode of operation results in power production significantly exceeding that of the combustion turbine assembly 12, because the power produced by the expansion turbine 16 results from the expansion of the total flow, which is a sum of the flow compressed by the compressor 14 and an additional flow from the compressed air storage 28; inlet guide vanes of compressor 14 may be closed to reduce power consumption by the compressor 14 to increase the electric power by the electric generator 20 to the electric grid 17;
(3) a conventional combustion turbine mode of operation, wherein the CACSRS is disconnected from the combustion turbine assembly 12, and valves 46 and 48 in the charging structure 34 and valves 55 and 54 in the connection structure 50 are closed and the valve 64 in the integrating structure 62 is closed while valve 66 in the flow path structure is open permitting compressed air to move from the compressor 14 through the flow path structure to the combustor 18 feeding the expansion turbine 16.
FIG. 4 is a schematic illustration of a third embodiment of the invention and includes a combined cycle plant with a combustion turbine assembly 12 with a conventional bottoming steam cycle components: a heat recovery steam generator 68, a steam turbine 70, a generator 71 coupled with the turbine 70, a condenser 72, a deaerator 74 and pumps 76. The combustion turbine assembly requires a provision to inject previously stored compressed air upstream of combustor 18 and a provision to extract the compressed air downstream of the compressor 14 for a further intercooling and compression in the boost compressor 60. Also, the capacity of the electric generator 20 may be upgraded if required.
The invented method also provides an additional CACSRS including an electric motor driven a boost compressor 60 fed by intercooler 58, the aftercooler 44, integrating structure 62 permitting communication between an outlet of the compressor 16 via the intercooler 58 to the boost compressor inlet and through the flow path structure 21 to the combustor 18 inlet. Charging structure 34 permits communication between an outlet of the boost compressor 60 and an inlet to the compressed air storage 28. Connection structure 50 permits communication between the compressed air storage 28 and a point upstream of combustor 18. Valves 46 and 48 are provided in the charging structure 34, valve 55 is provided in the connection structure 50, and valve 64 is provided in the integrating structure 62, while valve 66 is provided in the flow path structure 21, to selectively control flow through the charging structure 34, the connection structure 50 and the integrating structure 62 and the flow path structure 21.
The combustion turbine assembly 12 is integrated with a steam bottoming cycle, generally indicated at 78, and the additional CACSRS to provide for three modes of operation:
(1) a compressed air storage charging mode of operation, wherein flow goes through the compressor 14, through the integrating structure 62 having the intercooler 58, to the boost compressor 60, through the charging structure 34 having the aftercooler 44 to the compressed air storage 28; a turbine cooling flow, which is approximately 5-10% of the nominal flow is flowing from the compressed air storage 28 through the connection structure 50, and via an unfired combustor 18, to the expansion turbine 16 and then to the exhaust stack; valves 46 and 48 in the charging structure 34 are open, valve 55 in the connection structure 50 is partially open to provide the cooling flow via the unfired combustor 18 to the expansion turbine; and valve 64 in the integrating structure 62 is open and valve 66 is closed; the combustion turbine electric generator 20, fed by off-peak power from the grid 17, drives the combustion turbine shaft and the boost compressor 60 is driven by the electric motor 40, also fed by off-peak energy from the grid 17;
(2) an air augmentation mode of operation, where a conventional combustion turbine operation is integrated with additional compressed air flow from the air storage 28, which is injected upstream of the combustor 18; where compressed air from the air storage 28 goes through the connection structure 50 to a point upstream of the combustor 18; valves 46 and 48 in the charging structure 34 are closed, valve 55 in the connection structure 50 is open and controlling the additional flow from the air storage 28; valve 64 in the integrating structure 62 is closed and valve 66 is open; in addition, a conventional closed-loop steam/condensate flow path is provided where steam generated in the heat recovery steam generator 68 expands through the steam turbine 70 producing power to the grid 17, and then goes through the condenser 72, deaerator 74, feedwater pumps 76 and back to the heat recovery steam generator 68; this mode of operation results in power production by the combustion turbine assembly 12 significantly exceeding that of the conventional combustion turbine assembly without the additional air flow, because the power produced by the expansion turbine 16 results from the expansion of the total flow, which is a sum of the flow compressed by the compressor 14 and an additional flow from the compressed air storage 28; also, an additional power is produced by the steam turbine of the bottoming cycle 78 due to additional steam flow by the heat recovery steam generator 68 recovering heat from the expansion turbine 16 exhaust; inlet guide vanes of compressor 14 may be closed to reduce power consumption by the compressor 14 to increase the electric power by the electric generator 20 to the electric grid 17; and
(3) a conventional combustion turbine mode of operation, wherein CACSRS is disconnected from the combustion turbine assembly 12, and valves 46 and 48 in the charging structure 34, valves 55 and 54 in the connection structure 50 are closed and the valve 66 in the flow path structure 21 is open permitting compressed air to move from the compressor 14 through the flow path structure to the combustor 18 feeding the expansion turbine 16.
Practical applications of the inventive method are illustrated in FIG. 5, which is a schematic diagram with operating parameters applicable to the first and the second illustrative embodiments according to the present invention, where a GE Frame 7 EA combustion turbine assembly 12 operates in an air augmentation mode and at 90 F. ambient temperature. FIG. 5 illustrates that during air augmentation at an elevated ambient temperature of 90 F., the additional compressed air flow of 168 lbs/sec is retrieved from the compressed air storage 28 and injected upstream of the combustor 18 to increase the combustion turbine power output to 129.2 MW from 76.4 MW for the conventional combustion turbine assembly operation at the same 90 F. ambient temperature (see FIG. 1c). The amount of the retrieved air is limited by a number of design limitations. For a GE Frame 7 EA combustion turbine assembly, the limitation is the maximum expansion turbine power of 228 MW and is achieved when the combustion turbine assembly operates at 0 F. (see FIG. 1b).
Table 1a presents performance characteristics of the GE Frame 7 EA operating as a conventional combustion turbine assembly with air augmentation--applicable to the first and the second illustrative embodiments of the invention. Table 1a indicates that over the whole range of ambient temperatures higher than 0 F. air augmentation results in power increased by 52.8 MW for 90 F. ambient temperature and 32.8 MW for 59 F. Performance parameters for the air augmentation concept are heat rate characterizing the fuel consumption in BTU per kWh produced and an kWh consumption for the compressed air storage recharging. The cost of electricity (COE) produced is calculated as: COE=(Heat rate, BTU/kWh)×(cost of fuel, $/BTU)+(the off-peak energy for the air storage recharging, kWh)×(cost of off-peak energy, $/kWh)/total kWh produced in the air augmentation mode of operation.
TABLE 1a______________________________________ Ambient Temperature 0 59 70 90______________________________________Frame 7EA CT - Simple CycleGross Power, MW 102.5 85.4 82.4 76.4Heat Rate (LHV & Natural Gas 10,110 10,420 10,520 10,630Fuel), Btu/kWhAugmentation based onFrame 7EAGross Power Output, MW 102.5 118.0 122.2 129.2Incremental Gross Power, MW 0.0 32.6 39.8 52.8Heat Rate (LHV & Nat. Gas Fuel), 10,110 9,610 9,510 9,140btu/kWh w/o recup.Heat Rate with recuperator N/A 8,680 8,340 8,010Time of Augmentation Operation, N/A 9.8 8.5 6.0Hours______________________________________Compression and StorageCompression Energy, MH 210Storage Type Salt DomeVolume, Million Cu. Ft. 5.385Delta P in Cavern, psi 150______________________________________
Table 1b demonstrates performance characteristics of the third illustrative embodiment of the invention, i.e., the conventional combined cycle plant, based on GE Frame 7 EA, and the plant operation in an air augmentation mode. The findings are similar to the first and second illustrative embodiments.
TABLE 1b______________________________________ Ambient Temperature 0 59 70 90______________________________________Frame 7EA CT - Combined CycleGross Power, MW 155.6 134.1 130.7 123.4Heat Rate (LHV & Natural Gas 6,810 6,800 6,900 6,970Fuel), btu/kWhAugmentation based onFrame 7EA CombinedGross Power Output, MW 155.6 168.4 172.5 178.9Incremental Gross Power, MW 0.0 34.3 41.9 55.6Heat Rate (LHV & Natural Gas 6,810 6,730 6,740 6,600Fuel), btu/kWhTime of Augmentation Operation, N/A 9.8 8.5 6.0Hours______________________________________Compression and StorageCompression Energy, Mh 210Storage Type Salt DomeVolume, Million Cu. Ft. 5.385Delta P in Cavern, psi 150______________________________________
The cost of conversion of a combustion turbine system provided with air augmentation are as follows:
compressed air storage cost;
compressor train cost for the storage recharging;
costs of an interconnecting piping, valves and controls for the overall system integration
The compressed air storage shall be sized to store a sufficient mass of air to support air augmentation operations with maximum power output for a specified number of hours with elevated ambient temperatures. The stored compressed air pressure should be sufficient to inject the additional mass of air upstream of the combustor. For the embodiment shown in FIG. 5, and Tables 1a and 1b, when the air storage is sized to provide for continuous six (6) hours of operation at 90 F. with maximum power output of 129.2 MW, the properly sized compressed air storage in a salt dome requires 5.4 million cubic feet (with depth of approximately 1000 feet and the maximum minus minimum pressure difference of 150 p.s.i.) at cost of approximately $5 million. Engineering and cost estimates demonstrated that for the above conditions total costs for a providing the GE Frame 7 EA combustion turbine assembly to include air augmentation are approximately $8.8 million with 52.8 MW additional power at 90 F. ambient temperature (see Table 1a) or the specific cost of the modification is approximately $160/kW. This compares favorably with approximately $300/kW specific cost for a similar (50 MW) capacity combustion turbine assembly. A similar modification for a combined cycle plant (see Table 1b) will cost approximately $150/kW, which is even more attractive as compared with approximately $500/kW for a combined cycle power plant.
It has thus been seen that the objects of this invention have been fully and effectively accomplished. It will be realized, however, that the foregoing and preferred embodiments have been shown and described for the purposes of illustrating the structural and functional principles of the present invention, as well as illustrating the method of employing the preferred embodiments and are subject to change without departing from such principles. Therefore, this invention includes all modifications encompassed within the spirit of the following claims.
|
A method is provided to ensure that a combustion turbine power generation system may operate at maximum allowable power at elevated ambient temperature and/or at low air density. The method includes providing at least one combustion turbine assembly including a compressor, an expansion turbine operatively associated with the compressor, an upgraded generator coupled with the expansion turbine; a combustor feeding the expansion turbine; flow path structure fluidly connecting an outlet of the compressor to an inlet of the combustor; a compressed air storage; a charging compressor for charging the air storage; charging structure fluidly connecting an outlet of the charging compressor with an inlet to the air storage; connection structure fluidly connecting an outlet of the air storage to an inlet of the combustor; and valve structure associated with the connection structure and the charging structure to control flow through the connection structure and the charging structure, respectively. The valve structure is controlled to selectively permit one of the following modes of operation: (1) a combustion turbine mode of operation wherein air compressed from the compressor moves through the flow path structure to the combustor feeding the expansion turbine such that the expansion turbine drives the generator, (2) a compressed air augmentation mode of operation wherein compressed air from the air storage is supplied through the connection structure to the combustor in addition to the compressed air passing through the flow path structure to the combustor, which increases mass flow of compressed air and gas to the expansion turbine and thus permits the upgraded generator to provide an increased power due to the additional compressed air suppled to the expansion turbine, and (3) an air storage charging mode of operation wherein compressed air from the charging compressor moves through the charging structure to charge the air storage.
| 5
|
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority under 35 U.S.C. §119(e) from provisional application No. 60/326,297 filed Oct. 1, 2001. The No. 60/326,297 provisional application is incorporated by reference herein, in its entirety, for all purposes.
FIELD OF THE INVENTION
[0002] The present invention relates to building construction and the placement of solar energy collectors thereon. More specifically, the present invention relates to integrating solar collectors with building components so as to permit the simultaneous solar harvesting of heat and light, the conversion thereof to electrical energy, and the selective use of heat for heating and cooling.
BACKGROUND OF THE INVENTION
[0003] Traditional roof technologies construct elevated covers to buildings. A roof typically comprises a layer of impermeable tar, tarpaper or concrete laid over a wood or metal platform (deck) of corrugated metal sheeting. While a roof seals a building from the environment, it also results in substantially reduced daylight illumination, the loss of a heat source in cool seasons and the collection of heat in warm seasons. Skylights may or not be fitted to improve illumination but may add to the heat gain in the warmer months. Similarly, wall construction is primarily a means of sealing out the elements from the inside of a structure.
[0004] Solar energy is tantalizing in both its promise and its evasiveness. The ultimate objective is to utilize solar energy to heat, cool, provide electricity, and light structures efficiently and to reduce the need for energy from other sources. Various approaches have been suggested for achieving each of elements of this objective.
[0005] In a “German Roof” a series of windows are present on the roof of a building. In cross section these appear as a saw tooth pattern on the roof. They provide both light and heat (but usually only when they face the sun).
[0006] Referring to FIG. 1, the “Minnesota window heater” is illustrated. This unit is placed in a window 27 . The suns rays are absorbed on a black (or dark)) panel 25 heating the air in the vicinity of the panel. The air rises through the heater (as noted by the arrows, causing more cool air to be drawn into the heater through opening 24 . Heated air is expelled through opening 26 into the room.
[0007] Technologies that collect some aspect of solar energy introduce some negative side effects that require energy consumption to offset. Solar heat exchangers for water and space heating or for electrical energy collection cause a build up of heat in summer months. This heat needs to be actively dissipated or mechanically cooled at an expense. Similarly, solar technologies that are designed to heat water and convert solar energy to electrical energy ignore winter heating needs. Skylights and solar daylighters provide illumination but just as often add heat (via direct sunlight) as fast as illumination and increase the “solar oven” effect of most buildings.
[0008] At additional expense and effort, solar photovoltaic panels may be laid horizontally or framed to sit at an angle. For example, photovoltaic (amorphous) on plastic substrate is available to lay in pans of standing seam metallic roofing. While photovoltaic panels permit the production of electricity, the per-kilowatt cost of generation is high. Additionally, the panels block solar illumination of the structure thereby trading off one form of solar energy for another.
[0009] “The SOLARWALL® Solar Heating System” made by Conserval Engineering (Conserval Engineering) heats air in the winter. A southern wall is metal clad (aluminum or steel) on its exterior. A cavity is formed between the building's southern wall and the metal cladding. A ventilation fan, positioned at the top of the cavity creates reduced pressure within the cavity. Outside air is drawn in through holes in the metal cladding due to air pressure differential. The dark colored cladding is heated by solar radiation. The external air that is drawn over the metal cladding is heated and captured by openings in the metal cladding and collected in the wall cavity. The warmed air from the wall cavity rises to a plenum at the top of the cavity and is ducted to a circulation fan. The warmed air is circulated throughout the building. Applications include using the metal cladding as roofing material and overlaying the metal cladding with photovoltaic panels to produce electricity.
[0010] The Conserval Engineering approach, described above, is also described in U.S. Pat. No. 4,899,728 to Peter et. al, entiled “Method and Apparatus for Preheating Ventilation Air for a Building”, ('728) and U.S. Pat. No. 4,934,338 to Hollick et. al, entitle, “Method and Apparatus for Preheating Ventilation Air for a Building”, ('338). The description for patents '338 and '728 are virtually the same (the '338 patent is a divisional of the '728 patent). Effectively, both citations are for an exterior wall passive solar heat collector for heating outside air.
[0011] In Canadian Patent 1,196,825 issued to Hollick and entitled “Method for Preheating Ventilation Air in a Building” ('825), describes an outer transparent glazing to a south wall that allows solar energy to penetrate the glazing material (glass, plastic or the like) and be absorbed on a black painted building wall. There is a space between the glazing material and the building wall forming an air chamber. Outside air is drawn into the air chamber through an opening at the bottom of the glazed material. The air is heated by the building wall which has become heated from absorbing solar energy. The air rises and is distributed by fan and duct work through the building for heating purposes. If heating is not desired, the hot air is allowed to vent to the outside.
[0012] In U.S. Pat. No. 4,449,347 issued to Rooney and entitled “Solar Collection Building Truss,” ('347) describes a solar collector integrated into a building truss that can be fabricated at a building site or pre-fabricated at a factory. The '347 patent teaches use of reflective surfaces to direct light to a heat absorbing member connected to a heat exchanger or other means for storing heat generated by the heat absorbing member. A similar truss was described in U.S. Pat. No. 4,237,869 also issued to Rooney, entitled “Solar Collector.”
[0013] U.S. Pat. No. 6,201,179 issued to Dalacu and entitled “Array Of Photovoltaic Modules For A Integrated Solar Power Collection System,” describes a solar powered collection system comprising a variety of arrays for generating electricity.
[0014] U.S. Pat. No. 4,674,244 issued to Francovitch and entitled “Roof Construction Having Insulation Structure Membrane And Photovoltaic Cells,” teaches a means for roof construction that integrates photovoltaic cells into the roof structure.
[0015] U.S. Pat. No. 5,092,939 issued to Nath et. al., and entitled “Photovoltaic Roof Method Of Making Same,” describes a roof structure comprising panels in which a photovoltaic layers has been incorporated.
[0016] U.S. Pat. No. 5,452,710 issued to Palmer and entitled “Self Sufficient Apparatus And Method For Conveying Solar Heat Energy From An Attic,” ('710) describes a solar energy absorbing roof that heats air in the attic below the roof. In '710, solar-generated heat is collected from the attic stored and/or distributed within the building. Fans and other electrical apparatus needed to capture, distribute, and store the collected heat are powered by photovoltaic cells placed on the roof.
[0017] U.S. Pat. No. 4,466,424 issued to Lockwood and entitled “Solar Collector System For Standing Seam Roofs,” ('424) describes a solar collector system incorporated into a standing seam roof. The collector is formed by securing two transparent sheets to the standing seams of a roof panel to form two channels, one acting as a heat exchanger and the other an insulating chamber. Sun light impinges on the bottom of the roof panel and heats it. Air travels over the heated surface of the bottom of the roof panel and is heated and collected by ductwork located near the center ridge of the roof.
[0018] U.S. Pat. No. 4,103,825 issued to Zornig and entitled “Solar Heated And Cooled Dwelling,” describes means for collecting heated attic air during the heating season and removing unwanted heated attic air during the cooling season.
[0019] U.S. Pat. No. 4,201,188 issued to Cummings and entitled “Solar Collector And Heat Trap,” describes a solar collector and heat trap for the collection of heat in an attic area of the home for subsequent distribution throughout the home.
[0020] Finally, French Patent 2,621,943 was issued to Hernecq for a heat collection system in the attic of a home for distribution throughout the home.
[0021] While these inventions are useful for producing heat or photovoltaic energy, they do not represent an integral construction member that has the capability of not only collecting heat for use in heating inside air but also producing electrical energy from the heat air collected.
[0022] What would be useful is a means of integrated solar collection into construction that would make efficient use of sunlight for illumination and solar energy for generation of heat and electricity without unwanted structural heating, and that would intercept sunlight generated heat for capture and use during winter and diversion away during summer. It would also be useful if sunlight and solar generated heat could be used to generate electricity and hot water under all seasonal conditions during daytime periods of peak electrical power consumption.
SUMMARY OF THE INVENTION
[0023] An embodiment of the present invention is a roof component that integrates a solar collector into the structure of the roof itself. Another embodiment of the present invention is a wall component that integrates a solar collector is built into the structure of an exterior wall.
[0024] It is an object of the present invention to integrate solar collection capability into roof and wall building components.
[0025] It is an object of the present invention to minimize roof shading by indirect day lighting and to obviate daytime artificial lighting requirements.
[0026] It is another object of the present invention to minimize the direct solar heating of the enclosed structure.
[0027] It is a further object of the present invention to capture sunlight generated heat for diversion away from the enclosed structure during the summer, in order to minimize required cooling load and for use within the structure during winter in order to minimized the heating load.
[0028] It is yet another object of the present invention to use the captured sunlight generated heat to generate electricity and hot water for the structure year round.
[0029] It is still another object of the present invention to minimize electrical demand and reduce electrical lighting and mechanical space conditioning to ‘stand-by-status.’
[0030] These and other objectives of the present invention will become apparent from a review of the general and detailed descriptions that follow. In one embodiment of the present invention, a combined solar collector is built into two sides of an integrated truss collector structure, in lieu of a built up platform of roof decking and tar, etc. This truss structure rests upon the load bearing walls, apex up, orienting panels to the south and panels the north. The southerly facing solar energy collection panels collect solar energy for conversion to heat and/or electricity. The northerly facing sunlight collection panels (daylighter panels) collect light for illumination of the interior of an enclosed structure.
[0031] In an alternate embodiment of the present invention, a solar collector is built into a roof panel that is used over a conventional roof deck. In another embodiment of the present invention, a solar collector is built into a wall panel that is used to cover an exterior wall, oriented vertically on the side of a building.
BRIEF DESCRIPTION OF THE DRAWINGS
[0032] [0032]FIG. 1 illustrates a “Minnesota Window Heater”
[0033] [0033]FIG. 2 illustrates the integrated truss of the present invention.
[0034] [0034]FIG. 3 illustrates a top view of the present invention having a series of collectors.
[0035] [0035]FIG. 4 illustrates a side view of the present invention further illustrating airflow, turbine and electrical production elements.
[0036] [0036]FIG. 5 illustrates a side view of the present invention wherein heated air is recirculated back into the building.
[0037] [0037]FIG. 6 illustrates a side view of the present invention showing airflow and heat collection means.
[0038] [0038]FIG. 7 illustrates a side view of the present invention having photovoltaic cells on one surface of the collector.
[0039] [0039]FIG. 8 illustrates the flat roof collector.
[0040] [0040]FIG. 9 illustrates the flat roof collector and associated flow of heated air.
[0041] [0041]FIG. 10 illustrates a side view of the flat roof collector.
[0042] [0042]FIG. 11 illustrates a building having heat/electricity producing double walls.
DETAILED DESCRIPTION OF THE INVENTION
[0043] An embodiment of the present invention is a roof structure that integrates solar collectors into the structure of the roof itself. Referring to FIG. 2 a cross section of an integrated truss collector 8 is illustrated. The integrated truss collector 8 illustrated comprises two lower rails 6 , a cross member 12 , a truss air duct 10 , solar energy collection panel 16 and daylighter panel 18 . In an embodiment of the present invention, the solar energy collection panel 16 is oriented in a southerly direction and the daylighter panels 18 are oriented in a northerly direction. Each end of the integrated truss collector 8 is supported by a weight-bearing structure.
[0044] As illustrated In FIG. 2, the integrated truss collector 8 comprises a single panel length, however this is not meant as a limitation. As would be apparent to those skilled in the art of the present invention, the number of panels may be determined by the producer of the integrated truss collector 8 , subject to limitations of structural strength and loading. Additionally, integrated truss collector 8 may comprise supporting structures in addition to the lower rails 6 and, cross member 12 , which supporting structures would be apparent to those skilled in the art of the present invention. Additionally, truss air duct 10 , which as will be described in detail below receives heated air from solar energy collection panel 16 , is illustrated as tubular in cross section. However, this is not intended as a limitation. Other means of receiving heated air from solar energy collection panel 16 may be used without departing from the scope of the present invention. For example, in an embodiment of the present invention, the truss air duct 10 is integrated with the solar energy collection panel 16 .
[0045] Referring now to FIG. 3, a plurality of integrated truss collectors assembled on a building is illustrated. The integrated truss collectors 20 , 22 , 24 , 26 , 28 , 30 are generally oriented east-west with the sloped portions facing south for collecting solar energy and north for collecting light for illumination. A roof air duct 76 for collecting and distributing warm air runs in a north-south direction above the trusses 20 , 22 , 24 , 26 , 28 , 30 . The roof air duct 76 connects to each of the roof trusses at the truss air duct 10 (illustrated in FIG. 1). This roof air duct 76 may be steel, aluminum or other suitable material, including entirely or partially transparent material to allow further air heating. The roof air duct 76 may extend all the way to the south side of the roof, if a “South Wall” (described below) is fitted to the south face of the structure.
[0046] Referring to FIG. 4, warm collected from each of the integrated truss collectors is used in an electrical generator 82 to generate electricity for building use or/and distribution to an electrical grid. The electrical generator 82 comprises a low-pressure turbine 83 that is turned by the warm air flowing through the roof air duct 76 . The low-pressure turbine 83 in turn drives an electrical generator 84 . A louver 86 (illustrated in the closed position) or similar device directs the hot air exhaust to chimney 88 for venting into the atmosphere.
[0047] Referring now to FIG. 5, warm collected from each of the integrated truss collectors and flowing through the roof air duct 76 is used for heating the internal structure. In this embodiment, louver 86 is open to direct warm air into the internal structure through vent 90 . Low-pressure turbine 83 is not configured to produce electricity in this embodiment.
[0048] Referring to FIGS. 6 and 7, the airflow of an embodiment of the present invention is further illustrated. Oriented in the northerly direction is daylighter panel 30 . Oriented in the southerly direction is solar energy collection panel 40 . (In the southern hemisphere, the north-south designations are reversed.)
[0049] The daylighter panel 30 comprises outer glazing 32 and inner glazing 34 , however this is not meant as a limitation. Additional glazing may be used without departing from the scope of the present invention. Outer glazing 32 and inner glazing 34 form channel 58 that directs air from the daylighter panel 30 to solar energy collection panel 40 . The daylighter panel 30 allows daylight to enter the structure to illuminate the spaces within. The daylighter panel 30 is vented to draw inside air 36 from intake vent 38 (located in proximity to bottom rail 6 ) and to vent the air to solar energy collection panel 40 via the air gap 72 located below and external to the truss air duct 10 . In another embodiment, where the daylighter panel is triple glazed, air intake vent 38 would be located near the apex of the triangular cross-section of the integrated truss collector. In this embodiment, a second channel would be formed in daylighter panel 30 (not illustrated) and the air would flow down this second channel to channel 58 before flowing to the solar energy collection panel 40 as previously described.
[0050] Solar energy collection panel 40 comprises a single transparent layer 42 comprising glass, plastic or other transparent material that allows the sun to illuminate a light-absorbing layer 44 . In an embodiment according to the present invention illustrated in FIG. 7, a daylighter panel 30 and a solar energy collection panel 40 are deployed as described in reference to FIG. 6 with the exception that light-absorbing layer 44 is a photovoltaic (PV) material that absorbs solar energy to produce electricity. Solar energy not converted to electricity is converted to heat that is collected as described below.
[0051] In another embodiment, light-absorbing layer 44 is a rigid material that is optimized for heat absorption. By way of illustration not as a limitation, light-absorbing layer 44 is a metal or wood sheet that is painted black. A bottom layer 46 is solid, with an optionally silvered interior to enhance the reflectance characteristics from daylighter panel 30 .
[0052] Referring again to FIG. 6, the three layers of solar energy collection panel 40 form two channels, channels 60 and 62 . In operation, sunlight passes through the transparent panel 42 of the solar energy collection panel 40 and is absorbed by light-absorbing layer 44 . As the air within channel 60 is heated it expands, rises and induces a movement toward the top of the truss. This in turn causes air to move through channel 62 downward through an opening 64 in the light-absorbing layer 44 to be heated by the absorption panel. Air is drawn to the solar energy collection panel 40 through air gap 72 in the daylighter panel 30 on the north-facing surface. Relatively cool inside air 36 is drawn into channel 58 though inlet 38 . Air that is drawn into the system of the present invention travels through channel 58 , which is connected to channel 62 . Thus a low pressure region, formed by the heated air of the solar energy collection panel 40 , causes air to be transported through channels 58 and 62 from the daylighter panel 30 to the solar energy collection panel 40 through opening 64 at the bottom of the south facing solar energy collection panel 40 . The heated air is then accumulated at truss air duct 10 . Heated air is then collected from a plurality of integrated truss collectors 8 by roof air duct 76 through collection vents 78 in each of the plurality of truss air ducts 10 . Heated air travels to the roof air duct 76 through channel 80 .
[0053] When heating of the interior structure is desired, inside air 36 is drawn into the previously described channels, heated and distributed for return to the internal structure. During the middle of the day, warm air is from the roof through bypass 70 located on the solar energy collection panel 40 near lower rail 6 . This avoids removing all the cool air from inside the building during hot weather.
[0054] The intake capture of external heated air is dictated by bypass 70 . In one embodiment of the present invention, bypass 70 is opened or closed by the use of a bimetal hinge. The two metals of the hinge have differing expansion and contraction coefficients. It is the greater heat of summer time that opens the bypass. This is not meant as a limitation however. For example, bypass 70 may be mechanically or electrically actuated by a thermostat or other heat
[0055] In another embodiment of the present invention, the heated air from the roof air duct 76 is directed to a heat exchanger where the heated air is used for hot water production. In yet another embodiment of the present invention, the heated air is used to operate a low-pressure turbine that in turn drives an electrical generator to produce electricity.
[0056] As noted previously, in one embodiment (see FIG. 7) of the present invention, light-absorbing layer 44 comprises a PV panel. Electricity from the PV panel and from the electrical generator (see FIG. 4), feed into the structure's electrical system for dedicated internal load, with heavy amperage leads inside the structure dedicated to the external utility grid.
[0057] Referring to FIG. 8, another embodiment of the present invention is illustrated. In this embodiment, an integrated flat roof collector 92 comprises a panel having two vertical side components 90 connected near the midpoints of each side component by a horizontal component 96 . The vertical side components 90 are divided by the horizontal component into an upper segment 92 and a lower segment 94 . In another embodiment, a bottom component (not shown) connects the bottom of each side component to form a base. A single transparent layer 98 covers the top of the tray and is supported by the upper segments 92 of the vertical side components 94 of the panels.
[0058] Referring to FIG. 9, horizontal light-absorbing layer 100 is attached to or formed on horizontal component 96 . The panels are installed on roof decking, preferably facing south, side-by-side, forming parallel rectangular trays that extend for the full pitch of the roof. The vertical side components 90 are supported by decking 102 and form a first channel 112 bounded by the decking 102 (or, if implemented, the bottom component), the bottom of horizontal component 96 and the inside surfaces of the lower segments 94 of the vertical side components 96 . A single transparent layer 98 covers the top of the tray and is supported by the upper segments 92 of the vertical side components 94 of the panels. A second channel 114 is formed by the inside surfaces of the upper segments 94 , the top of the light-absorbing layer 100 , and the bottom of the transparent layer 98 .
[0059] Transparent layer 98 comprises glass, plastic or other suitable transparent material that permits the passage of the suns rays. Light-absorbing layer 100 (which is not transparent) is supported by or formed on the horizontal component 96 and comprises photovoltaic (PV) material or a light absorbing material. In one embodiment, the light absorbing material is a layer of dark paint applied to horizontal component 96 .
[0060] In this configuration, air is drawn in from the attic space 108 through opening 110 . Air rising on the upper side of the panel through second channel 114 draws air from the attic space 108 through first channel 112 , through a junction 64 connecting first channel 112 and second channel 114 , and into second channel 114 The heated air from second channel 114 rises and passes into a roof cap collector 104 . At this point, the heated air is available for use. In one embodiment, the heat air drives a low-pressure turbine that in turn drives an electrical generator. In another embodiment, the heated air is passed through a heat exchanger to heat water. In yet another embodiment, the heated air is returned through ductwork to heat the inside of a building. The airflow path is completed by chimney 106 that allows the air to vent to the outside. In another embodiment, airflow path is completed through a vent in roof cap collector 104 .
[0061] In an alternate embodiment, flat panels are used to create an integrated wall collector (or “south wall” collector) as illustrated in FIGS. 10 and 11. The integrated wall collector may be used as a standalone collection system or in conjunction with an integrated truss collector or an integrated flat roof collector as previously described.
[0062] Referring to FIG. 10, another embodiment of the present invention is illustrated. In this embodiment, a solar collector comprises a panel having two vertical side components 190 connected near the midpoints of each side component by a horizontal component 196 . The side component 190 is divided by the horizontal component into an upper segment 192 and a lower segment 194 . In another embodiment, a bottom component (not shown) connects the bottom of each side component to form a base. Horizontal light-absorbing layer 200 is attached to or formed on horizontal component 196
[0063] The panels are installed on an exterior wall of a building, preferably a southerly facing wall, side-by-side forming parallel rectangular trays that extend for the full height of the wall. The lower segments 194 are supported by exterior wall 202 (FIG. 11) and form a first channel 212 bounded by the exterior wall 202 , the bottom horizontal component 196 and the inside surfaces of the lower segments 194 (FIG. 10). A transparent layer 198 covers the top of the tray and is supported by the upper segments 192 of the panels. A second channel 214 is formed by the inside surfaces of the upper segments 192 , the top of the light-absorbing layer 200 , and the bottom of the transparent layer 198 .
[0064] It should be noted that production of the various wall can occur in a number of ways. For example the vertical components and horizontal component can be of a single piece of metal that is formed with the various angles required. However, where manufacturing concerns dictate, especially where a coating is to be applied to the metal components, the vertical components and the horizontal component can be constructed of a number of separate pieces that are assembled to achieve the angles and surfaces noted in FIG. 10.
[0065] Transparent layer 198 comprises glass, plastic or other suitable transparent material that permits the passage of the suns rays. Light-absorbing layer 200 is supported by the base of the panel and comprises photovoltaic (PV) material or a light absorbing material. In one embodiment, the light absorbing material is a layer of dark paint applied to horizontal component 196 .
[0066] In this configuration, air is drawn in from the interior space 208 through opening 210 . Air rising on the upper side of the panel through second channel 214 draws air from the interior space 208 through first channel 212 , through a junction 164 connecting first channel 212 and second channel 214 , and into second channel 214 The heated air from second channel 214 rises and passes into a wall collector 204 . At this point, the heated air is available for use. In one embodiment, the heat air drives a low-pressure turbine that in turn drives an electrical generator. In another embodiment, the heated air is passed through a heat exchanger to heat water. In yet another embodiment, the heated air is returned through ductwork to heat the inside of a building. If the integrated wall collector is used in conjunction with an integrated truss collector or a flat panel, the heated air received at wall collector 204 may be conveyed to the either roof air duct 76 (see FIG. 6 and related description) the or roof cap collector 104 (see FIG. 9 and related description).
[0067] Referring now to FIG. 11, a conceptual view of the present invention when employed in a full building wall is illustrated. A building employing the present invention has a first surface of glass 302 at least on the south facing wall of the building (in the northern hemisphere for example). When the sun's ray impinge on the glass wall 302 heat is produced and captured in the space between the glass wall 302 and glass surface of a second wall 303 that constitutes the wall of the offices floors 304 , 306 , 308 , 310 .
[0068] Each office floor has vents 314 , 316 , 318 , and 320 , which vent to the space between glass wall 302 and office wall 303 .
[0069] Heat produce between glass wall 302 and office wall 303 rises and is captures in air duct 312 . Air duct 312 is in turn connected to a turbine that causes electricity to be produced as described in FIG. 4. Further, because of the flow of warm air between walls 302 and 303 , air in the floors is circulated through the floor and vented to the space between the walls 302 and 303 . In this manner, there is a constant airflow through the floors cooling them and generating electricity that can be stored in ways known in the art.
[0070] It will be appreciated by those skilled in the art that the number of floors in the building is not a limitation. This figure is for illustrative purposes only.
[0071] Solar collectors integrated into roof and wall-building components have now been illustrated. As described herein, the integrated solar collectors provide efficient means for collection of solar energy for conversion to heat and electricity and for collection sunlight for building illumination. It will be understood by those skilled in the art of the present invention may be embodied in other specific forms without departing from the scope of the invention disclosed and that the examples and embodiments described herein are in all respects illustrative and not restrictive. Those skilled in the art of the present invention will recognize that other embodiments using the concepts described herein are also possible.
|
A structurally integrated solar collector. Roof and wall covering components are integrated with solar collectors to permit solar energy to be converted to heat, electricity and hot water for use within a building. A roof truss is described that additionally captures sunlight for illuminating a building. The roof and wall components are adaptable to heating and cooling seasons so as to minimize the loss of air-conditioned air in the summer time and to maximize solar heating during cold months. Solar energy captured by a structurally integrated solar collector can be directly converted to electricity through use of photovoltaic materials or by harnessing airflow through structurally integrated solar collector to obtain electricity through mechanical conversion.
| 8
|
FIELD OF INVENTION
[0001] The present invention relates to novel heterocyclic compounds which contain a heterocylic ring bearing at least one substituent, linked together by a linker containing an acetylenic group, a vinylic group or an azo group. In addition, the present invention relates to pharmaceutical compositions containing novel invention compounds.
BACKGROUND OF THE INVENTION
[0002] Unsaturated heterocylic compounds find a wide variety of uses. For example, compounds of this class find uses as modulators of physiological processes that are mediated by ligand-activated receptors Receptors that are activated by ligands are located throughout the nervous, cardiac, renal, digestive and bronchial systems, among others. Therefore, in the nervous system, for example, heterocyclic compounds are capable of functioning as agonists or antagonists of receptors for neurotransmitters, neurohormones and neuromodulators. Ligand-activated receptors have been identified in a wide variety of species, including humans, other mammals and vertebrates as well as in invertebrate species. Therefore, compounds of this class are also able to modulate receptor-mediated processes throughout phylogeny and find uses in a wide variety of applications, e.g., as insecticides and fingicides.
[0003] Accordingly, there is a continuing need in the art for new members of this compound class.
BRIEF DESCRIPTION OF THE INVENTION
[0004] In accordance with the present invention, there is provided a novel class of heterocyclic compounds. Compounds of the invention contain a substituted, unsaturated five, six or seven membered heterocyclic ring that includes at least one nitrogen atom and at least one carbon atom. The ring additionally includes three, four or five atoms independently selected from carbon, nitrogen, sulfur and oxygen atoms. The heterocyclic ring has at least one substituent located at a ring position adjacent to a ring nitrogen atom. This mandatory substituent of the ring includes a moiety (B), linked to the heterocyclic ring via a carbon-carbon double bond, a carbon-carbon triple bond or an azo group. The mandatory substituent is positioned adjacent to the ring nitrogen atom.
[0005] Invention compounds are useful for a wide variety of applications. For example heterocyclic compounds can act to modulate physiological processes by functioning as agonists and antagonists of receptors in the nervous system. Invention compounds may also act as insecticides, and as fungicides. Pharmaceutical compositions containing invention compounds also have wide utility.
DETAILED DESCRIPTION OF THE INVENTION
[0006] In accordance with the present invention, there are provided compounds having the structure:
A—L—B
[0007] or enantiomers, diastereomeric isomers or mixtures of any two or more thereof, or pharmaceutically acceptable salts thereof, wherein:
[0008] A is a 5-, 6- or 7-membered ring having the structure:
[0009] wherein at least one of W, X, Y and Z is (CR) p , wherein p is 0, 1 or 2;
[0010] the remainder of W, X, Y and Z are each independently O, N or S; and
[0011] each R is independently halogen, substituted or unsubstituted hydrocarbyl, substituted or unsubstituted aryl, heterocycle, mercapto, nitro, carboxyl, carbamate, carboxamide, hydroxy, ester, cyano, amine, amide, amidine, amido, sulfonyl or sulfonamide, wherein q is 0, 1, 2 or 3;
[0012] L is substituted or unsubstituted alkenylene, alkynylene, or azo; and
[0013] B is substituted or unsubstituted hydrocarbyl, substituted or unsubstituted cyclohydrocarbyl, substituted or unsubstituted heterocycle, optionally containing one or more double bonds, or substituted or unsubstituted aryl;
[0014] provided, that the following compounds are excluded: the compounds wherein
[0015] A is a 6-membered ring wherein:
[0016] W, X, Y and Z are (CR) p wherein p is 1; and
[0017] R at the W position is hydrogen, lower alkyl, hydroxy, hydroxy-lower alkyl, amino-lower alkyl, lower alkylamino-lower alkyl, di-lower alklamino-lower alkyl, unsubstituted or hydroxy-substituted lower alkyleneamino-lower alkyl, lower alkoxy, lower alkanoyloxy, amino-lower alkoxy, lower alkylamino-lower alkoxy, di-lower alkylamino-lower alkoxy, phthalimido-lower alkoxy, unsubstituted or hydroxy- or 2-oxo-imidazolidin-1-yl-substitued lower alkyleneamino-lower alkoxy, carboxy, esterified or amidated carboxy, carboxy-lower alkoxy or esterified carboxy-lower-alkoxy; R at the X position is hydrogen; R at the Y position is hydrogen, lower alkyl, carboxy, esterified carboxy, amidated carboxy, hydroxy-lower alkyl, hydroxy, lower alkoxy or lower alkanoyloxy; and R at the Z position is hydrogen, lower alkyl, hydroxy-lower alkyl, carboxy, esterified carboxy, amidated carboxy, unsubstituted or lower alkyl-, lower alkoxy-, halo- and/or trifluoromethyl-substituted N-lower alkyl-N-phenylcarbamoyl, lower alkoxy, halo-lower alkyl or halo-lower alkoxy;
[0018] L is substituted or unsubstituted alkenylene, alkynylene or azo,
[0019] B is substituted or unsubstituted aryl or heterocycle having two or more double bonds, wherein substituents are independently lower alkyl, lower alkenyl, lower alkynyl, phenyl, phenyl-lower alkynyl, hydroxy, hydroxy-lower alkyl, lower alkoxy, lower alkenyloxy, lower alkylenedioxy, lower alkanoyloxy, phenoxy, phenyl-lower alkoxy, acyl, carboxy, esterified carboxy, amidated carboxy, cyano, nitro, amino, acylamino, N-acyl-N-lower alkylamino, halo and halo-lower alkyl, wherein phenyl, phenyl-lower alkynyl, phenoxy, and phenyl-lower alkoxy may bear further substituents; and
[0020] the compounds wherein
[0021] A is a 6-membered ring wherein:
[0022] W, X, Y and Z are (CR) p wherein p is 1; R at the X position is not hydrogen; and R at the W, Y and Z positions are hydrogen;
[0023] L is alkenylene or alkynylene; and
[0024] B is a substituted or unsubstituted aryl or heterocycle containing two or more double bonds; and
[0025] the compounds wherein
[0026] A is a 5-membered ring wherein:
[0027] one of W, X, Y and Z is (CR) p , and p is 0, two of W, X, Y and Z are (CR) p and p is 1, and the remaining variable ring member is O or S; or
[0028] one of W, X, Y and Z is N, one of W, X, Y and Z is (CR) p and p is 1, one of W, X, Y and Z is (CR) p and p is 0, and the remaining variable ring member is O, S or (CR) p , and p is 1; or
[0029] two of W, X, Y and Z are N, one of W, X, Y and Z is (CR) p , and p is 0, and the remaining variable ring member is, O or S or (CR) p , and p is 1;
[0030] each R is independently hydrogen, nitro, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -haloalkylthio, C 3 -C 6 -alkenyl or C 3 -C 8 -cycloalkyl;
[0031] L is alkynylene; and
[0032] B is substituted or unsubstituted aryl, wherein substituents are independently nitro, cyano, C 1 -C 6 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkthio, C 1 -C 4 -haloalkylthio, C 1 -C 4 -alkoxycarbonyl, C 3 -C 6 -alkenyl, phenyl or phenoxy, wherein phenyl and phenoxy may bear further substituents; and
[0033] the compounds wherein
[0034] A is a 6-membered ring wherein:
[0035] W, X, Y and Z are (CR)p, wherein p is 1 and R is hydrogen,
[0036] L is alkynylene; and
[0037] B is unsubstituted 1-cyclopenten-1-yl or unsubstituted 1-cyclohexen-1-yl; and
[0038] the compounds wherein
[0039] A is a 5-membered ring wherein:
[0040] W is (CR)p, and p is 0, Y and Z are (CR)p, and p is 1, X is N or S; and R is phenyl; or
[0041] W is (CR)p, and p is 0, X and Z are (CR)p, and p is 1, Y is O, N or S; and R is phenyl;
[0042] L is unsubstituted alkenylene and
[0043] B is unsubstituted phenyl; and
[0044] the compounds wherein A is a 5-membered ring containing two double bonds, wherein one of W, X, Y and Z is (CR) p , and p is 0, and the remaining ring members are (CR) p and p is 1; and
[0045] the compounds wherein A is unsubstituted heterocycle containing two or more double bonds; L is alkenylene or alkynylene, and B is unsubstituted phenyl.
[0046] As employed herein, “hydrocarbyl” refers to straight or branched chain univalent and bivalent radicals derived from saturated or unsaturated moieties containing only carbon and hydrogen atoms, and having in the range of about 1 up to 12 carbon atoms. Exemplary hydrocarbyl moieties include alkyl moieties, alkenyl moieties, dialkenyl moieties, trialkenyl moieties, alkynyl moieties, alkadiynal moieties, alkatriynal moieties, alkenyne moieties, alkadienyne moieties, aLkenediyne moieties, and the like. The term “substituted hydrocarbyl” refers to hydrocarbyl moieties further bearing substituents as set forth below;
[0047] “alkyl” refers to straight or branched chain alkyl radicals having in the range of about 1 up to 12 carbon atoms; “substituted alkyl” refers to alkyl radicals further bearing one or more substituents such as hydroxy, alkoxy, mercapto, aryl, heterocycle, halogen, trifluoromethyl, pentafluoroethyl, cyano, cyanomethyl, nitro, amino, amide, amidine, amido, carboxyl, carboxamide, carbamate, ester, sulfonyl, sulfonamide, and the like;
[0048] “alkenyl” refers to straight or branched chain hydrocarbyl radicals having at least one carbon-carbon double bond, and having in the range of about 2 up to 12 carbon atoms (with radicals having in the range of about 2 up to 6 carbon atoms presently preferred), and “substituted alkenyl” refers to alkenyl radicals further bearing one or more substituents as set forth above;
[0049] “alkenylene” refers to straight or branched chain divalent alkenyl moieties having at least one carbon-carbon double bond, and having in the range of about 2 up to 12 carbon atoms (with divalent alkenyl moieties having in the range of about 2 up to 6 carbon atoms presently preferred), and “substituted lower alkenylene” refers to divalent alkenyl radicals further bearing one or more substituents as set forth above;
[0050] “alkynyl” refers to straight or branched chain hydrocarbyl radicals having at least one carbon-carbon triple bond, and having in the range of about 2 up to 12 carbon atoms (with radicals having in the range of about 2 up to 6 carbon atoms presently being preferred), and “substituted alkynyl” refers to alkynyl radicals further bearing one or more substituents as set forth above;
[0051] “alkynylene” refers to straight or branched chain divalent alkynyl moieties having at least one carbon-carbon triple bond, and having in the range of about 2 up to 12 carbon atoms (with divalent alkynyl moieties having two carbon atoms presently being preferred), and “substituted alkynylene” refers to divalent alkynyl radicals further bearing one or more substituents as set forth above;
[0052] “cyclohydrocarbyl” refers to cyclic (i.e., ring-containing) univalent radicals derived from saturated or unsaturated moieties containing only carbon and hydrogen atoms, and having in the range of about 3 up to 20 carbon atoms. Exemplary cyclohydrocarbyl moieties include cycloalkyl moieties, cycloalkenyl moieties, cycloalkadienyl moieties, cycloalkatrienyl moieties, cycloalkynyl moieties, cycloalkadiynyl moieties, spiro hydrocarbon moieties wherein two rings are joined by a single atom which is the only common member of the two rings (e.g., spiro[3.4]octanyl, and the like), bicyclic hydrocarbon moieties wherein two rings are joined and have two atoms in common (e.g., bicyclo [3.2.1]octane, bicyclo [2.2.1]hept-2-ene, and the like), and the like. The term “substituted cyclohydrocarbyl” refers to cyclohydrocarbyl moieties further bearing one or more substituents as set forth above;
[0053] “cycloalkyl” refers to ring-containing radicals containing in the range of about 3 up to 20 carbon atoms, and “substituted cycloalkyl” refers to cycloalkyl radicals further bearing one or more substituents as set forth above;
[0054] “cycloalkenyl” refers to ring-containing alkenyl radicals having at least one carbon-carbon double bond in the ring, and having in the range of about 3 up to 20 carbon atoms, and “substituted cycloalkenyl” refers to cyclic alkenyl radicals further bearing one or more substituents as set forth above;
[0055] “cycloalkynyl” refers to ring-containing alkynyl radicals having at least one carbon-carbon triple bond in the ring, and having in the range of about 3 up to 20 carbon atoms, and “substituted cycloalkynyl” refers to cyclic alkynyl radicals further bearing one or more substituents as set forth above;
[0056] “aryl” refers to mononuclear and polynuclear aromatic radicals having in the range of 6 up to 14 carbon atoms, and “substituted aryl” refers to aryl radicals further bearing one or more substituents as set forth above, for example, alkylaryl moieties;
[0057] “heterocycle” refers to ring-containing radicals having one or more heteroatoms (e.g., N, O, S) as part of the ring structure, and having in the range of 3 up to 20 atoms in the ring. Heterocyclic moieties may be saturated or unsaturated when optionally containing one or more double bonds, and may contain more than one ring. Heterocyclic moieties include, for example, monocyclic moieties such as imidazolyl moieties, pyrimidinyl moieties, isothiazolyl moieties, isoxazolyl moieties, moieties, and the like, and bicyclic heterocyclic moieties such as azabicycloalkanyl moieties, oxabicycloalkyl moieties, and the like. The term “substituted heterocycle” refers to heterocycles further bearing one or more substituents as set forth above;
[0058] “azo” refers to the bivalent moiety —N═N—, wherein each bond is attached to a different carbon atom;
[0059] “halogen” refers to fluoride, chloride, bromide or iodide radicals.
[0060] In accordance with the present invention, A is a 5-, 6- or 7-membered unsaturated heterocyclic moiety, containing a ring having at least one nitrogen atom located on the ring in a position adjacent to a carbon atom which bears a linking moiety as a substituent. The ring further contains 3, 4 or 5 independently variable atoms selected from carbon, nitrogen, sulfur and oxygen. Thus, A can be pyridinyl, imidazolyl, pyridazinyl, pyrimidinyl, pyrazoyl, pyrazinyl, triazolyl, triazinyl, tetrazolyl, tetrazinyl, isoxazolyl, oxazolyl, oxadiazolyl, oxatriazolyl, oxadiazinyl, isothiazolyl, thiazoyl, dioxazolyl, oxathiazolyl, oxathiazinyl, azepinyl, diazepinyl, and the like. Those of skill in the art will recognize that multiple isomers exist for a single chemical formula; each of the possible isomeric forms of the various empirical formulae set forth herein are contemplated by the invention. When a variable ring atom is carbon, it bears a hydrogen, or is optionally substituted with halogen, substituted or unsubstituted hydrocarbyl, substituted or unsubstituted aryl, thiol, nitro, carboxyl, ester, cyano, amine, amide, carboxamide, amidine, amido, sulfonamide, and the like, with presently preferred embodiments having no substituent (.i.e., q is 0) or bearing the following substituents: halogen, alkyl, containing one up to four carbon atoms, fluorinated alkyl, containing one up to four carbon atoms, and amine. Substitution at position Z of the ring is presently preferred.
[0061] In accordance with one embodiment of the invention, A is a 5-, 6- or 7-membered ring containing, as ring members, a nitrogen atom and a sulfur atom. Moieties contemplated for use by this embodiment of the invention include those wherein A is isothiazol-3-yl (1,2-thiazol-3-yl), thiazol-4-yl (1,3,-thiazol-4-yl), thiazol-2-yl (1,3-thiazol-2-yl), 1,2-thiazin-3-yl, 1,3-thiazin-4-yl, 1,4-thiazin-3-yl, 1,3-thiazin-2-yl, thiazepinyl, and the like. Presently preferred moieties include those wherein A is isothiazol-3-yl (1,2-thiazol-3-yl), thiazol-4-yl (1,3-thiazol-4-yl) and thiazol-2-yl (1,3-thiazol-2-yl).
[0062] In accordance with another embodiment of the invention, A is a 5-, 6- or 7-membered ring containing, as ring members, a nitrogen atom and an oxygen atom. Moieties contemplated by this embodiment of the invention include those wherein A is 1,2-oxazin-3-yl, 1,3-oxazin-4-yl, 1,4-oxazin-3-yl, 1,3-oxazin-2-yl, oxazol-2-yl, isoxazol-3-yl, oxazol-4-yl, oxazepinyl, and the like. Presently preferred moieties include those wherein A is oxazol-2-yl, isoxazol-3-yl and oxazol-4-yl.
[0063] In accordance with another embodiment of the invention, A is a 5-, 6-, or 7-membered ring containing as ring members two nitrogen atoms. Moieties contemplated by this embodiment of the invention include those wherein A is 3-pyridazinyl (1,2-diazin-3-yl), pyrimidin-4-yl (1,3-diazin-4-yl), pyrazin-3-yl (1,4-diazin-3-yl), pyrimidin-2-yl (1,3-diazin-2-yl), pyrazol-3-yl (1,2-diazol-3-yl), imidazol-4-yl (1,3-isodiazol-4-yl, imidazol-2-yl (1,3-isodiazol-2-yl), diazepinyl, and the like. Presently preferred moieties include those wherein A is 3-pyridazinyl (1,2-diazin-3-yl), pyrimidin-4-yl (1,3-diazin-4-yl), pyrazin-3-yl (1,4-diazin-3-yl), pyrimidin-2-yl (1,3-diazin-2-yl), 1,3-isodiazol-4-yl and 1,3-isodiazol-2-yl.
[0064] In accordance with still another embodiment of the invention, A is a 5-, 6-, or 7-membered ring containing, as ring members, three nitrogen atoms. Moieties contemplated by this embodiment of the invention include those wherein A is 1,2,3-triazin-4-yl, 1,2,4-triazin-6-yl, 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl, 1,3,5-triazin-2-yl, 1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl, triazepinyl, and the like. Presently preferred moieties include those wherein A is 1,2,3-triazin-4-yl, 1,2,4-triazin-6-yl, 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl, 1,3,5-triazin-2-yl, 1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl.
[0065] In accordance with still another embodiment of the invention, A is a 5-, 6-, or 7-membered ring containing, as ring members, four nitrogen atoms. Moieties contemplated for use in the practice of the invention include those wherein A is tetrazin-2-yl, tetrazin-3-yl, tetrazin-5-yl, tetrazolyl, tetrazepinyl, and the like. Presently preferred moieties include those wherein A is tetrazolyl.
[0066] In accordance with yet another embodiment of the invention, A is a 5-, 6-, or 7-membered ring containing, as ring members, one sulfur atom and two nitrogen atoms. Moieties contemplated by this embodiment of the invention include those wherein A is 1,2,6-thiadiazin-3-yl, 1,2,5-thiadiazin-3-yl, 1,2,4-thiadiazin-3-yl, 1,2,5-thiadiazin-4-yl, 1,2,3-thiadiazin-4-yl, 1,3,4-thiadiazin-5-yl, 1,3,4-thiadiazin-2-yl, 1,2,4-thiadiazin-5-yl, 1,3,5-thiadiazin-4-yl, 1,3,5-thiadiazin-2-yl, 1,2,4-thiadiazol-3-yl, 1,2,3-thiadiazol-4-yl, 1,3,4-thiadiazol-2-yl, 1,2,5-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, thiadiazepinyl, and the like. Presently preferred moieties include those wherein A is 1,2,4-thiadiazol-3-yl, 1,2,3-thiadiazol-4-yl, 1,3,4-thiadiazol-2-yl, 1,2,5-thiadiazol-3-yl and 1,2,4-thiadiazol-5-yl.
[0067] In accordance with yet another embodiment of the invention, A is a 5-, 6-, or 7-membered ring containing, as ring members, one oxygen atom and two nitrogen atoms. Moieties contemplated by this embodiment of the invention include those wherein A is 1,2,6-oxadiazin-3-yl, 1,2,5-oxadiazin-3-yl, 1,2,4-oxadiazin-3-yl, 1,2,5-oxadiazin-4-yl, 1,2,3-oxadiazin-4-yl, 1,3,4-oxadiazin-5-yl, 1,3,4-oxadiazin-2-yl, 1,2,4-oxadiazin-5-yl, 1,3,5-oxadiazin-4-yl, 1,3,5-oxadiazin-2-yl, 1,2,4-oxadiazol-3-yl, 1,2,3-oxadiazol-4-yl, 1,3,4-oxadiazol-2-yl, 1,2,5-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, oxadiazepinyl, and the like. Presently preferred moieties include those wherein A is 1,2,4-oxadiazol-3-yl, 1,2,3-oxadiazol-4-yl, 1,3,4-oxadiazol-2-yl, 1,2,5-oxadiazol-3-yl and 1,2,4-oxadiazol-5-yl.
[0068] In accordance with still another embodiment of the invention, A is a 5-, 6-, or 7-membered ring containing as ring members, one up to six nitrogen atoms, and/or one up to six carbon atoms, and/or zero up to five sulfur atoms, and/or zero up to five oxygen atoms.
[0069] Further, in accordance with the present invention, L is a linking moiety which links moieties A and B. L is selected from substituted or unsubstituted alkenylene moieties, alkynylene moieties or azo moieties. Presently preferred compounds of the invention are those wherein L is alkenylene or alkynylene moieties containing two carbon atoms, with alkynylene most preferred.
[0070] Further, in accordance with the present invention, B is a moiety linked through bridging moiety L to moiety A. Radicals contemplated for use in the invention are those wherein B is substituted or unsubstituted hydrocarbyl, substituted or unsubstituted cyclohydrocarbyl, substituted or unsubstituted heterocycle, optionally containing one or more double bonds, substituted or unsubstituted aryl, and the like.
[0071] Presently preferred compounds of the invention are those wherein B is a substituted or unsubstituted hydrocarbyl selected from substituted or unsubstituted alkyl moieties, alkenyl moieties, dialkenyl moieties, trialkenyl moieties, alkynyl moieties, alkadiynyl moieties, alkatriynyl moieties, alkenynyl moieties, alkadienynyl moieties, alkenediynyl moieties, and the like.
[0072] Further preferred compounds of the invention are those wherein B is a substituted or unsubstituted cyclohydrocarbyl selected from substituted or unsubstituted cycloalkyl moieties, cycloalkenyl moieties, cycloalkadienyl moieties, cycloalkatrienyl moieties, cycloalkynyl moieties, cycloalkadiynyl moieties, bicyclic hydrocarbon moieties wherein two rings have two atoms in common, and the like. Especially preferred compounds are those wherein B is cycloalkyl and cycloalkenyl having in the range of 4 up to about 8 carbon atoms.
[0073] Still further preferred compounds of the invention are those wherein B is a substituted or unsubstituted heterocycle, optionally containing one or more double bonds. Exemplary compounds include pyridyl, thiazolyl, furyl, dihydropyranyl, dihydrothiopyranyl, piperidinyl, and the like. Also preferred are compounds wherein B is substituted or unsubstituted aryl. Especially preferred compounds are those wherein substituents are methyl, trifluoromethyl and fluoro and wherein B is 3,5-di-trifluoromethyl phenyl.
[0074] Those of skill in the art recognize that invention compounds may contain one or more chiral centers, and thus can exist as racemic mixtures. For many applications, it is preferred to carry out stereoselective syntheses and/or to subject the reaction product to appropriate purification steps so as to produce substantially optically pure materials. Suitable stereoselective synthetic procedures for producing optically pure materials are well known in the art, as are procedures for purifying racemic mixtures into optically pure fractions. Those of skill in the art will further recognize that invention compounds may exist in polymorphic forms wherein a compound is capable of crystallizing in different forms. Suitable methods for identifying and separating polymorphisms are known in the art.
[0075] As used herein, with reference to compounds not embraced by the scope of the claims, esterified carboxy is, for example, lower alkoxycarbonyl, phenyl-lower alkoxycarbonyl or phenyl-lower alkoxycarbonyl substituted in the phenyl moiety by one or more substituents selected from lower alkyl, lower alkoxy, halo and halo-lower alkyl. Esterified carboxy-lower-alkoxy is, for example, lower alkoxycarbonyl-lower alkoxy. Amidated carboxy is, for example, unsubstituted or aliphatically substituted carbamoyl such as carbamoyl, N-lower alkylcarbamoyl, N,N-di-lower alkylcarbamoyl unsubstituted or lower alkyl-, lower alkoxy-, halo- and/or trifluoromethyl-substituted N-phenyl- or N-lower-alkyl-N-phenyl-carbamoyl.
[0076] As used herein, with reference to compounds not embraced by the scope of the claims, acyl is, for example, lower alkanoyl, lower alkenoyl or unsubstituted or lower alkyl-, lower alkoxy-, halo- and/or trifluoromethyl-substituted benzoyl. Acylamino is, for example, lower alkanoylamino, and N-acyl-N-lower alkylamino is, for example, N-lower alkanoyl-N-lower-alkylamino or unsubstituted or lower alkyl-, lower alkoxy- halo- and/or trifluoromethyl-substituted benzoylamino.
[0077] As referred to in reference to compounds not embraced by the scope of the claims “lower” groups are understood to comprise up to and including seven carbon atoms. N-lower-alkyl-N-phenylcarbamoyl is, for example, N-C 1 -C 4 alkyl-N-phenylcarbamoyl, such as N-methyl, N-ethyl, N-propyl, N-isopropyl or N-butyl-N-phenylcarbamoyl.
[0078] As used herein, with reference to compounds not embraced by the scope of the claims, amino-lower alkyl is, for example, amino-C 1 -C 4 alkyl, preferably of the formula —(CH 2 ) n ,—NH 2 in which n is 2 or 3, such as aminomethyl, 2-aminoethyl, 3-aminopropyl or 4-aminobutyl. Hydroxy-lower alkyl is, for example, hydroxy-C 1 -C 4 alkyl, such as hydroxymethyl, 2-hydroxy ethyl, 3-hydroxypropyl, 2-hydroxyisopropyl or 4-hydroxybutyl. Halo-lower alkyl is, for example, polyhalo-C 1 -C 4 alkyl, such as trifluoromethyl.
[0079] As used herein, with reference to compounds not embraced by the scope of the claims, lower alkoxy is, for example, C 1 -C 7 alkoxy, preferably C 1 -C 4 alkoxy, such as methoxy, ethoxy, propyloxy, isopropyloxy or butyloxy, but may also represent isobutyloxy, sec.butyloxy, tert.-butyloxy or a C 5 -C 7 alkoxy group, such as a pentyloxy, hexyloxy or heptyloxy group amino-lower alkoxy is, for example, amino-C 2 -C 4 alkoxy preferably of the formula —O—(CH 2 ) n —NR a R b in which n is 2 or 3, such as 2-aminoethoxy, 3-aminopropyloxy or 4-aminobutyloxy. Carboxy-lower-alkoxy is, for example, carboxy-C 1 -C 4 alkoxy, such as carboxymethoxy, 2-carboxyethoxy, 3-carboxypropyloxy or 4-carboxybutyloxy. Lower alkanoyloxy is, for example, C 1 -C 7 alkanoyloxy, such as acetoxy, propionyloxy, butyryloxy, isobutyryloxy or pivaloyloxy. Halo-lower alkoxy is, for example, halo- or polyhalo-C 1 -C 7 alkoxy, preferably halo- or polyhalo-C 1 -C 4 alkoxy, such as halo- or polyhaloethoxy, halo- or polyhalopropyloxy or butyl-oxy, wherein “poly” refers, for example, to tri- or pentahalo, and “halo” denotes, for example, fluoro or chloro.
[0080] As used herein, with reference to compounds not embraced by the scope of the claims, lower alkylamino-lower alkoxy is, for example, C 1 -C 4 alkylamino-C 2 -C 4 alkoxy, preferably of the formula —O—(CH 2 ) n —NR a R b in which n is 2 or 3 and R a and R b , independently of each other, denote lower alkyl groups as defined hereinbefore, such as methyl, ethyl, propyl or butyl. Lower alkylamino-lower alkyl is, for example, C 1 -C 4 alkylamino-C 1 -C 4 alkyl, preferably of the formula —(CH 2 ) n —NR a R b in which n is 2 or 3 and R a and R b , independently of each other, denote lower alkyl groups as defined hereinbefore, such as methyl, ethyl, propyl or butyl. Di-lower alkylamino-lower alkyl is, for example, Di—C 1 —C 4 alkylamino-C 1 -C 4 alkyl, preferably of the formula —(CH 2 ) n —NR a P b in which n is 2 or 3 and R a and R b , independently of each other, denote lower alkyl groups such as methyl, ethyl, propyl or butyl. Di-lower alkylamino-lower alkoxy is, for example, Di-C 1 -C 4 alkylamino-C 2 -C 4 alkoxy, preferably of the formula —O—(CH 2 ) n —NR a R b in which n is 2 or 3 and R a and R b , independently of each other, denote lower alkyl groups such as methyl, ethyl, propyl or butyl.
[0081] As used herein, with reference to compounds not embraced by the scope of the claims, optionally hydroxy-substituted lower alkyleneamino-lower alkyl is, for example, unsubstituted or hydroxy-substituted 5- to 7-membered alkyleneamino-C 1 -C 4 alkyl, preferably of the formula —(CH 2 ) n —R c in which n is 2 or 3 and Rc pyrrolidino, hydroxypyrrolidino, piperidino, hydroxypiperidino, homopiperidino or hydroxyhomopiperidino. Furthermore, optionally hydroxy-substituted lower alkyleneamino-lower alkoxy is, for example, unsubstituted or hydroxy-substituted 5- to 7-membered alkyleneamino-C 1 -C 4 alkoxy, preferably of the formula —O—(CH 2 ) n —R c in which n is 2 or 3 and R C pyrrolidino, hydroxypyrrolidino, piperidino, hydroxypiperidino, homopiperidino or hydroxyhomopiperidino.
[0082] In accordance with another embodiment of the present invention, there are provided pharmaceutical compositions comprising heterocyclic compounds as described above, in combination with pharmaceutically acceptable carriers. Optionally, invention compounds can be converted into non-toxic acid addition salts, depending on the substituents thereon. Thus, the above-described compounds (optionally in combination with pharmaceutically acceptable carriers) can be used in the manufacture of medicaments useful for the treatment of a variety of indications.
[0083] Pharmaceutically acceptable carriers contemplated for use in the practice of the present invention include carriers suitable for intravenous, subcutaneous, transcutaneous, intramuscular, intracutaneous, intrathecal, inhalation, intracranial, epidural, vaginal, oral, sublingual, rectal, and the like administration. Administration in the form of creams, lotions, tablets, dispersible powders, granules, syrups, elixirs, sterile aqueous or non-aqueous solutions, suspensions or emulsions, patches, and the like, is contemplated.
[0084] For the preparation of oral liquids, suitable carriers include emulsions, solutions, suspensions, syrups, and the like, optionally containing additives such as wetting agents, emulsifying and suspending agents, sweetening, flavoring and perfuming agents, and the like.
[0085] For the preparation of fluids for parenteral administration, suitable carriers include sterile aqueous or non-aqueous solutions, suspensions, or emulsions. Examples of non-aqueous solvents or vehicles are propylene glycol, polyethylene glycol, vegetable oils, such as olive oil and corn oil, gelatin, and injectable organic esters such as ethyl oleate. Such dosage forms may also contain adjuvants such as preserving, wetting, emulsifying, and dispersing agents. They may be sterilized, for example, by filtration through a bacteria-retaining filter, by incorporating sterilizing agents into the compositions, by irradiating the compositions, or by heating the compositions. They can also be manufactured in the form of sterile water, or some other sterile injectable medium immediately before use.
[0086] Invention compounds can optionally be converted into non-toxic acid addition salts. Such salts are generally prepared by reacting the compounds of this invention with a suitable organic or inorganic acid. Representative salts include hydrochloride, hydrobromide, sulfate, bisulfate, methanesulfonate, acetate, oxalate, adipate, alginate, aspartate, valerate, oleate, laurate, borate, benzoate, lactate, phosphate, toluenesulfonate (tosylate), citrate, malate, maleate, fumarate, succinate, tartrate, napsylate, methanesulfonate, 2-naphthalenesulfonate, nicotinate, benzenesulfonate, butyrate, camphorate, camphorsulfonate, cyclopentanepropionate, digluconate, dodecylsulfate, glucoheptanoate, glycerophosphate, heptanoate, hexanoate, undecanoate, 2-hydroxyethanesulfonate,ethanesulfonate, and the like. Salts can also be formed with inorganic acids such as sulfate, bisulfate, hemisulfate, hydrochloride, chlorate, perchlorate, hydrobromide, hydroiodide, and the like. Examples of a base salt include ammonium salts; alkali metal salts such as sodium salts, potassium salts, and the like; alkaline earth metal salts such as calcium salts, magnesium salts, and the like; salts with organic bases such as dicyclohexylamine salts, N-methyl-D-glucamine, phenylethylamine, and the like; and salts with amino acids such as arginine, lysine, and the like. Such salts can readily be prepared employing methods well known in the art.
[0087] In accordance with another embodiment of the present invention, there are provided methods for the preparation of heterocyclic compounds as described above. For example, many of the heterocyclic compounds described above can be prepared using synthetic chemistry techniques well known in the art (see Comprehensive Heterocyclic Chemistry, Katritzky, A. R. and Rees, C. W. eds., Pergamon Press, Oxford, 1984) from a precursor of the substituted heterocycle of Formula 1 as outlined in Scheme 1.
[0088] Thus in Scheme 1, a substituted heterocycle precursor (prepared using synthetic chemistry techniques well known in the art) is reacted with an alkyne derivative. In Scheme 1, (R) q , W, X, Y, Z and B are as defined above and D and E are functional groups which are capable of undergoing a transition metal-catalyzed cross-coupling reaction. For example, D is a group such as hydrogen, halogen, acyloxy, fluorosulfonate, trifluoromethanesulfonate, alkyl- or arylsulfonate, alkyl- or arylsulfinate, alkyl- or arylsulfide, phosphate, phosphinate, and the like, and E is hydrogen or a metallic or metalloid species such as Li, MgX (X is halogen), SnR 3 , B(OR) 2 , SiR 3 , GeR 3 , and the like. The coupling may be promoted by a homogeneous catalyst such as PdCl 2 (PPh 3 ) 2 , or by a heterogeneous catalyst such as Pd on carbon in a suitable solvent (e.g., tetrahydrofuran (THF), dimethoxyethane (DME), acetonitrile, dimethylformamide (DMF), etc.). Typically, a co-catalyst such as copper (I) iodide and a base (e.g., NEt 3 , K 2 CO 3 etc.) will also be present in the reaction mixture. The coupling reaction typically proceeds by allowing the reaction temperature to warm slowly from about 0° C. up to ambient temperature over a period of several hours. The reaction mixture is then maintained at ambient temperature, or heated to a temperature anywhere between 30° C. and 150° C. The reaction mixture is then maintained at a suitable temperature for a time in the range of about 4 up to 48 hours, with about 12 hours typically being sufficient. The product from the reaction can be isolated and purified employing standard techniques, such as solvent extraction, chromatography, crystallization, distillation, and the like.
[0089] Another embodiment of the present invention is illustrated in Scheme 2. A substituted heterocycle precursor is reacted with an alkene derivative in a manner similar to the procedure described for Scheme 1.
[0090] The alkene derivative product from Scheme 2 may be converted to an alkyne derivative using the approach outlined in Scheme 3.
[0091] Thus, the alkene derivative may be contacted with a halogenating agent such as chlorine, bromine, iodine, NCS (N-chlorosuccinimide), NBS (N-bromosuccinimide), NIS (N-iodosuccinimide), iodine monochloride, etc. in a suitable solvent (CCL 4 , CHCl 3 , CH 2 Cl 2 , acetic acid, and the like). The resulting halogenated derivative (G=halogen) is then treated with a suitable base such as NaOH, KOH, DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), DBN (diazabicyclononene), DABCO (1,4-diazabicyclo[2.2.2]octane), and the like, which promotes a double elimination reaction to afford the alkyne. The reaction is carried out in a suitable solvent such as ethanol, acetonitrile, toluene, etc. at an appropriate temperature, usually between about 0° C. and 150° C.
[0092] In another embodiment of the present invention, a substituted heterocyclic derivative is reacted with an aldehyde or ketone to provide a substituted alkene. (See Scheme 4.)
[0093] Thus, in Scheme 4, J is hydrogen, PR 3 , P(O)(OR) 2 , SO 2 R, SiR 3 , and the like, K is hydrogen, alkyl or aryl (as defined previously) and R is hydrogen, acetyl, and the like. Suitable catalysts for this reaction include bases such as NaH, n-buytllithium, lithium dilsopropylamide, lithium hexamethyl disilazide, H 2 NR, HNR 2 , NR 3 etc., or electropositive reagents such as Ac 2 O, ZnCl 2 , and the like. The reaction is carried out in a suitable solvent (THF, acetonitrile, etc.) at an appropriate temperature, usually between about 0° C. and 150° C. Sometimes an intermediate is isolated and purified or partially purified before continuing through to the alkene product.
[0094] In yet another embodiment of the present invention, a substituted heterocyclic aldehyde or ketone is reacted with an activated methylene-containing compound to provide a substituted alkene. (See Scheme 5.)
[0095] Thus, in Scheme 5, J, K, R, the catalyst and reaction conditions are as described for Scheme 4. Again, as in Scheme 4, sometimes an intermediate is isolated and purified or partially purified before continuing through to the alkene product.
[0096] The alkene products from the reactions in Scheme 4 and Scheme 5 may be converted to an alkyne derivative using reagents and conditions as described for Scheme 3.
[0097] Another method for the preparation of heterocyclic compounds of Formula I is depicted in Scheme 6.
[0098] In scheme 6, Y is O or S and G is halogen or a similar leaving group, and L and B are as defined previously. The reagents are contacted in a suitable solvent such as ethanol, DMF, and the like and stirred until the product forms. Typically reaction temperatures will be in the range of ambient through to about 150° C., and reaction times will be from about 1 h to about 48 h, with about 70° C. and 4 h being presently preferred. The heterocycle product can be isolated and purified employing standard techniques, such as solvent extraction, chromatography, crystallization, distillation, and the like. Often, the product will be isolated as the hydrochloride or hydrobromide salt, and this material may be carried onto the next step with or without purification.
[0099] Yet another method for the preparation of heterocyclic compounds of Formula I is depicted in Scheme 7.
[0100] In Scheme 7, W may be O or S, G is halogen or a similar leaving group, and L and B are as defined previously. The reaction conditions and purification procedures are as described for Scheme 6.
[0101] In another embodiment of the present invention, depicted in Scheme 8, an alkynyl-substituted heterocycle precursor (prepared using synthetic chemistry techniques well known in the art) is reacted with a species B, bearing a reactive functional group D (See Scheme 8.)
[0102] In Scheme 8, (R) q , W, X, Y, Z and B are as defined above and D and E are functional groups which are capable of undergoing a transition metal-catalyzed cross-coupling reaction. For example, D is a group such as hydrogen, halogen, acyloxy, fluorosulfonate, trifluoromethanesulfonate, alkyl- or arylsulfonate, alkyl or arylsulfinate, alkyl- or arylsulfide, phosphate, phosphinate, and the like, and E is hydrogen or a metallic or metalloid species such as Li, MgX (X is halogen), SnR 3 , B(OR) 2 , SiR 3 , GeR 3 , and the like. The coupling may be promoted by a homogeneous catalyst such as PdCl 2 (PPh 3 ) 2 , or by a heterogeneous catalyst such as Pd on carbon in a suitable solvent (e.g. tetrahydrofuran (THF), dimethoxyethane (DME), acetonitrile, dimethylformamide (DMF), etc.). Typically a co-catalyst such as copper (I) iodide and the like and a base (e.g. NEt 3 , K 2 CO 3 , etc.) will also be present in the reaction mixture. The coupling reaction is typically allowed to proceed by allowing the reaction temperature to warm slowly from about 0° C. up to ambient temperature over a period of several hours. The reaction mixture is then maintained at ambient temperature, or heated to a temperature anywhere between about 30° C. up to about 150° C. The reaction mixture is then maintained at a suitable temperature for a time in the range of about 4 up to about 48 hours, with about 12 hours typically being sufficient. The product from the reaction can be isolated and purified employing standard techniques, such as solvent extraction, chromatography, crystallization, distillation, and the like.
[0103] Another embodiment of the present invention is illustrated in Scheme 9.
[0104] An alkenyl-substituted heterocycle precursor is reacted with an alkene derivative in a manner similar to the procedure described for Scheme 8. The product alkene derivative from Scheme 9 may be converted to an alkyne derivative using the approach outlined previously in Scheme 3 above.
[0105] In yet another embodiment of the present invention, depicted in Scheme 10, an alkynyl-substituted heterocycle precursor is reacted with a species composed of a carbonyl group bearing substituents R′ and CHR″R′″.
[0106] Thus in Scheme 10, R′, R″ and R′″ may be hydrogen or other substituents as described previously, or may optionally combine to form a ring (this portion of the molecule constitutes B in the final compound). E is hydrogen or a metallic or metalloid species such as Li, MgX, wherein X is halogen, SnR 3 , B(OR) 2 , SiR 3 , GeR 3 , and the like. Suitable catalysts for this reaction include bases such as NaH, n-butyllithium, lithium diusopropylamide, lithium hexamethylsilazide, H 2 NR, HNR 2 , NR 3 , nBu 4 NF, ethylmagnesium halide, etc. R in Scheme 10 may be hydrogen, Ac, and the like. Typically the reaction is carried out in a suitable solvent such as diethylether, THF, DME, toluene, and the like, and at an appropriate temperature, usually between −100° C. and 25° C. The reaction is allowed to proceed for an appropriate length of time, usually from about 15 minutes to about 24 hours. The intermediate bearing the —OR group may be isolated and purified as described above, partially purified or carried on to the next step without purification. Elimination of the —OR group to provide the alkene derivative may be accomplished using a variety of methods well known to those skilled in the art. For example, the intermediate may be contacted with POCl 3 in a solvent such as pyridine and stirred at a suitable temperature, typically between about 0° C. and about 150° C., for an appropriate amount of time, usually between about 1 h and about 48 h. The product from the reaction can be isolated and purified employing standard techniques, such as solvent extraction, chromatography, crystallization, distillation, and the like.
[0107] The following examples are intended to illustrate but not to limit the invention in any manner, shape, or form, either explicitly or implicitly. While they are typical of those that might be used, other procedures, methodologies, or techniques known to those skill in the art may alternatively be used.
EXAMPLE 1
Synthesis of 2-(1-Cyclohexen-1-ylethynyl)-1,3-thiazole
[0108] Triphenylphosphine (570 mg, 2.0 mmol) was dissolved in tetrahydrofuran (THF) (20 mL), then argon was bubbled through the solution for several minutes to deoxygenate it. Palladium(II) acetate (120 mg, 0.54 mmol) was added, and the reaction mixture was heated to 60° C. for 0.5 h, and then cooled to ambient temperature. CuI (308 mg, 1.6 mmol), 2-bromo-1,3-thiazole (3.0 g, 18 mmol), 1-ethynylcyclohexene (2.4 g, 20 mmol), potassium carbonate (6 g, 45 mmol) and water (1.0 mL, 58 mmol) were dissolved in 50 mL dimethyoxyether (DME) and argon was bubbled through the solution for several minutes to deoxygenate the mixture. The catalyst solution of triphenylphosphine and palladium (II) acetate in THF was added to the reaction flask which was heated to 75° C. for 2h. After 2 h, heating was discontinued and the reaction was allowed to cool to ambient temperature. After stirring for 16 h, gas chromatography/mass spectrometry (GC/MS) analysis showed the reaction to be complete. The mixture was filtered through Celite™, the filter pad was washed thoroughly with ethyl acetate, and the combined filtrates were concentrated in vacuo. The residue was dissolved in ethyl acetate (200 mL) and washed with water (200 mL), brine (200 mL), dried over Na 2 SO 4 , filtered, and concentrated in vacuo. The residue was purified by column chromatography eluting with hexane then 97:3 hexane:ethyl acetate to afford 2-(1-cyclohexen-1-ylethynyl)-1,3-thiazole (2.56 g, 74% yield) as a brown oil. 1 H NMR (CDCl 3 ,300 MHz) δ7.79 (d, J=3.0 Hz, 1H), 7.31 (d, J=3.0 Hz, 1H), 6.37-6.35 (m, 1H), 2.23-2.14 (m, 4H), 1.71-1.57 (m, 4H). MS (ESI) 190.0 (M + +H).
EXAMPLE 2
Synthesis of 2-Methyl-4-(1,3-thiazol-2-yl)-3-butyn-2-ol
[0109] 2-Bromo-1,3-thiazole (6.0 g, 37 mmol) and CuI (1.3 g, 7.3 mmol) were combined in DME (150 mL) and argon gas was bubbled through the suspension for several minutes to deoxygenate the mixture. Triethylamine (25 mL, 180 mmol) and PdCl 2 (PPh 3 ) 2 (2.5 g, 3.7 mmol) were added and 2-methyl-3-butyne-2-ol (4.6 g, 55 mmol) was added dropwise. After stirring at ambient temperature for 16 h, GC/MS showed the reaction was not complete. The reaction was heated to reflux for 2 h. The mixture was filtered through Celite™, the filter pad was washed thoroughly with ethyl acetate, and the combined filtrates were concentrated in vacuo. The residue was dissolved in ethyl acetate (600 mL), washed with water (600 mL), brine (600 mL), dried over Na 2 SO 4 , filtered and concentrated in vacuo. The residue was purified by column chromatography eluting with hexane then 7:3 hexane:ethyl acetate to afford 4-(2-thiazolyl)-2-methyl-3-butyn-2-ol contaminated with 2,7-dimethyl-but-3,5-diyne-2,7-diol. (The dimer of 2-methyl-3-butyne-2-ol) The product was crystallized from boiling hexane to afford 2-methyl-4-(1,3-thiazol-2-yl)-3-butyn-2-ol (2.18 g, 36% yield) as off white crystals that were contaminated with a small amount of 2,7-dimethyl-but-3,5-diyne-2,7-diol. M.p. 69-70° C. 1 H NMR (CDCl 3 , 300 MHz) δ7.80 (d, J=3.0 Hz, 1H), 7.34 (d, J=3.0 Hz, 1H), 4.40 (s, 1H), 1.65 (s, 6H). MS (ESI) 168.1 (M + +H).
EXAMPLE 3
Synthesis of 5-Chloro-3-pyridinyl trifluoromethanesulfonate
[0110] Trifluoromethanesulfonic anhydride (5.0 mL, 30 mmol) was dissolved in CH 2 Cl 2 (100 mL), and cooled to 0° C. 5-Chloro-3-pyridinol (3.10 g, 23.9 mmol), and triethylamine (6.5 mL, 47 mmol) were dissolved in CH 2 Cl 2 (50 mL), and the resulting solution was added to the cold trifluoromethanesulfonic anhydride solution dropwise via cannula. The resulting dark brownish-red solution was stirred at 0° C. for 5 minutes, and then the ice bath was removed and the reaction mixture was allowed to warm to ambient temperature. After stirring for 16 h at ambient temperature the reaction was quenched by pouring into water and basified by addition of saturated aqueous sodium carbonate. The basic aqueous phase was extracted with CH 2 Cl 2 (2×50 mL), the combined organics dried over Na 2 SO 4 , filtered and concentrated in vacuo. The resulting black viscous oil was filtered through a plug of silica gel and fractions were collected while eluting with 1:1 hexane:ethyl acetate. Fractions containing the desired product were combined, concentrated in vacuo, and further purified by column chromatography eluting with 15:1 then 10:1 hexane:ethyl acetate to afford 5-chloro-3-pyridinyl trifluoromethanesulfonate (3.68 g, 59% yield) as a golden liquid. 1 H NMR (CDCl 3 , 300 MHz) δ8.65 (d, J=2 Hz, 1H), 8.52 (d, J=2 Hz, 1H), 7.70 (t, J=3Hz, 1H). MS (ESI) 261 (M + , 35 Cl), 263 (M + , 37 Cl).
EXAMPLE 4
Synthesis of 3-Chloro-5-[(trimethylsilyl)ethynyl]pyridine
[0111] 5-Chloro-3-pyridinyl trifluoromethanesulfonate (4.0 g, 15 mmol) and Cul (580 mg, 3.0 mmol) were combined in DME (100 mL) and argon gas was bubbled through the suspension for several minutes to deoxygenate the mixture. Triethylamine (10.6 mL, 76.5 mmol), and PdCl 2 (PPh 3 ) 2 (1.1 g, 1.5 mmol) were added, then trimethylsilyl-acetylene (3.3 ml, 23 mmol) was added dropwise. The reaction mixture was stirred at ambient temperature for 1 h at which time GC/MS analysis indicated that the reaction was complete. The mixture was filtered through Celite™, and the filter pad was washed thoroughly with ethyl acetate. The combined filtrates were concentrated in vacuo and the residue was dissolved in ethyl acetate (300 mL), washed with water (300 mL), brine (300 mL), dried over Na 2 SO 4 filtered, and concentrated in vacuo. The residue was purified by column chromatography eluting with hexane then 99:1 hexane:ethyl acetate to afford 3-chloro-5-[(trimethylsilyl)ethynyl]pyridine (2.8 g, 87% yield) as a brown solid. 1 H NMR (CDCl 3 ,300 MHz) δ8.51 (s, 1H), 8.44 (s, 1H), 7.70(s, 1H), 0.22 (s, 9H). MS (EI ionization) 209 (M + ).
EXAMPLE 5
Synthesis of 3-Chloro-5-ethynylpyridine
[0112] 3-Chloro-5-[(trimethylsilyl)ethynyl]pyridine (1.4 g, 6.7 mmol) was dissolved in methanol (15 ml) and cooled to 0° C., to the resulting solution was added potassium carbonate (93 mg, 0.67 mmol). The ice bath was removed and the reaction mixture was stirred at ambient temperature for 0.5 h at which time thin layer chromatography (TLC) and GC/MS analysis indicated that the reaction was complete. The solvent was removed in vacuo and the residue was dissolved in diethyl ether (50 mL), washed with water (100 mL), brine (100 mL), dried over Na 2 SO 4 , filtered, and concentrated in vacuo to afford 3-chloro-5-ethynylpyridine (822 mg, 90% yield) which was pure by GC/MS analysis. MS (EI ionization) 137 ( 35 Cl M + ), 139 ( 37 Cl M + ). This material was carried on to the next step without further purification.
EXAMPLE 6
Synthesis of 3-Chloro-5-(1,3-thiazol-2-ylethynyl)pyridine.
[0113] 2-Bromo-1,3-thiazole (980 mg, 6.0 mmol) and CuI (230 mg, 1.2 mmol) were combined in DME (15 mL) and argon gas was bubbled through the suspension for several minutes to deoxygenate the mixture. Triethylamine (4.2 mL, 30 mmol) and PdCl 2 (PPh 3 ) 2 (420 mg, 0.60 mmol) were added, then 3-chloro-5-ethynylpyridine (820 mg, 19 mmol) was added dropwise. After stirring at ambient temperature for 16 h, GC/MS analysis showed starting material remaining. The reaction mixture was heated at reflux for 2 h. The mixture was filtered through Celite™, the filter pad was washed thoroughly with ethyl acetate, and the combined filtrates were concentrated in vacuo. The residue was dissolved in ethyl acetate (100 mL), and washed with water (100 mL), brine (100 mL), dried over Na 2 SO 4 filtered and concentrated in vacuo. The residue was purified by column chromatography eluting with hexane then 9:1 hexane:ethyl acetate to afford 3-chloro-5-(1,3-thiazol-2-ylethynyl)pyridine which contained some dimer. This material was crystallized from hot ethyl acetate to afford 3-chloro-5-(1,3-thiazol-2-ylethynyl)pyridine (300 mg 23% yield) as light orange crystals M.p. 124-125° C. 1 H NMR (CDCl 3 , 300 MHz) δ8.70 (d, J=1.5 Hz, 1H), 8.59 (d, J=3.0 Hz, 1H), 7.93 (d, J=3.0 Hz, 1H), 7.88 (t, J=2.0 Hz, 1H), 7.48 (d, J=3.0 Hz, 2H). MS (ESI) 221.1 (M + +H).
EXAMPLE 7
Synthesis of 2-(Cyclohexylethyl)-1,3-thiazole
[0114] 2-Bromo-1,3-thiazole (3.1 g, 19 mmol) and CuI (290 mg, 1.5 mmol) were combined in DME (30 mL) and argon gas was bubbled through the suspension for several minutes to deoxygenate the mixture. Triethylamine (13 mL, 95 mmol) and PdCl 2 (PPh 3 ) 2 (530 mg, 0.76 mmol) were added and cyclohexylethyne (2.0 g, 19 mmol) was added dropwise. The reaction mixture was stirred at ambient temperature for 16 h at which time GC/MS analysis indicated that the reaction was complete. The mixture was filtered through Celite™, and the filter pad was washed thoroughly with ethyl acetate. The combined filtrates were concentrated in vacuo and the residue was dissolved in ethyl acetate (300 mL), washed with water (300 mL), brine (300 mL), dried over Na 2 SO 4 , filtered, and concentrated in vacuo. The residue was purified by column chromatography eluting with hexane then 99:1 hexane:ethyl acetate to afford 2-(cyclohexylethynyl)-1,3-thiazole (1.6 g, 44% yield) as a yellow oil. 1 H NMR (CDCl 3 , 300 MHz) δ7.76 (d, J=9.0 Hz, 1H), 7.28 (d, J=3.0 Hz, 1H), 2.68-2.59 (m, 1H), 1.91-1.28 (m, 10H). MS (ESI) 191.7 (M + ).
EXAMPLE 8
2 -(1-Pentynyl)-1,3-thiazole
[0115] 2-Bromo-1,3-thiazole (2.0 g, 12 mmol) and CuI (183 mg, 0.96 mmol) were combined in DME (30 mL) and argon gas was bubbled through the suspension for several minutes to deoxygenate the mixture. Triethylamine (8 mL, 60 mmol) and PdCl 2 (PPh 3 ) 2 (337 mg, 0.48 mmol) were added and 1-pentyne (979 mg, 14.4 mmol) was added dropwise. The reaction mixture was stirred at ambient temperature for 6 h at which time GC/MS analysis indicated that the reaction was not complete. Additional 1-pentyne (3.0 mL, 29 mmol) was added and the reaction was heated to 35° C. under a condenser. After heating for 16 h, GC/MS analysis indicated that the reaction was complete. The mixture was filtered through Celite™, and the filter pad was washed thoroughly with ethyl acetate. The combined filtrates were concentrated in vacuo and the residue was dissolved in ethyl acetate (300 mL), washed with water (300 mL), brine (300 mL), dried over Na 2 SO 4 filtered, and concentrated in vacuo. The residue was purified by column chromatography eluting with hexane, 99:1, then 97:3 hexane:ethyl acetate to 2-(1-pentynyl)-1,3-thiazole (820 mg, 44% yield) as a yellow oil. 1 H NMR (CDCl 3 , 300 MHz) δ7.76 (d, J=3.0 Hz, 1H), 7.28 (d, J=3.0 Hz, 1H), 2.47-2.42 (m, 2H), 1.68-1.60 (m, 2H), 1.08 -0.99 (m, 3H). MS (ESI) 151.6 (M + ).
EXAMPLE 9
2-(3-Cyclohexyl-1-propynyl)-1,3-thiazole
[0116] 2-Bromo-1,3-thiazole (2.0 g, 12 mmol) and CuI (185 mg, 0.97 mmol) were combined in DME (30 mL) and argon gas was bubbled through the suspension for several minutes to deoxygenate the mixture. Triethylamine (8.5 mL, 61 mmol) and PdCl 2 (PPh 3 ) 2 (340 mg, 0.49 mmol) were added and 3-cyclohexyl-1-propyne (2.9 g, 24 mmol) was added dropwise. The reaction was stirred at ambient temperature for 16 h at which time GC/MS analysis indicated that the reaction was complete. The mixture was filtered through Celite™, and the filter pad was washed thoroughly with ethyl acetate. The combined filtrates were concentrated in vacuo. The residue was dissolved in ethyl acetate (300 mL), washed with water (300 mL), brine (300 mL), dried over Na 2 SO 4 , filtered, and concentrated in vacuo. The residue was purified by column chromatography eluting with hexane, then 98:2 hexane:ethyl acetate to afford 2-(3-cyclohexyl-1-propynyl)-1,3-thiazole (1.14 g, 46% yield) as a yellow oil. 1 H NMR (CDCl 3 , 300 MHz) δ7.76 (d, J=3.0 Hz, 1H), 7.27 (d, J=3.0 Hz, 1H), 2.35 (d, J=6 Hz, 2H), 1.89-1.61 (m, 5H), 1.3-1.03 (m, 6H). MS (ESI) 205.9 (M + +H).
EXAMPLE 10
Synthesis of 2-(1-Cyclohexen-1-ylethynyl)-5-nitro-1,3-thiazole
[0117] 2-Bromo-5-nitro-1,3-thiazole (2.5 g, 12 mmol) and CuI (460 mg, 2.5 mmol) were combined in DME (30 mL) and argon gas was bubbled through the suspension for several minutes to deoxygenate the mixture. Triethylamine (8.4 mL, 60 mmol) and PdCl 2 (PPh 3 ) 2 (840 mg, 1.2 mmol) were added and 1-ethynycyclohexene (1.5 g, 14.4 mmol) was added dropwise. The reaction was heated under reflux for 16 h at which time GC/MS analysis indicated that the reaction was complete. The mixture was filtered through Celite™, and the filter pad was washed thoroughly with ethyl acetate. The combined filtrates were concentrated in vacuo and the residue was dissolved in ethyl acetate (300 mL), washed with water (300 mL), brine (300 mL), dried over Na 2 SO 4 , filtered, and concentrated in vacuo. The residue was purified by column chromatography eluting with hexane, 99:1 then 98.5:1.5 hexane:ethyl acetate to afford 2-(1-cyclohexen-1-ylethynyl)-5-nitro-1,3-thiazole (1.4 g, 51.8% yield) as a yellow powder. M.p. 85-86° C. 1 H NMR (CDCl 3 , 300 MHz) δ8.5 (s, 1H), 6.52 (br s, 1H), 2.24 (br s, 4H), 1.63 (br s, 4H). MS (ESI) 235.1 (M + +H).
EXAMPLE 11
Synthesis of 2-(3,3-Dimethyl-1-butynyl-1,3-thiazole
[0118] Triphenylphosphine (380 mg, 1.5 mmol) was dissolved in TBF (20 mL), then argon was bubbled through the solution for several minutes to deoxygenate it. Palladium(II) acetate (82 mg, 0.37 mmol) was added, and the reaction mixture was heated to 60° C. for 0.5 h, and then cooled to ambient temperature. CuI (210 mg, 1.1 mmol), 2-bromo-1,3-thiazole (1.6 g, 9.8 mmol), potassium carbonate (4.2 g, 31 mmol) and water (0.70 mL, 39 mmol) were dissolved in DME (30 mL) and argon was bubbled through the mixture for several minutes to deoxygenate the mixture. 3,3-dimethyl-1-butyne (1.0 g, 12.2 mmol) was then added to mixture. The catalyst solution of triphenylphosphine and palladium (II) acetate in THF was added to the reaction flask which was heated to 30° C. for 2 h. After this time heating was discontinued and the mixture was allowed to stir at ambient temperature. After stirring for 16 h, GC/MS analysis showed the reaction to be complete. The mixture was filtered through Celite™, the filter pad was washed thoroughly with ethyl acetate, and the combined filtrates were concentrated in vacuo. The residue was dissolved in ethyl acetate (200 mL), washed with water (200 mL), brine (200 mL), dried over Na 2 SO 4 , filtered, and concentrated in vacuo. The residue was purified by column chromatography eluting with hexane, then 99:1 hexane:ethyl acetate to afford 2-(3,3-dimethyl-1-butynyl)-1,3-thiazole (0.45 g, 28% yield) as a yellow oil. 1 H NMR (CDCl 3 , 300 MHz) δ7.74 (d, J=3.0 Hz, 1H), 7.28 (d, J=3.0 Hz, 1H), 1.33 (s, 9H). MS (ESI) 166.1 (M + +H).
EXAMPLE 12
Synthesis of 1-(1,3-Thiazol-2-ylethynyl)cyclopentanol
[0119] 2-Bromo-1,3-thiazole (3.1 g, 19 mmol) and CuI (360 mg, 1.9 mmol) were combined in DME (30 mL) and argon gas was bubbled through the suspension for several minutes to deoxygenate the mixture. Triethylamine (13 mL, 94 mmol) and PdCl 2 (PPh 3 ) 2 (660 mg, 0.94 mmol) were added and 1-ethynycyclopentanol (2.5 g, 23 mmol) was added dropwise. The reaction was heated at 50° C. for 16 h at which time GC/MS analysis indicated that the reaction was complete. The mixture was filtered through Celite™, and the filter pad was washed thoroughly with ethyl acetate. The combined filtrates were concentrated in vacuo and the residue was dissolved in ethyl acetate (300 mL), washed with water (300 mL), brine (300 mL), dried over Na 2 SO 4 , filtered, and concentrated in vacuo. The residue was purified by column chromatography eluting with hexane, 6:1 then 3:1 hexane:ethyl acetate to afford 1-(1,3-thiazol-2-ylethynyl)cyclopentanol (2.3 g, 52% yield) as a yellow powder. 1 H NMR (CDCl 3 , 300 MHz) δ7.80 (d, J=3 Hz, 1H), 7.65 (d, J=3 Hz, 1H), 2.04-1.73 (m, 10.8H). MS (EI ionization) 193 (M + ).
EXAMPLE 13
Synthesis of 2-(1-Cyclopenten-1-ylethynyl)-1,3-thiazole
[0120] 1-(1,3-Thiazol-2-ylethynyl)cyclopentanol was dissolved in pyridine (20 ml) and phosphorus oxychloride (1.2 g, 6.2 mmol) was added dropwise under argon. The reaction was stirred at ambient temperature for 1 h at which time a precipitate had appeared. At this time GC/MS analysis indicated that the reaction was complete and the pyridine was removed in vacuo. The residue was dissolved in ethyl acetate (200 mL) and washed with water (200 mL), brine (200 mL), dried over Na 2 SO 4 , filtered, and concentrated in vacuo. The residue was purified by column chromatography eluting with hexane then 99:1 hexane:ethyl acetate to 2-(1-cyclopenten-1-ylethynyl)-1,3-thiazole (0.25 g, 24% yield) as a light brown solid. M.p. 70.5-72° C., 1 H NMR (CDCl 3 , 300 MHz)δ7.80 (d, J=3.0 Hz, 1H), 7.34 (d, J=3.0 Hz, 1H), 6.31-6.30 (m, 1H), 2.60-2.45 (m, 4H), 2.00-1.90 (m, 2H). MS (ESI) 176.1 (M + +H).
EXAMPLE 14
Synthesis of Methyl 3-(1,3-thiazol-2-yl)-2-propynyl ether
[0121] 2-Bromo-1,3-thiazole (2.0 g, 12 mmol) and CuI (456 mg, 2.4 mmol) were combined in DME (30 mL) and argon gas was bubbled through the suspension for several minutes to deoxygenate the mixture. Triethylamine (8.6 mL, 60 mmol) and PdCl 2 (PPh 3 ) 2 (842 mg, 1.2 mmol) were added and methyl propargyl ether (1.00 g, 14.4 mmol) was added dropwise. The reaction was stirred at 55° C. under a condenser. After stirring at 55° C. for 16 h, GC/MS analysis indicated that the reaction was complete. The mixture was filtered through Celite™, and the filter pad was washed thoroughly with ethyl acetate. The combined filtrates were concentrated in vacuo and the residue was dissolved in ethyl acetate (300 mL), washed with water (300 mL), brine (300 mL), dried over Na 2 SO 4 filtered, and concentrated in vacuo. The residue was purified by column chromatography eluting with hexane, 99:1, 97:3, then 96:4 hexane:ethyl acetate to afford methyl 3-(1,3-thiazol-2-yl)-2-propynyl ether (250 mg, 13% yield) as a yellow oil. 1 H NMR (CDCl 3 , 300 MHz) δ7.78 (d, J=3.0 Hz, 1H), 7.37 (d, J=3.0 Hz, 1H), 4.37 (s, 2H), 3.47 (s, 3H). MS (ESI) 154.1 (M + +H).
EXAMPLE 15
Synthesis of 2-Methyl-4-(3-pyridinyl)-3-butyn-2-ol
[0122] 3-Bromopyridine (3.0 mL, 31 mmol), triethylamine (22 mL, 160 mmol), CuI (1.2 g, 6.2 mmol), and PdCl 2 (PPh 3 ) 2 (1.1 g, 1.5 mmol) were combined in DME (92 mL) and cooled to 0° C. 2-Methyl-3-butyne-2-ol (9.0 mL, 93 mmol) was then added and the reaction was allowed to slowly warm to ambient temperature. The mixture was then heated to 55-60° C. for 16 h. The mixture was filtered through Celite™, and the pad was washed thoroughly with ethyl acetate. The combined filtrates were washed with brine (3×100 mL), dried over MgSO 4 , and filtered. The solution was concentrated in vacuo, and the residue was purified by column chromatography eluting with 90:10 hexane:ethyl acetate then ethyl acetate to afford 2-methyl-4-(3-pyridinyl)-3-butyn-2-ol (2.0 g, 40% yield) as a brown oil 1 H NMR (CDCl 3 , 300 MHz) δ8.76 (br s, 1H), 8.52 (br s, 1H), 7.74-7.70 (m, 1H), 4.08 (br s, 1H), 1.63 (s, 3H). MS (EI ionization) 161 (M + ).
EXAMPLE 16
Synthesis of 3-Ethynylpyridine
[0123] 2-Methyl-4-(3-pyridinyl)-3-butyn-2-ol (611 mg, 3.79 mmol) was dissolved in toluene (12 mL) at ambient temperature. A small amount (spatula tip) of NaH (60% dispersion in mineral oil) was added, and the reaction was heated to reflux. After 15 minutes the reaction was cooled to ambient temperature, and quenched by the addition of 1M aqueous HCl (30 mL). Crude product from a previous preparation (˜200 mg) was added to the workup mixture. The acidic aqueous was extracted with ethyl acetate (2×20 mL), basified by the addition of saturated aqueous NaHCO 3 , and extracted with CH 2 Cl 2 . The CH 2 Cl 2 extracts were dried over MgSO 4 , filtered, and concentrated in vacuo to afford crude 3-ethynylpyridine (1.5 g, >100%) as a brown liquid. 1 H NMR (CDCl 3 , 300 MHz) δ8.73 (br s, 1H), 8.58 (br s, 1H), 7.80-7.76 (m, 1H), 7.29-7.16 (m, 1H), 3.28 (s, 1H). A portion of this material was carried on to the next step without further purification.
EXAMPLE 17
Synthesis of 3-(1,3-Thiazol-2-ylethynyl)pyridine
[0124] 2-Bromo-1,3-thiazole (0.15 mL, 1.6 mmol), CuI (98 mg, o.51 mmol), PdCl 2 (PPh 3 ) 2 (120 mg, 0.17 mmol) and triethylamine (2.8 mL, 20 mmol) were combined in DMF (6.8 mL) and cooled in an ice bath. 3-Ethynylpyridine (520 mg, 5.04 mmol) was then added to the mixture as a solution in DMF (3.0 ML). The ice bath was removed and the reaction was allowed to stir at ambient temperature for 16 h. The reaction mixture was filtered through a pad of Celite™, and the pad was washed thoroughly with ethyl acetate. The filtrate was washed with brine (3×20 mL). A partial emulsion was observed. The mixture was concentrated in vacuo and the residue was taken up in CH 2 Cl 2 , washed with brine, dried over Na 2 SO 4 , filtered and concentrated in vacuo. The crude product was purified by column chromatography on silica gel eluting with 80:20 followed by 30:20 hexane:ethyl acetate to afford 3-(1,3-thiazol-2-ylethynyl)pyridine (160 mg) as a mixture with another product exhibiting a mass of 204 in the GC/MS, assigned as pyridylalkyne dimer. A portion of the mixture (100 mg) was further purified by preparative reverse phase HPLC eluting with a gradient of 80:20 to 0:100 water:acetonitrile over twenty minutes. The fractions containing the desired product were collected (detection by uv at 210 nm) to afford 3-(1,3-thiazol-2-ylethynyl)pyridine as a white waxy solid (15 mg). 1 H NMR (CDCl 3 , 300 MHz) δ9.3-8.5 (br s, 2H), 7.92-7.90 (m, 2H), 7.50-7.30 (m, 2H). MS (ESI) 187.0 (M + +H).
EXAMPLE 18
Synthesis of 3,3,5,5-Tetramethyl-1-(2-pyridinylethynyl)cyclohexanol.
[0125] To a solution of 2-ethynylpyridine (1.0 g, 10 mmol) in THF at −78° C. was added a 1.0 M solution of ethyl magnesium bromide in THF (10 mL, 10 mmol). After stirring at reduced temperature for 30 minutes a solution of 3,3,5,5-tetramethyl-cyclohexanone (1.5 g, 10 mmol) in THF was added rapidly. The mixture was allowed to warm to ambient temperature over 16 hours, then partitioned between water and ethyl acetate. The organic layer was dried over anhydrous Na 2 SO 4 , and concentrated in vacuo. The resultant product was purified by flash column chromatography on silica gel eluting with 1:1 hexane:ethyl acetate to afford 3,3,5,5-tetramethyl-1-(2-pyridinylethynyl)cyclohexanol (250 mg, 10% yield) as a white solid. M.p. 126-127° C. 1 H NMR (DMSO-d 6 , 300 MHz) δ8.57 (m, 1H), 7.64 (m, 1H), 7.39 (d, J=5 Hz, 1H), 7.22 (m, 1H), 1.91 (d, J=9 Hz, 2H), 1.71 (d, J=9 Hz, 2H), 1.26 (s, 2H), 1.14 (s, 6H), 1.09 (s, 6H).
EXAMPLE 19
Synthesis of 2-[(3,3,5,5-Tetramethyl-1-cyclohexen-1-yl)ethynyl]pyridine
[0126] 3,3,5,5-Tetramethyl-1-(2-pyridinylethynyl)cyclohexanol (200 mg, 0.78 mmol) was dissolved in pyridine. POCl 3 (153 mg, 1.0 mmol) was added, and the mixture was heated to reflux for 6 h. After cooling, the POCl 3 and pyridine were removed in vacuo. The residue was purified by flash column chromatography on silica gel eluting with 2:1 hexane:ethyl acetate to afford 2-[(3,3,5,5-tetramethyl-1-cyclohexen-1-yl)ethynyl]pyridine (148 mg, 80% yield) as a light tan solid. M.p. 55-56° C. 1 H NMR (CDCl 3 , 300 MHz) δ8.56 (m, 1H), 7.62 (m, 1H), 7.40 (d, J=7 Hz, 1H), 7.18 (m 1H), 6.09 (s, 1H), 2.00 (s, 2H), 1.35 (s, 2H), 1.05 (s, 6H), 0.99 (s, 6H).
EXAMPLE 20
Synthesis of 2-[(5-Methyl-1-cyclohexen-1-yl)ethvnyl]pyridine and 2-[(3-methyl-1-cyclohexen-1-yl)ethynyl]pyridine (1:1)
[0127] Using the procedures for Examples 18 and 19 but with the appropriate starting materials, 2-[(5-methyl-1-cyclohexen-1-yl)ethynyl]pyridine and 2-[(3-methyl-1-cyclohexen-1-yl) ethynyl]pyridine were obtained as a mixture of racemic regioisomers. 1 H NMR (CDCl 3 , 300 MHz) δ8.56 (m, 1H), 7.62 (m, 1H), 7.40 (m, 1H), 7.19 (m, 1H), 6.32 (s, 0.5H), 6.20 (s, 0.5 H), 2.25 (m, 3H), 1.73 (m, 3H), (m, 1H), 1.01 (m, 3H). MS (El ionization) Two peaks: 197 (M + ).
EXAMPLE 21
General Procedure for 2-pyridylenynes
[0128] To a cooled a solution of 2-ethynylpyridine in THE to −78° C. was added n-BuLi (1.6 M in hexane, 1 equiv). After 20 minutes stirring at reduced temperature this material was mixed with a solution of the appropriate ketone (1 equiv) in THF. The solution was allowed to warm slowly to ambient temperature. The reaction mixture was then quenched and partitioned between water and ethyl acetate. The organic layer was dried over Na 2 SO 4 , and concentrated in vacuo. The resultant product was purified by flash column chromatography on silica gel eluting with 1:1 hexane:ethyl acetate. The resulting product was dissolved in pyridine or a mixture of pyridine and methylene chloride (1:1). POCl 3 (1.2 equiv) was added and the solution refluxed for 4 to 8 hours. The resultant mixture was partitioned between 1M K 2 CO 3 and ethyl acetate. The organic layer was dried over Na 2 SO 4 , and concentrated in vacuo. The resultant product was purified by flash column chromatography on silica gel eluting with 2:1 hexane:ethyl acetate.
[0129] Using this general procedure the following example compounds (see Examples 22-33) were obtained.
EXAMPLE 22
Synthesis of 2-[(4-Methyl-1-cyclopenten-1-yl)ethynyl]pyridine and 2-[(3-Methyl-1-cyclopenten-1-yl)ethynyl]pyridine (1:1)
[0130] Reactants: 2-ethynylpyridine (620 mg, 6.0 mmol), 3-methylcyclopentanone (0.64 mL, 6.0 mmol); yields 2-[(4-methyl-1-cyclopenten-1-yl)ethynyl]pyridine and 2-[(3-methyl-1-cyclopenten-1-yl)ethynyl]pyridine (1:1) as a transparent oil (200 mg, 18% overall yield), as mixture of regio- and stereoisomers. 1 H NMR (CDCl 3 , 300 MHz) δ8.56 (m, 1H), 7.64 (m, 1H), 7.44 (m, 1H), 7.20 (m, 1H), 6.19 (m, 0.5H), 6.18 (m, 0.5H), 2.90 (m, 0.5H), 2.70 (m, 2.5H), 2.21 (m, 2H), 1.48 (m, 0.5H), 1.08 (app d, J=7.5 Hz, 3H). Two peaks: 182 (M + ), 167 (M + −Me).
EXAMPLE 23
Synthesis of 2-(Bicyclo[2.2.1]hept-2-en-2-ylethynyl)pyridine
[0131] Reactants: 2-ethynylpyridine (1.0 g, 10.0 mmol), norcamphor (1.1 g, 10.0 mmol); yields 2-(bicyclo[2.2.1]hept-2-en-2-ylethynyl)pyridine as a black oil (215 mg, 11% over two steps). This material was mixed with fumaric acid (128 mg, 1.11 mmol), dissolved in MeOH and the resulting solution was concentrated in vacuo to afford a dark brown solid. This was triturated with a mixture of ethyl acetate:ethanol (1:1) and the resultant solids were partitioned between aqueous K 2 CO 3 and ethyl acetate. The organics were dried over Na 2 SO 4 , and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel eluting with 2:1 hexane:ethyl acetate to afford 2-(bicyclo[2.2.1]hept-2-en-2-ylethynyl)pyridine (30 mg, 1.5% overall yield) as a translucent brown oil. 1 H NMR (DMSO-d 6 , 300 MHz) δ8.58 (d,J=5Hz, 1H), 7.64 (m, 1H), 7.40 (m, 1H), 7.19 (m, 1H), 6.48 (d, J=4 Hz, 1H), 3.07 (s, 1H), 2.97 (s, 1H), 1.76 (m, 2H), 1.51 (m, 1H), 1.23 (m, 1H), 1.11 (m, 1H). MS (EI ionization) 195 (M + ).
EXAMPLE 24
Synthesis of 2-[(2,6-Dimethyl-1-cyclohexen-1-yl)ethenyl]pyridine
[0132] Reactants: 2-ethynylpyridine (5.0 mmol, 515 mg), 2,6-dimethylcyclopentanone (6.0 mmol, 0.82 mL); yields 2-[(2,6-dimethyl-1-cyclohexen-1-yl)ethynyl]pyridine as a transparent oil (200 mg, 19% overall yield). 1H NMR (CDCl 3 , 300 MHz) 67 8.56 (m, 1H), 7.60 (m, 1H), 7.42 (m, 1H), 7.19 (m, 1H), 2.40 (m, 1H), 2.10 (m, 2H), 2.01 (s, 3H), 1.76 (m, 2H), 1.56 (m, 1H), 1.34 (m, 1H) (app d, J=7 Hz, 3H). MS (EI ionization) 211 (M + ).
EXAMPLE 25
Synthesis of 2-(1-Cyclohepten-1-ylethynyl)pyridine
[0133] Reactants: 2-ethynylpyridine (5.0 mmol, 515 mg), cycloheptanone (6.0 mmol, 0.71 mL); yields 2-(1-cyclohepten-1-ylethynyl)pyridine as a transparent oil (200 mg, 18% overall yield). 1 H NMR (CDCl 3 , 300 MHz) δ8.54 (m, 1H), 7.59 (m, 1H), 7.40 (m, 1H), 7.16 (m, 1H), 6.52 (t, J=7 Hz, 1H), 2.47 (m, 2H), 2.26 (m, 2H), 1.77 (s, 2H),1.61 (m, 2H), 1.56 (m, 2H). MS (EI ionization) 197 (M + ).
EXAMPLE 26
Synthesis of 2-(1-Cycloocten-1-ylethynyl)pyridine
[0134] Reactants: 2-ethynylpyridine (515 mg, 5.0 mmol), cyclooctanone (756 mg, 6.0 mmol); yields 2-(1-cycloocten-1-ylethynyl)pyridine as a transparent oil (250 mg, 24% overall yield). 1 H NMR (CDCl 3 , 300 MHz) δ8.57 (m, 1H), 7.62 (m, 1H), 7.40 (m, 1H), 7.18 (m, 1H), 6.33 (t, J=7 Hz, 1H), 2.41 (m, 2H), 2.23 (m, 2H), 1.66 (s,2H), 1.52 (br m, 6H). MS (EI ionization) 211 (M + ).
EXAMPLE 27
Synthesis of 2-[(4-Methyl-1-cyclohexen-1-yl)ethynyl]pyridine
[0135] Reactants: 2-ethynylpyridine (6.0 mmol, 618 mg), 4-methylcyclohexanone (6.0 mmol, 672 mg); yields 2-[(4-methyl-1-cyclohexen-1-yl)ethynyl]pyridine as a transparent oil (250 mg, 21% overall yield). 1 H NMR (CDCl 3 , 300 MHz) δ8.57 (m, 1H), 7.59 (m, 1H), 7.39 (m, 1H), 7.20 (m, 1H), 6.30 (m, 1H), 2.22 (m, 3H), 1.25 (m, 1H), 0.99 (m, 3H). MS (EI ionization) 197 (M + ).
EXAMPLE 28
Synthesis of 2-(3,6-Dihydro-2H-thiopyran-4-ylethynyl)pyridine
[0136] Reactants: 2-ethynylpyridine (6.0 mmol, 618 mg), tetrabydrothiopyran-4-one (6.0 mmol, 696 mg); yields 2-(3,6-dihydro-2H-thiopyran-4-ylethynyl)pyridine as a transparent oil (150 mg, 12% overall yield). 1 H NMR (CDCl 3 , 300 MHz) δ8.57 (m, 1H), 7.61 (m, 1H), 7.40 (m, 1H), 7.21 (m, 1H), 6.46 (m, 1H), 3.27 (m, 2H), 2.57 (m, 2H). MS (EI ionization) 201 (M + ).
EXAMPLE 29
Synthesis of 2-(3,6-Dihydro-2H-pyran-4-ylethynyl)pyridine
[0137] Reactants: 2-ethynylpyridine (6.0 mmol, 618 mg), tetrahydro-4H-pyran-4-one (6.0 mmol, 600 mg); yields 2-(3,6-dihydro-2H-pyran-4-ylethynyl)pyridine as a transparent oil (200 mg, 18% overall yield). 1 H NMR (CDCl 3 , 300 MHz) δ8.57 (m, 1H), 7.63 (m, 1H), 7.44 (m, 1H), 7.21 (m, 1H), 6.29 (m, 1H), 4.25 (m, 2H) 3.81 (m, 2H), 2.36 (m, 2H). MS (EI ionization) 185 (M + ).
EXAMPLE 30
Synthesis of 2-{[(1R)-1,7,7-Trimethylbicyclo[2.2.1]hept-2-en-2-yl]ethynyl}pyridine
[0138] Reactants: 2-ethynylpyridine (6.0 mmol, 618 mg), (1R)-(+)-camphor (6.0 mmol, 912 mg); yields 2-{[(1R)-1,7,7-trimethylbicyclo[2.2.1]hept-2-en-2-yl]ethynyl}pyridine as a transparent yellow oil (125 mg, 9% overall yield). 1 H NMR (CDCl 3 , 300 MHz) δ8.57 (, 1H), 7.64 (m, 1H), 7.43 (m, 1H), 7.17 (m, 1H), 6.49 (d, J=3 Hz, 1H), 2.41 (t, J=3 Hz, 1H), 1.92 (br m, 1H), 1.65 (m, 1H), 1.18 (m, 1H), 1.17 (s, 3H), 1.09 (br m, 1H), 0.84 (s, 3H), 0.82 (s, 3H). MS (EI ionization) 237 (M + ).
EXAMPLE 31
Synthesis of 2-[(3,5-Dimethyl-1-cyclohexen-1-yl)ethynyl]pyridine
[0139] Reactants: 2-ethynylpyridine (6.0 mmol, 618 mg), 3,5-dimethylcyclohexanone (6.0 mmol, 0.85 mL); yields 2-[(3,5-dimethyl-1-cyclohexen-1-yl)ethynyl]pyridine as a transparent yellow oil (500 mg, 39% overall yield) as a mixture of diastereomers. 1 H NMR (CDCl 3 , 300 MHz) 67 8.57 (m, 1H), 7.62 (m, 1H), 7.40 (m, 1H), 7.19 (m, 1H), 6.15 (br s, 1H), 2.29 (m, 2H), 1.80 (br m, (2H), 1.00 (m, 6H), 0.88 (br m, 2H). MS (EI ionization) 211 (M + ).
EXAMPLE 32
Synthesis of 2-{[(5R)-5-Methyl-1-cyclohexen-1-yl]ethynyl}pyridine compound with 2-{[(3R)-3-methyl-1-cyclohexen-1-yl]ethynyl}pyridine (1:1)
[0140] Reactants: 2-ethynylpyridine (6.0 mmol, 618 mg), (3R)-(+)-3-methylcyclohexanone (6.0 mmol, 0.73 mL); yields 2-{[(5R)-5-methyl-1-cyclohexen-1-yl]ethynyl}pyridine and 2-{[(3R)-3-methyl-1-cyclohexen-1-yl]ethynyl}pyridine (1:1) as a transparent yellow oil (440 mg, 37% overall yield) as a mixture of regioisomers. 1H NMR (CDCl 3 , 300 MHz) δ8.56 (m, 1H), 7.62 (m, 1H), 7.40 (m, 1H), 7.18 (m, 1H), 6.31 (m, 0.5H), 6.19 (m, 0.5H), 2.30 (m, 3H), 1.85 (m, 2.5H), 1.22 (m, 1H), 0.98 (m, 3.5H). MS (EI ionization) 197 (M + ) two peaks resolved.
EXAMPLE 33
Synthesis of 2-[(3E)-3-Methyl-3-penten-1-vinyl]pyridine, 2-(3-ethyl-3-buten-1 -ynyl pyridine and 2-[(3Z)-3-methyl-3-penten-1-]pyridine
[0141] Reactants: 2-ethynylpyridine (6.0 mmol, 618 mg), 2-butanone (6.0 mmol, 0.54 mL); yields 2-[(3E)-3-methyl-3-penten-1-yny]pyridine, 2-(3-ethyl-3-buten-1 -ynyl)pyridine and 2-[(3Z)-3-methyl-3-penten-1-ynyl]pyridine as a transparent oil (135 mg, 14% overall yield) as a mixture of E, Z and exo-methylene isomers. 1 H NMR (CDCl 3 , 300 MHz) δ8.59 (m, 1H), 7.65 (m, 1H)7.44 (m, 1H), 7.20 (m, 1H), 5.88 (m, 0.75H), 5.53 (s, 0.33H) 5.40 (s, 0.33 H), 2.29 (q, J=7 Hz, 0.65H), 1.93 (m, 4.5H), 1.17 (t, J=7 Hz, 1H). MS (EI ionization) 157 (M + ) two peaks resolved.
EXAMPLE 34
Synthesis of 5-Ethyl-2-(phenylethynyl)pyrimnidine hydrochloride
[0142] 2-Chloro-5-ethylpyrimdine (500 mg, 3.5 mmol), PdCl 2 (PPh 3 ) 2 (250 mg, 0.35 mmol), CuI (203 mg, 1.06 mmol), triethylamne (6.0 mL, 43 mmol), and n-Bu 4 NI (3.85 g, 10.4 mmol) were combined in dimethylformamide (DMF) (30 mL). The mixture was cooled in an ice bath and then phenylacetylene (1.5 mL, 14 mmol) was added. The reaction mixture was then heated to 45-50° C. and after 1.5 h, additional phenylacetylene (1.5 mL, 14 mmol) was added. After an additional 17 h the reaction was diluted with ethyl acetate, washed with brine (4×15 mL), dried over Na 2 SO 4 , filtered, and concentrated in vacuo. The resulting black oil was purified by column chromatography eluting with hexane then 90:10 hexane:ethyl acetate to afford 5-ethyl-2-(phenylethynyl)pyrimdine (770 mg, >100%) as a black oil. MS (EI ionization) 208 (M + ). This material was carried on to the salt formation without further purification.
[0143] 5-Ethyl-2-(phenylethynyl)pyrimdine (730 mg, 3.7 mmol) was dissolved in CH 2 Cl 2 (3.0 mL) and treated with HCl in diethyl ether (4.1 mL of a 1N solution, 4.1 mmol). Upon addition of the HC 1 solution a solid precipitated from the solution. The mixture was diluted with diethyl ether (2 mL) and the supernatant decanted. The resultant solid was dried under high vacuum at 50° C. to afford 5-ethyl-2-(phenylethynyl)pyrimdine hydrochloride (450 mg, 49% yield) as an orange solid. M.p. 101-104° C. 1 H NMR (CD 3 OD, 300 MHz) δ8.75 (s, 2H), 7.58-7.55 (m, 2H), 7.41-7.32 (m, 3H), 2.67 (q, J=7.6 Hz, 2H), 1.21 (t, J=7.6 Hz, 3H).
EXAMPLE 35
Synthesis of 4,6-Dimethoxy-2-(phenylethenyl)pyrimdine hydrochloride
[0144] 2-Chloro-4,6-dimethoxypyrimdine (500 mg, 2.9 mmol), PdCl 2 (PPh 3 ) 2 (200 mg, 0.28 mmol), CuI (160 mg, 0.84 mmol), triethylamne (4.8 mL, 34 mmol), and n-Bu 4 NI (3.2 g, 8.7 mmol) were combined in DMF (24 mL). The mixture was cooled in an ice bath and then phenylacetylene (1.25 mL, 11.4 mmol) was added. The reaction mixture was allowed to warm to ambient temperature. After 2.5 h at ambient temperature the reaction mixture was heated to 45-50° C. After 2 h, additional phenylacetylene (1.0 mL, 9.1 mmol) was added. After an additional 17 h stirring at 45-50° C., the reaction mixture was filtered through a pad of Celite™, and the filter pad was washed thoroughly with ethyl acetate. The combined filtrates were washed with brine (4×20 mL), dried over MgSO 4 , filtered and concentrated in vacuo. The resulting black oil was purified by column chromatography eluting with hexane, 90:10, then 85:15 hexane:ethyl acetate to afford product contaminated with an impurity. Careful column chromatography of this impure material eluting with hexane then 90:10 hexane:ethyl acetate afforded 4,6-dimethoxy-2-(phenylethynyl)pyrimdine (320 mg, 46% yield) as a yellow solid. This material was carried on to the salt formation without further purification.
[0145] 4,6-Dimethoxy-2-(phenylethynyl)pyrimdine (320 mg, 1.3 mmol) was dissolved in CH 2 Cl 2 (1.0 mL), and treated with HCI in diethyl ether (1.6 mL of a 1.0M solution, 1.6 mmol). A yellow solid precipitated immediately. The mixture was diluted with ethyl acetate and allowed to stand in the freezer for 16 h. The cold supernatant was decanted and the remaining solids were triturated with ethyl acetate (1.5 mL), and then hexane (3×2 mL). The remaining solid was dried in vacuo to afford 4,6-dimethoxy-2-(phenylethynyl)pyrimdine hydrochloride (174 mg, 47% yield) as a yellow solid. M.p. 137-138. 1 H NMR (CD 3 OD, 300 MHz) δ7.65-7.62 (m, 2H), 7.46-7.42 (m, 3H), 6.16 (s, 1H), 3.97 (s, 6H).
EXAMPLE 36
Synthesis of 2-[(E)-2-(3-Fluorophenol)ethenyl]-6-methylpyrazine
[0146] 2,6-Dimethylpyrazine (5.0 g, 46 mmol) was dissolved in THF (200 mL) and cooled to 0° C. Potassium t-butoxide (46 mL of a 1.0M solution in THf, 46 mmol) was added to afford a dark red solution. The solution was allowed to warm to ambient temperature and stir for 1 hr. The solution was then cooled to 0° C., and 3-fluorobenzaldehyde (4.9 mL, 46 mmol) was added via syringe pump over 2 h. The reaction was then allowed to slowly warm to ambient temperature. After stirring at ambient temperature for 18 h, the reaction mixture was cooled to 0° C. and quenched by the addition of concentrated aqueous HCl (10 mL). The resulting suspension was allowed to warm to ambient temperature for 15 minutes, then cooled to 0° C. and brought to pH=8 by addition of solid NaHCO 3 . The layers were separated, and the aqueous layer was extracted with ethyl acetate (3×200 mL). The combined organic layers were washed with brine (200 mL), dried over MgSO 4 , filtered, and concentrated in vacuo. The crude product was purified by column chromatography eluting with 90:10, 85:15, then 80:20 hexane:ethyl acetate to afford 2-[(E)-2-(3-fluorophenyl)ethenyl]-6-methylpyrazine (4.14 g, 42% yield) as a light yellow solid. M.p. 43-44° C. 1 H NMR (CDCl 3 , 300 MHz) δ8.44 (s, 1H), 8.31 (s, 1H), 7.29 (d, J=16 Hz, 1H), 7.37-7.26 (m, 3H), 7.12 (d, J=16 Hz, 1H), 7.05-6.98 (m, 1H), 2.59 MS (ESI) 214.5 (M + ). This material was carried on to the next step without further purification.
EXAMPLE 37
Synthesis of 2-[1,2-Dibromo-2-(3-fluorophenyl)ethyl[-6-methyl]pyrazin
[0147] 2-[(E)-2-(3-Fluorophenyl)ethenyl]-6-methylpyrazine from Example 36 (4.14 g, 19.3 mmol) was dissolved in CCl 4 (40 mL). To this solution was added a solution of bromne (1.2 mL, 23 mmol) in CC 4 (20 mL). The brown mixture was then heated to 60° C. After 6 h the suspension was treated with saturated aqueous NaHCO 3 (200 mL) and diluted with ethyl acetate (700 mL). The organic layer was washed with 5% aqueous Na 2 S 2 O 3 (100 mL), brine (100 mL), dried over MgSO 4 , filtered, and concentrated in vacuo. The crude product was purified by column chromatography eluting with 80:20 hexane:ethyl acetate then 95:5, 94:6, and 90:10 CH 2 Cl 2 :ethyl acetate to afford 2-[1,2-dibromo-2-(3-fluorophenyl)ethyl]-6-methylpyrazine (2.97 g, 17% over two steps) as a white solid. This material was carried on to the next step without further purification.
EXAMPLE 38
Synthesis of 2-[(3-Fluorophenyl)ethynyl]-6-methylpyrazine hydrochloride
[0148] 2-[1,2-Dibromo-2-(3-fluorophenyl)ethyl]-6-methylpyrazine (2.97 g, 7.94 mmol) was dissolved in THF (40 mL), treated with DBU (8.7 mL, 63 mmol), and heated to reflux. After 16 h the reaction mixture was cooled, filtered, concentrated in vacuo, and purified by column chromatography eluting with 80:20 then 75:25 hexane:ethyl acetate to afford 2-[(3-fluorophenyl)ethynyl]-6-methylpyrazine (427 mg, 25% yield). This material was carried on to the salt formation without further purification.
[0149] 2-[(3-Fluorophenyl)ethynyl]-6-methylpyrazine (520 mg, 2.45 mmol) was dissolved in CH 2 Cl 2 (3 mL), and the resulting solution was treated with HC 1 in diethyl ether (2.7 mL of a 1.0M solution, 2.7 mmol). The mixture was sonicated, and the solvent decanted. The remaining solid was dried under high vacuum to afford 2-[(3-fluorophenyl)ethynyl]-6-methylpyrazine hydrochloride (338 mg, 60% yield) as a light yellow solid. M.p. 62-63° C. 1 H NMR (CDCl 3 , 300 MHz) δ8.73 (s, 1H), 8.57 (s, 1H), 7.54-7.35 (m, 3H), 7.28-7.20 (m, 3H), 2.84 (s, 3H).
EXAMPLE 39
Synthesis of 1-Chloro-4-(1-cyclohexen-1-yl-3-butyn-2-one
[0150] Anhydrous ZnCl 2 (5.0 g, 37 mmol) was dissolved in TBF (25 mL) and the solution cooled to 0° C. in an ice bath. In another flask 1-ethynylcyclohexene (4.3 mL, 36.3 mmol) was dissolved in THF (25 mL), cooled to 0° C. in an ice bath, and treated with n-butyllithium (15.7 mL of a 2.2M solution in hexane, 34.5 mmol). After 20 minutes the cyclohexenylethynyllithium solution was added via cannula to the ZnCl 2 solution. After an additional 20 minutes Pd(PPh 3 ) 4 (620 mg, 0.54 mmol) was added to the alkynylzinc solution. The resulting yellow solution was treated with chloroacetyl chloride (4.2 mL, 55 mmol) dropwise over 10 minutes. After 2 h at 0° C. the reaction mixture was quenched by the addition of saturated aqueous NH 4 Cl(500 mL), and diluted with ethyl acetate. The aqueous phase was extracted with ethyl acetate (3×200 ml) and the combined organic layers were washed with water (200 ml), brine (200 ml), dried over Na 2 SO 4 , and filtered. The filtrate was concentrated in vacuo to afford a dark brown oil that was purified by column chromatography eluting with hexane, then 99:1 hexane:ethyl acetate to afford 1-chloro-4-(1-cyclohexen-1-yl)-3-butyn-2-one (4.4 g, 67% yield) as an orange oil. 1 H NMR (CDCl 3 , 300 MHz) δ6.56 (m, 1H), 4.23 (s, 2H), 2.19 (m, 4H), 1.68-1.62 (m, 4H). MS (EI ionization) 182 ( 35 Cl M + ), 184 ( 37 Cl M + ). The material was carried on to the next step without further purification.
EXAMPLE 40
Synthesis of 4-(1-Cyclohexen-1-ylethynyl)-2-methyl-1,3-thiazole, p-toluenesulfonic acid salt
[0151] 1-Chloro-4-(1-cyclohexen-1-yl)-3-butyn-2-one (2.0 g, 11.0 mmol) was dissolved in DMF (10.0 mL), thioacetarnide (950 mg, 12.6 mmol) was added, and the resulting pale brown solution was stirred at ambient temperature for 64 h. The reaction mixture was diluted with ethyl acetate (300 mL), washed with saturated NaHCO 3 solution (300 mL), water (300 mL), brine (300 mL), dried over Na 2 SO 4 , filtered, and concentrated in vacuo. The residue was dissolved in ethyl acetate, adsorbed onto silica gel and purified by column chromatography eluting with hexane, 99:1 then 98:2 hexane:ethyl acetate to afford 4-(1-cyclohexen-1-ylethynyl)-2-methyl-1,3-thiazole (620 mg, 28% yield) as a yellow powder. 1H NMR (CDCl 3 , 300 MHz) δ7.22 (s, 1H), 6.27-6.24 (m, 1H). 2.7 (s, 3H) 2.22-2.12 (m, 4H), 1.68-1.58 (m, 4H).
[0152] 4-(1-Cyclohexen-1-ylethynyl)-2-methyl-1,3-thiazole (620 mg, 3.1 mmol) was dissolved in ethanol (30 mL) at ambient temperature. p-Toluenesulfonic acid monohydrate (580 mg, 3.1 mmol) was added in one portion to afford a brown solution. After all of the acid had dissolved the reaction mixture was stirred for several minutes and then concentrated in vacuo to afford a dark brown oil which solidified under high vacuum. The crude material was dissolved in hot ethyl acetate. After cooling to ambient temperature the material was stored in the freezer for few hours. The supernatant solution was decanted and the crystalline solids were dried under high vacuum to afford crystalline 4-(1-cyclohexen-1-ylethynyl)-2-methyl-1,3-thiazole p-toluenesulfonate salt (882 mg , 74% yield) as yellow crystals. M.p. 128-129° C. 1 H NMR (CD 3 OD, 300 MHz) δ7.87 (s, 1H), 7.71-7.68 (d, J=9 Hz, 2H), 7.24 (m, 7.21 (d, J=9Hz, 3H), 6.38 (m,1H), 2.88, (s, 3H), 2.36 (s, 3H), 2.21-2.17 (m, 4H), 1.68-1.64 (m, 4H).
EXAMPLE 41
Synthesis of 4-(1-Cyclohexen-1-ylethynyl)-1,3-thiazol-2-ylamne, p-toluenesulfonic acid salt
[0153] 1-Chloro-4-(1-cyclohexen-1-yl)-3-butyn-2-one (2.0 g, 11 mmol) was dissolved in DMF (10.0 mL), thiourea (996 mg, 13.1 mmol) was added, and the resulting pale brown solution was stirred at ambient temperature for 16 h. The reaction mixture was diluted with ethyl acetate (200 mL), washed with saturated NaHCO 3 solution (100 mL), water (100 mL), brine (100 mL), dried over Na 2 SO 4 , filtered, and concentrated in vacuo. The dark oil was dissolved in ethyl acetate, adsorbed onto silica gel and purified by column chromatography eluting with 9:1 then 3:1 hexane:ethyl acetate to afford 4-(1-cyclohexen-1-ylethynyl)-1,3-thiazol-2-ylam;ne (1.1 g, 49% yield) as an off-white solid. MS (EI ionization) 204 (M + ).
[0154] 4-(1-Cyclohexen-1-ylethynyl)-1,3-thiazol-2-ylam;ne (1.1 g, 5.4 mmol) was dissolved in ethanol (40 mL) at ambient temperature. p-Toluenesulfonic acid monohydrate (1.0 g, 5.4 mmol) was added in one portion to afford a brown solution. After all of the acid had dissolved the reaction mixture was stirred for several minutes and then concentrated in vacuo to afford a dark brown oil which solidified under high vacuum. The crude material was dissolved in hot ethyl acetate. After cooling to ambient temperature the material was stored in the freezer. After several hours in the freezer, the supernatant solution was decanted and the crystalline solids were dried under high vacuum to afford 4-(1-cyclohexen-1-ylethynyl)-1,3-thiazol-2-ylamne p-toluenesulfonate salt (1.84 g, 87% yield) as off-white powder. M.p. 188-189° C. 1 H NMR (CD 3 OD, 300 MHz) δ7.72 -7.69 (d, J=9 Hz, 2H), 7.24-7.22 (d, J=6 Hz, 2H) 6.94 (s, 1H), 6.34-6.32 (m, 1H), 2.36 (s, 3H), 2.19-2.15 (m, 4H) 1.70-1.61 (m, 4H).
EXAMPLE 42
Synthesis of 2-(1-Cyclohexen-1-ylethynyl)-6-methylpyridine
[0155] 2-Bromo-6-methyl pyridine (2.0 g, 12 mmol) and CuI (440 mg, 2.3 mmol) were combined in DME (30 mL), and argon gas was bubbled through the suspension for several minutes to deoxygenate the mixture. Triethylamne (8.0 mL, 58 mmol) and PdCl 2 (PPh 3 ) 2 (814 mg, 1.16 mmol) were added, followed by the dropwise addition of 1-ethynylcyclohexene (1.7 g, 15 mmol). The reaction was stirred at ambient temperature overnight. GC/MS showed no starting 2-bromo-6-methylpyridine remaining. The mixture was diluted with ethyl acetate (100 mL), and filtered through Celite™. The pad was then thoroughly washed with ethyl acetate and the combined filtrates were washed with water (200 mL), brine (200 mL), dried over Na 2 SO 4 , and filtered. The filtrate was concentrated in vacuo, and the residue was purified by column chromatography eluting with hexane then 99:1, 98:2 hexane:ethyl acetate to afford 2-(1-cyclohexen-1-ylethynyl)-6-methylpyridine (1.8 g, 79% yield) as a red oil. 1 H NMR (CDCl 3 , 300 MHz) δ7.51-7.46 (m, 1H), 7.21 (d, J=9 Hz, 1H), 7.03 (d, J=9 1H), 6.32-6.29 (m, 1H), 2.53 (s, 3H), 2.24-2.21 (m, 2H), 2.14-2.12 (m, 2H), 1.67-1.57 (m, 4H). MS (ESI) 198.1 (M + ).
EXAMPLE 43
Synthesis of 2-(Cyclohexylethynyl)-6-methylpyridine
[0156] 2-Bromo-6-methyl pyridine (2.0 g, 11.6 mmol) and Cui (440 mg, 2.3 mmol) were combined in DME (30 mL), and argon gas was bubbled through the suspension for several minutes to deoxygenate the mixture. Triethylamne (8.0 mL, 58 mmol) and PdCl 2 (PPh 3 ) 2 (814 mg, 1.16 mmol) were added, followed by the dropwise addition of cyclohexylethyne (1.25 g, 11.6 mmol). The reaction was stirred at ambient temperature overnight. GC/MS showed no starting 2-bromo-6-methylpyridine remaining. The mixture was diluted with ethyl acetate (100 mL), and filtered through Celite™. The pad was then thoroughly washed with ethyl acetate and the combined filtrates were washed with water (200 mL), brine (200 mL), dried over Na 2 SO 4 , and filtered. The filtrate was concentrated in vacuo, and the residue was purified by column chromatography eluting with hexane then 98:2, 96:4 hexane:ethyl acetate to afford 2-(cyclohexylethynyl)-6-methylpyridine (1.78 g, 77% yield) as a pale brown liquid that partially solidified on standing in the freezer. 1 H NMR (CDCl 3 , 300 MHz) δ7.52-7.46 (m, 1H), 7.20 (d, J=9 Hz, 1H), 7.03 (d, J=9 Hz, 1H), 2.6 (m, 1 H), 2.54 (s, 3H), 2.93-2.89 (m, 2H), 1.78-1.73 (m, 2H), 1.57-1.54 (m, 3H), 1.36-1.32 (m, 3H). MS (ESI) 200.1 (M + +H).
[0157] While the invention has been described in detail with reference to certain preferred embodiments thereof, it will be understood that modifications and variations are within the spirit and scope of that which is described and claimed.
|
In accordance with the present invention, there is provided a novel class of heterocyclic compounds. Compounds of the invention contain a substituted, unsaturated five, six or seven membered heterocyclic ring that includes at least one nitrogen atom and at least one carbon atom. The ring additionally includes three, four or five atoms independently selected from carbon, nitrogen, sulfur and oxygen atoms. The heterocyclic ring has at least one substituent located at a ring position adjacent to a ring nitrogen atom. This mandatory substituent of the ring includes a moiety (B), linked to the heterocyclic ring via a carbon-carbon double bond, a carbon-carbon triple bond or an azo group. The mandatory substituent is positioned adjacent to the ring nitrogen atom. Invention compounds are capable of a wide variety of uses. For example heterocyclic compounds can act to modulate physiological processes by functioning as agonists and antagonists of receptors in the nervous system. Invention compounds may also act as insecticides, and as fungicides. Pharmaceutical compositions containing invention compounds also have wide utility.
| 2
|
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a method for preparing a copper layer on a substrate and, more particularly, to a method which is suitable for depositing a seedlayer or copper connectors, and providing a copper film with (111) crystallization orientation on a semiconductor.
[0003] 2. Description of Related Art
[0004] In the existing semiconductor industry, the main method for preparing copper connectors is electroplating which has fast deposition, stability and produces a high purity deposited layer. However, before performing the electroplating, a continuous and conductive copper seedlayer must be provided, which makes the process more complex.
[0005] The commonly conductive copper seedlayer can be made by using chemical vapor deposition (CVD), physical vapor deposition (PVD), or electroless plating, but each has different disadvantages. The precursor of CVD usually has strong toxicity and low stability, also, its rate of deposition is slow, and the purity of the plating film is difficult to control. The main flaw of PVD is that the ability of step-coverage is poor; especially when the width of copper connectors is less than 90 nm or the aspect ratio of depth to width is greater than 5, the rate of step-coverage will become seriously insufficient, as a result, the seedlayer spreads unevenly and is unable to construct continuously conductive films, which will diminish the reliability of the feature. The quantity of the stabilizer of a conventional electroless plating is hard to control, which easily causes high concentration of stabilizer and results in abnormal deposition. Additionally, after the sensitizing and activating process, the deposited layer becomes more difficult to adhere, which results in problems such as deteriorating in conductivity of the deposited layer.
[0006] Furthermore, with the limitation of the width of the copper connectors as set forth above, electroplating will become obsolete. Therefore, a new technique for preparing copper connectors in the ULSI is in demand. A technique using just one single step to produce a seedlayer with thin thickness, high rate of step-coverage, and good substrate-adhesion will be an advantage for producing copper connectors in the ULSI, which will compact the process and also have high quality results.
SUMMARY OF THE INVENTION
[0007] The present invention relates to a method for depositing a copper layer on a substrate using electroless plating, which comprises the following steps: (a) providing a substrate, a plating tank with heating and cooling devices, a copper plating bath which is placed inside the plating tank; (b) using the heating device to heat the plating bath; then using the cooling device to cool the heated bath; and (c) placing a substrate into the plating bath with a gap between the heating device and the substrate; wherein the gap is filled with the plating solution; the heating temperature of the heating device is T1, the heating solution in the designed clearance shows temperature gradient; the substrate can have sub-micro or nano-trench or deep-via pattern.
[0008] The present invention also comprises another method for depositing a copper layer on a substrate using electroless plating, following step (c), step (d) rinsing and then drying the substrate.
[0009] In the method of the present invention, the heating and cooling device can heat and cool only part of the plating bath, so the plating bath can become a solution with a temperature gradient. The plating solution in the gap is connected to the plating bath in the plating tank; in-between the designed clearance, the heating temperature of the heating device is T1, which has no temperature limitation; a good temperature range is between 70˜400° C., and the best temperature range is between 80˜250° C.; additionally, the temperature of the plating solution on the surface of the substrate is lower than the temperature of heating device. Thus, the plating solution between the surface of the substrate and the heating device shows a temperature gradient. Besides, the size of the gap is not limited either; a good range is between 2 μm˜3000 μm, and the best range is between 50 μm˜500 μm. Because the gap is related to the plating tank, the plating bath in the tank can instantly replenish the consumed the concentration of the metallic ion from the bulk bath into the designed clearance, which helps the reaction process.
[0010] Moreover, the electroless copper plating bath of the present invention can be any kind in the prior art; a good solution is the solution mainly containing copper sulfate and Ethylene Diaminetetraacetic Acid (EDTA), and the best solution is the solution which contains an inhibitor, such as a surfactant. In general, a surfactant can reduce surface tension, and also restrain the growth of the metal deposited layer; thus, a surfactant can be taken as a kind of inhibitor. A suitable surfactant for the present invention can be any kind in the prior art; beneficial kinds include polyol, such as glycerin, polyethylene glycols (PEG), butylene glycol; alkylammonium bromide, such as cetyl trimethyl ammonium bromide (CTAB) octadecyl trimethyl ammonium bromide (OTAB) tetradecyl trimethyl ammonium bromide (TTAB); hydrosulfate and sulfonate, such as octylsulfate sodium, sodium dodecyl sulfate (SDS), sodium dodecylbenzene sulfonate (SDBS), dodecylbenzene sulfonic acid (DBSA); perfluorate, such as lithium perfluorooctane sulfonate (LiFOS), sodium perfluorooctanoate (SPFO); and any combination of the above.
[0011] If previously mentioned surfactants are applied in a non-isothermal deposition system, an extra thin seedlayer or pinhole-less copper conductor can be made, wherein the category of alkylammonium bromides has the best results. Additionally, the concentration of the surfactant depends on the plating conditions, and a good range is between 10˜700 ppm.
[0012] Furthermore, a substrate, has 3D-structure patterns is suitable for preparing copper connectors of the present invention, and such patterns can be any pattern used in conventional methods. The beneficial kinds can be trenches and/or deep-vias of sub-micro type and/or nano type; for convenience, the substrate can be fixed on a terrace.
[0013] The method of the present invention is to produce a copper layer by using electroless plating, which is suitable for producing a seedlayer, copper connectors or a copper film with (111) crystallization orientation.
[0014] The present invention relates to a method of producing seedlayer and copper connectors, by using high temperature heating method, a part of the solution of the extremely small clearance between the substrate and the heater is heated directly. Through the electroless plating process, metal nano-particles are formed from the plating solution in-between the heating device and the cooling device by self-assembly nucleation and deposited on the substrate by diffusion, such as heat diffusion or mass transfer of nano-particles. The nano-particles are deposited in a 2D order and stacked in 3D structures directly on the trenches or deep-vias. Furthermore, the cooling device takes the extra heat energy away, so the non-reacted plating bath can stay stable and will not spontaneously decompose.
[0015] During the process illustrated above, depending on the amount of surfactants added, ultra-thin and continuous film and void-free copper connectors can be obtained. Furthermore, as the temperature increases, the copper crystallization in the plating bath of a non-isothermal system can enhance the (111) preferred crystallization orientation. Usually, convectional electroless plating will produce hydrogen during the chemical reaction, but non-isothermal bath is a high temperature system, so it can release the remained hydrogen in the deposited layer accompanying by the deposition of copper, some zero- and one-dimensional crystalline defects and vacancies can be partly eliminated by the non-isothermal system, additionally, the non-isothermal system assists the recrystallization of copper which makes coarsing grains and decreasing the grain boundaries. In the conventional method, the copper film has to go through high temperature annealing in order to obtain excellent (111) crystalline textures. In the method of the present invention, a seedlayer or a copper connector can directly undergo the heating treatment, by which the annealing step of the conventional method can be omitted.
[0016] The plating bath used in the method of present invention has high stability, and a non-conductive or non-catalytically-active substrate can immediately be used for chemical deposition without going through noble metal sensitizing and activating process first. Therefore, without the noble metal process, the deposited layer will not be difficult to adhere to the surface, and its conductivity will not deteriorate. Additionally, the cooling device can maintain a low temperature of the plating bath in the non-reaction area, which can prevent problems such as the Cannizzaro reaction or over consumption of formaldehyde. In the meantime, the distinguishing features of electroless plating are not affected, for example, the deposited layer is homogeneously covered and forms a geometric shape as the substrate. Furthermore, by using the non-isothermal heating system, the temperature of the solution in the designed clearance between the heating device and the substrate increases, and the addition of surfactants can decrease the surface tension of the solution; thus, the solution will enter and fill the nano or sub-micro inner structures easily.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1 is a schematic drawing of the device of the present invention.
[0018] FIG. 2 is a partially enlarged schematic drawing of FIG. 1 .
[0019] FIG. 3 is an image of the copper connectors produced in accordance with the method of the present invention.
[0020] FIG. 4 is an image of the seedlayer produced in accordance with the method of the present invention, wherein the thin deposited layer is the seedlayer (its shade is brighter), and the thickness of the layer is around 20 nm.
[0021] FIG. 5 is an image of the copper connectors produced in accordance with the method of the present invention.
[0022] FIG. 6 is an image of the copper connectors produced in accordance with the method of the present invention.
[0023] FIG. 7 is an image of the copper connectors produced in accordance with the method of the present invention.
[0024] FIG. 8 is an image of the copper connectors produced in accordance with the method of the present invention.
[0025] FIG. 9 is an image of the copper connectors produced in accordance with the method of the present invention.
[0026] FIG. 10 is an image of the copper connectors produced in accordance with the method of the present invention.
[0027] FIG. 11 is a relative diagram of the ratio between the (111) crystallization and (200) crystallization orientation under different temperatures.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0028] The main purpose of the present invention is to prepare seedlayers and copper connectors on a substrate 10 with patterns of trenches or deep-vias, and to investigate the influence of various deposition conditions on plating copper using electroless plating under the non-isothermal system. The main component of a plating bath 20 used in the present invention is copper sulphate, which can produce ultra thin and homogeneous seedlayers or non-pinhole copper layers. Furthermore, the present invention also selectively adds surfactants in the process, which can decrease the activity on the surface of the deposited layer, and control the thickness of seedlayer or overcome the defects of blocking which are caused by non-linear diffusion.
[0029] The method for producing seedlayers and copper connectors comprises steps as follows. FIG. 1 is a schematic drawing of the device for producing seedlayers and copper connectors, and FIG. 2 is the enlarged image of part of the FIG. 1 . First, a substrate 10 with patterns of trenches or deep-vias is placed and cleaned in an organic solvent, which removes the oil sludge and impurities on the surface, so the lubricity on the surface of the substrate 10 can be increased, wherein, the size of the trenches or deep-vias can be of the order of nanometer or sub-micrometer. Second, the plating bath 20 is poured into a plating tank 30 , and the heating device 40 and cooling device 50 are switched on at the same time, which will enable the solution 20 to have gradient temperature. The substrate 10 is placed and fixed on top of the base 60 which has a vacuum sucking disc 61 . When the temperature of the solution reaches the targeted reaction temperature, the substrate 10 is placed in the plating tank to go through the chemical deposition of non-isothermal. The base 60 comprises at least one adjustable pillar 62 , which enables a designed clearance to be formed between the substrate 10 and the heating device 40 , and the size of the gap can be varied by adjusting the pillar 62 . For example, the size of the gap can around 3 mm, but if the clearance is too big, the metal particles will easily diffuse from the inside of the gap to the outer solution. As a result, the amount of the deposited metal particles will be smaller as the distance of the gap increases. In another example, a suitable width of the gap is around 50˜500 μm, which enables the plating solution 20 in the gap to result in homogeneous self-assembly nucleation and metal nano-particles 70 (as shown in FIG. 2 ) are deposited on the surface of the substrate 10 . Then, the nano-particles will form an ultra-thin and continuous metal film. The distinguishing feature of the present invention is using one single process to prepare seedlayers or copper connectors for an ULSI. The examples of the method for producing seedlayers, copper connectors, and copper film with preferred (111) orientation of copper crystallization are as follows:
EXAMPLE 1
[0030] A non-conductive substrate with trenches (width of trenches is 12 μm and depth is 32 μm) on the surface is cleaned using acetone for 60 seconds at room temperature, and then is rinsed by de-ionized water for 20 seconds. Immediately, the cleaned substrate is placed into a plating tank containing a plating bath. The designed clearance between the substrate and the heating device is maintained at 150 μm; at this point, the temperature of the contact point between the plating solution and the heating device has reached 100° C., and the temperature of the plating bath in the plating tank becomes non-isothermal. After 10 minutes of deposition reaction, the substrate is removed from the plating tank, cleaned by the de-ionized water for 20 seconds at room temperature, and dried by nitrogen for 60 seconds; where after the process for forming the copper connectors is completed. As shown in FIG. 3 , while the non-isothermal deposition is being performed, because of the non-linear diffusion problem, the seedlayers will have defects such as voids and pinholes. Such situation is similar to the results of using electroplating method, i.e., voids and pinholes in the deposited layer, which are caused by non-homogeneous electric current density. The composition of the plating bath is as follows:
Composition of plating bath Concentration Copper sulphate 0.03M Formaldehyde 0.33M Ethylene diaminetetraacetic acid 0.24M (EDTA) Sodium hydroxide Adjust pH of the solution to about 12.5
EXAMPLE 2
[0031] In this example, a non-conductive substrate with trenches (width of trenches is 0.25 μm and depth is 0.37 μm) on the surface is used to prepare seedlayers by using non-isothermal deposition, which is the same as the procedure in example 1. However, in this example, the plating bath has added thereto a 350 ppm of alkylammonium bromide, such as cetyl trimethyl ammonium bromide, while the other conditions remain the same. As shown in FIG. 4 , the activity area of the surface of the seedlayer is covered by excessive cetyl trimethyl ammonium bromide, which reduces its activity and restrains the growth of interior and exterior microstructure of copper layers. As a result, ultra-thin and even seedlayer with thickness around 20 nm is produced. Additionally, based on the mentioned conditions, if the quantity of the surfactant is increased, the surfactant can effectively and quickly restrain the growth of the copper layer. As a result, a thinner seedlayer will be obtained. The composition of the plating bath is as follows:
Composition of plating bath Concentration Copper sulphate 0.03M Formaldehyde 0.33M Ethylene diaminetetraacetic acid 0.24M (EDTA) Cetyl trimethyl ammonium 350 ppm bromide (CTAB) Sodium hydroxide Adjust pH of the solution to about 12.5
EXAMPLE 3
[0032] The procedure is similar to example 1, and a non-conductive substrate with trenches (width of trenches is 10 μm and depth is 30 μm) on the surface is used in this case. However, in this example, the plating bath has added thereto a 40 ppm of alkylammonium bromide, such as: cetyl trimethyl ammonium bromide, while the other conditions remain the same. As shown in FIG. 5 , the problem of non-linear diffusion has obviously improved, and the defect inside the deposited layer has decreased. The composition of the plating bath is as follows:
Composition of plating bath Concentration Copper sulphate 0.03M Formaldehyde 0.33M Ethylene diaminetetraacetic acid (EDTA) 0.24M Cetyl trimethyl ammonium bromide 40 ppm (CTAB) Sodium hydroxide Adjust pH of the solution to about 12.5
EXAMPLE 4
[0033] The procedure is similar to example 1, and a non-conductive substrate with trenches (width of trenches is 12 μm and depth is 32 μm) on the surface is used for producing a copper conductor. However, in this example, the plating bath has added thereto a 70 ppm of alkylammonium bromide, such as cetyl trimethyl ammonium bromide (CTAB), while the other variables remain the same. As shown in FIG. 6 , the problem of non-linear diffusion has obviously been solved, and the defect inside the deposited layer is not found; such result indicates that the surfactant, according to the adsorption theorem, will adhere to the corner of microstructure to inhibit the reaction of deposition. As the trenches and microstructures of the vias get deeper, the surfactants will be influenced by the gradient density and the non-isothermal behavior, as depth increases, the quantity of surfactant contained gets lower, so the inhibition in the interior of trenches and deep-vias becomes unobvious. Therefore, the addition of the surfactant obviously restrains the non-linear diffusion. A peer test was performed on the deposited layer using tapes (3M CO. No. 250), and it was found that the adhesion of copper connectors and the substrate is very effective. Additionally, the surfactant can also restrain the growth of the deposited layer on the image surface, which will reduce the time of Chemical Mechanical Polishing (CMP), meaning the probability for the erosion of the copper connectors by the polisher of CMP is correspondingly reduced. The composition of the plating bath is as follows:
Composition of plating bath Concentration Copper sulphate 0.03M Formaldehyde 0.33M Ethylene diaminetetraacetic acid (EDTA) 0.24M Cetyl trimethyl ammonium bromide 70 ppm (CTAB) Sodium hydroxide Adjust pH of the solution to about 12.5
EXAMPLE 5
[0034] The procedure is similar to example 1, and a non-conductive substrate with trenches (width of trenches is 10 μm and depth is 30 μm) on the surface is used for producing copper conductor. However, in this example, the plating bath has added thereto a 130 ppm of alkylammonium bromide, such as cetyl trimethyl ammonium bromide (CTAB), while the other variables remain the same. As shown in FIG. 7 , the problem of non-linear diffusion has been completely solved, and there is no defect shown inside the deposited layer. Furthermore, as the quantity of the surfactant increases, the image surface of deposited layer becomes thinner. Such result leads to a CMP procedure being no longer necessary. The composition of the plating bath is as follows:
Composition of plating bath Concentration Copper sulphate 0.03M Formaldehyde 0.33M Ethylene diaminetetraacetic acid (EDTA) 0.24M Cetyl trimethyl ammonium bromide 130 ppm (CTAB) Sodium hydroxide Adjust pH of the solution to about 12.5
EXAMPLE 6
[0035] The procedure is similar to the example 1, and a non-conductive substrate with trenches (width of trenches is 0.25 μm and depth is 0.37 μm) on the surface is used for producing a copper conductor. However, in this example, the plating bath has added thereto another 100 ppm of alkylammonium bromide, such as: cetyl trimethyl ammonium bromide (CTAB), while the other variables remain the same. As shown in FIGS. 8 ˜ 10 , void-free copper connectors can be obtained under these circumstances. A peer test on the deposited layer was performed using tapes (3M CO. No. 250), whereby the adhesion of both the conductive copper layer and the substrate is deemed to be very beneficial, and abruption does not happen. Furthermore, if the variables described above are applied to the production of 60 nm copper connectors, void-free and pinhole-free copper layers can be obtained. The composition of the plating bath is as follows:
Composition of plating bath Concentration Copper sulphate 0.03M Formaldehyde 0.33M Ethylene diaminetetraacetic acid (EDTA) 0.24M Cetyl trimethyl ammonium bromide 100 ppm (CTAB) Sodium hydroxide Adjust pH of the solution to about 12.5
[0036] As shown in the descriptions and results of examples 2 to 6, the plating bath with addition of the surfactant will stick at the comers of the openings of the substrates, which slows down the growth rate of the deposited layer and overcomes the infection of blockings that are caused by non-linear diffusion; as the quantity of the surfactant increases, the growth of interior and exterior microstructures of the deposited layer can be restrained. As a result, ultra-thin and even seedlayers can be obtained.
EXAMPLE 7
[0037] The purpose of this example is to show the changes of (111) crystallization orientation of the copper film under different heating temperatures, hydrogen will be released which remain in the deposited layer, crystalline defects and vacancies can be partly annihilated, grain boundaries degrease and grains become larger are all accompanied by elevating temperature. The procedure is similar to the example 1; however, besides the substrate, a silicon wafer with a flat surface is also used. As shown in FIG. 11 , the increase of temperature is an advantage to the (111) crystallization orientation of the copper film in the non-isothermal system. As the heating temperature increases, the ratio between (111) crystallization and (200) crystallization orientation gets bigger. The result shows that the non-isothermal system has both depositing and annealing capabilities, by which the step of annealing in the conventional method can be omitted. The composition of the plating bath is as follows:
Composition of plating bath Concentration Copper sulphate 0.03M Formaldehyde 0.33M Ethylene diaminetetraacetic acid 0.24M (EDTA) Heating temperature 80˜200° C. Sodium hydroxide Adjust pH of the solution to about 12.5
[0038] In conclusion, by using the chemical deposition of non-isothermal system, the present invention relates to a method of producing copper connectors or seedlayers on an un-conductive substrate which has patterns of trenches and deep-vias. Unlike conventional methods, the method of the present invention can be done in one process, without the step of annealing.
[0039] Although the present invention has been explained in relation to its preferred embodiment, it is to be understood that many other possible modifications and variations can be made without departing from the spirit and scope of the invention as hereinafter claimed.
|
A method for depositing a copper layer on a substrate is disclosed. The method is achieved by heating a plating solution located between a heating device and a target substrate. Through the process illustrated above, metal nano-particles come out from the plating solution and deposit on a substrate with high aspect ratio. Surfactant can be selectively added for obtaining ultra-thin continuous film, void-free copper connectors. Furthermore, a copper film would achieve a preferred (111) crystallization orientation.
| 2
|
This application is a continuation of application Ser. No. 660,930, filed Oct. 15, 1984 now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a magnetic powder composition and, more particularly, to a magnetic powder composition suitable for manufacturing a compressed powder core in which electric insulation between magnetic powder particles is improved.
2. Description of the Prior Art
In the prior art, in electrical instruments such as an electric power converting device, including a device for converting an alternate current to a direct current, a device for converting an alternate current having a certain frequency to another alternate current having a different frequency and a device for converting a direct current to an alternate current such as so called inverter, or a non-contact breaker, etc., there have been employed, as electrical circuit constituent elements thereof, semiconductor switching elements, typically thyristor and transistor, and reactors for relaxation of turn-on stress in a semiconductor switching element, reactors for forced commutation, reactors for energy accumulation or transformers for matching connected to these elements.
Iron cores used in such reactors or transformers are conventionally classified as follows:
(a) So called laminated iron cores produced by laminating thin electromagnetic steel plates or permalloy sheets with an insulating interlayer interposed therebetween.
(b) So called dust cores obtained produced by a powder such as a carbonyl iron or permalloy powder with kaolin or a polymeric binder such as a phenol resin.
(c) So called ferrite cores produced by sintering an oxide magnetic material.
Such iron cores used in reactors or transformers which are connected to the semiconductor switching elements must satisfy specific magnetic property requirements. For example, such an iron core must have good frequency characteristics of magnetic permeability, high magnetic flux density, and small iron loss at high frequencies. Especially when a semiconductor switching element is operated, in addition to a current having a period of a switching frequency, a current having a frequency component which is far higher than the switching frequency, e.g., several tens of kilohertz to 500 kHz or higher, may flow in the iron core. In view of these, the iron core must definitely have good characteristics in a high-frequency range.
Of the three types of iron cores, although laminated iron cores exhibit excellent electrical characteristics within a commercial frequency range, they are subject to a large iron loss within a high-frequency range. In particular, in a laminated iron core, the eddy current loss increases in proportion to a square of the frequency. Furthermore, with an increase in the depth from the surface of the plate or sheet material constituting the iron core, the magnetizing force is less subject to changes due to the skin effect of the iron core material. Therefore, the laminated iron core can only be used at a magnetic flux density which is far lower than a saturated magnetic flux density of the laminated iron core material in a high-frequency range. The laminated iron core also has a very large eddy current loss.
In addition to the above disadvantages, laminated iron cores have a very low effective magnetic permeability at high frequencies as compared to an effective magnetic permeability within a commercial frequency range.
When a laminated iron core having these problems is used for a reactor or transformer connected to a semiconductor switching element through which a high-frequency current flows, the iron core itself must be rendered large so as to compensate for the low effective magnetic permeability and magnetic flux density. When the iron core is thus rendered large, the iron loss of the iron core is increased, and the length of the coil windings wound around the iron core is also increased, thereby increasing copper loss.
Dust cores, as the second types of iron core described above, are also conventionally used as iron cores. For example, Japanese Patent Registration No. 112,235 discloses the manufacture of a dust core for use as an iron core by compressing and forming a mixture of an iron powder or an ion alloy powder with an organic or inorganic binder and heating the formed mixture.
However, a dust core prepared in this manner generally has a low magnetic flux density and a low magnetic permeability. Even a dust core prepared using a carbonyl iron powder having a relatively high magnetic flux density has a magnetic flux density at a magnetizing force of 10,000 A/m of slightly higher than 0.1 T and a magnetic permeability of about 1.25×10 -5 H/m. Therefore, in a reactor or transformer using such a dust core as an iron core material, the iron core must be rendered large in order to compensate for a low magnetic flux density and a low magnetic permeability. With such an increase in the size of the iron core, the coil windings become longer, also resulting in a large copper loss of the reactor or transformer.
Ferrite cores, as the third type of iron cores, are frequently used for small electric equipment and have a high specific resistance and relatively good high-frequency characteristics. However, a ferrite core has a low magnetic flux density of about 0.4 T at a magnetizing force of 10,000 A/m. In addition to this, the permeability and the magnetic density at the same magnetizing force change by several tens of percentages within a temperature range of -40° to +120° C., which is the temperature range wherein the iron core is used. Thus, when a ferrite core is used as an iron core material of a reactor or transformer connected to a semiconductor switching element, the iron core must be rendered large to compensate for a low magnetic flux density, resulting in the same problem as with the two other types of iron cores.
Furthermore, since ferrite is a sintered body, the manufacture of a large iron core with ferrite is difficult. For this reason, it is difficult to use a ferrite core for handling high power. Due to the longer coil windings and larger copper loss owing to a low magnetic flux density and the great temperature dependencies of magnetic permeability and magnetic flux density, when a ferrite core is used for a reactor or transformer, the core is subject to great variations in its characteristics. When a ferrite core is compared with an electromagnetic steel plate or the like, it has a higher magnetostriction and generates a higher noise from the iron core.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a magnetic powder composition which can be suitably used for the manufacture of a powder core, in particular, a powder core used for a reactor or transformer connected to a semiconductor switching element.
It is another object of the present invention to provide a powder core which is manufactured from the above magnetic powder composition and which has excellent frequency characteristics of magnetic permeability, high magnetic flux density, and small iron loss at high frequencies.
The magnetic powder composition of the present invention esentially consists of:
(a) a magnetic powder of a soft magnetic metal or alloy, or a mixture thereof;
(b) an electrically insulating polymer for binding the powder; and
(c) an organometallic coupling agent for accelerating coupling between the powder and the polymer.
In the second aspect, the present invention is directed to a powder core manufactured by compressing and forming the above-mentioned composition and heating the formed composition to a sufficient temperature for curing the polymer.
When the composition further contains a powder of an inorganic compound having an electrical insulating property, the forming or packing density of the powder core can be increased, and at the same time the effective electric resistance against AC magnetization of the overall powder core can be improved.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a representation showing a state wherein a titanium coupling agent is bonded to the surfaces of the magnetic powder particles;
FIG. 2 is a representation showing a state wherein a silane coupling agent is bonded to the surfaces of the magnetic powder particles; and
FIGS. 3 to 7 are graphs showing changes in effective magnetic permeability within a high-frequency range of an iron core of each Example of the present invention and of an iron core of each Comparative Example.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A magnetic powder used in the composition of the present invention is pure iron or alloys such as an Fe--Si alloy (e.g., Fe-3% Si), an Fe--Al alloy, an Fe--Si--Al alloy, an Fe--Ni alloy such as a permalloy, or an Fe--Co alloy. An amorphous magnetic alloy consisting of at least one of Fe, Co, Ni and Nb, and at least one of Si, B, and C can also be used.
The magnetic powder has a specific electrical resistance of from 10 μΩ-cm to several tens of micro-ohm centimeters. In view of this, in order to obtain satisfactory iron core material characteristics with an AC current including high-frequency components which would cause the skin effect, the magnetic powder must be formed into a fine powder to allow contribution to magnetization from the surface right to the inside of each particle.
In an iron core which is excited with a current having frequency components of up to several tens of kilohertz and which must therefore have good magnetic permeability characteristics up to such a frequency range, the magnetic powder preferably has an average particle size of 300 μm or less. In an iron core excited with a current having frequency components exceeding 100 kHz and which must therefore have good magnetic permeability characteristics up to such a frequency range, the magnetic powder preferably has an average particle size of 100 μm or less. However, when the average particle size of the magnetic powder becomes as small as 10 μm or less, it is hard to obtain an iron core from such a fine powder. Furthermore, even if such a fine powder is obtained, when the powder is compressed, a satisfactory density of the resultant iron core cannot be obtained with a compression pressure below 1,000 MPa. This imposes a problem of a low magnetic flux density. In view of this, the magnetic powder preferably has a particle size of 10 μm or more.
The magnetic powder is preferably contained in the composition in an amount of 55 to 99% by volume. When the amount of the magnetic powder exceeds 99% by volume, the resin content has a binder becomes too small and the binding power of the iron core becomes weak. However, when the amount of the magnetic powder is below 55% by volume, the magnetic flux density at a magnetizing force of 10,000 A/m is lowered to an equivalent to that obtained with ferrite.
An electrically insulating polymer is used herein as a binder for binding each particle of the magnetic material. At the same time, the polymer serves to cover the surface of each particle of the magnetic powder to electrically insulate one particle from another, thereby providing a satisfactory and effective electrical resistance for an AC magnetization of the overall iron core. Such a binder may, for example, be an epoxy resin, a polyamide resin, a polyimide resin, a polyester resin, or a polycarbonate resin. Such polymers may be used singly or in an admixture of more than one. The polymer is preferably used in the amount of 0.7% by volume or more based on the total volume of the composition. When the amount of the polymer used is less than 0.7% by volume, the binding force of the iron core is deteriorated.
A coupling agent used herein serves to improve wettability and adhesion between the magnetic powder and the binder resin. Due to these effects, the binder resin is introduced well between the magnetic powder particles to improve electrical insulation. Consequently, the iron loss of the iron core is reduced and the releasing force of the compressed body from the mold can be low.
Examples of the coupling agent which may be used herein preferably include a titanium coupling agent, a silane coupling agent, an aluminium coupling agent but may also include an indium coupling agent or a chromium coupling agent. Among these, a Ti, silane or Al coupling agent having a particularly good adhesion force with the magnetic powder is particularly preferable.
The Ti coupling agent has the following general formula:
R.sub.m --Ti--X.sub.n
wherein R is a group which is easily hydrolyzed, X is a lipophilic group which is not easily hydrolyzed, and m and n are positive integers. Since Ti has a coordination number of 4 or, 6, m+n must be 4 to 6 and m must fall within a range of 1 to 4.
The group R which is easily hydrolyzed is a monoalkoxyl group, a hydroxyacetic acid residue, or an ethylene glycol residue. Such a group R readily reacts with water adsorbed in the surface of each magnetic power particle at room temperature to be hydrolyzed. Then, as shown in FIG. 1, for example, Ti atoms of the Ti coupling agent are strongly bonded to the surface of a magnetic powder 1 through oxygen atoms O. The group X is one of several lipophilic groups including hydrocarbon moiety. The group X does not react with the hydroxyl group on the magnetic powder surface and has good wettability and adhesion with the binder polymer which is an organic material.
Examples of such a Ti coupling agent are enumerated below:
○1 isopropyltriisostearoyl titanate ##STR1## ○2 dicumylphenyloxyacetate titanate ##STR2## ○3 4-aminobenzenesulfonyl dodecylbenzenesulfonyl ethylene titanate ##STR3## ○4 isopropyl tri(N-aminoethyl-amino-ethyl)titanate ##STR4## ○5 tetraoctyl bis(ditridecylphosphite)titanate
(C.sub.8 H.sub.17 -O).sub.4 Ti·[P-(O-C.sub.13 H.sub.27).sub.2 OH].sub.2
○6 tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecylphosphite)titanate ##STR5##
These Ti coupling agents are available from Kenrich Petrochemical Co., U.S.A.
The silane coupling agent has the following general formula: ##STR6## wherein RO is an alkoxy group, and X is an organic functional group. Since Si has a coordination number of 4, n is 2 or 3. The alkoxyl group RO may be a methoxyl group or an ethoxyl group. The RO group is hydrolyzed by water adsorbed in the magnetic powder surface or in air to produce a silanol group --SiOH. Then, as shown in FIG. 2, for example, silicone atoms Si of the silane coupling agent are strongly coupled to the surface of the magnetic powder 1 through oxygen atoms O. The organic functional group X may be an epoxy group, a methacryl group or an amino group and has good wettability and adhesion with the binder polymer.
Examples of such a silane coupling agent are enumerated below:
○1 γ-glycidoxypropyl trimethoxysilane ##STR7## ○2 β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane ##STR8## ○3 γ-aminopropyl triethoxysilane
H.sub.2 N(CH.sub.2).sub.3 --Si--(OC.sub.2 H.sub.5).sub.3
○4 N-β(aminoethyl)-γ-aminopropyl methyldimethoxysilane ##STR9##
These silane coupling agents are available from Union Carbide Co., U.S.A.
The Al coupling agent has the following general formula:
(RO).sub.n --Al--X.sub.3-n
wherein RO is an alkoxyl group, and X is a lipophilic group including a hydrocarbon moiety. The RO group may be a methoxy group, an ethoxy group, an isopropoxyl group, or a secondary butoxy group. The RO group is hydrolyzed by water in the air or water adsorbed in the magnetic powder surface and can therefore be coupled to the surface of the magnetic powder through oxygen atoms O of the coupling agent. Al generally has a coordination number of 3, and so n is 1 or 2. However, an another part of the lipophilic groups X are at times weakly coupled to aluminum atom which then has a pseudo coordination number of 4. In this case, the coupling agent is less subject to decomposition and is preferable.
An example of such an Al coupling agent is ethylacetoacetate aluminum diisopropylate having the structural formula: ##STR10##
According to the present invention, the coupling agent is preferably contained in the amount of 0.3% by volume based on the total volume of the composition. When the amount of the coupling agent is less than 0.3% by volume, the polymer cannot completely surround the magnetic powder particles, resulting in poor insulation and an unsatisfactory reduction in iron loss.
The composition of the present invention may further contain a powder of an inorganic compound. The inorganic compound particles serve to reduce the friction between the magnetic powder particles during formation of the iron core so as to increase the forming density of the iron core. The inorganic compound particles are also present between the conductive magnetic powder particles to increase the effective electrical resistance for the AC magnetization of the overall iron core, thereby reducing iron loss. Such an inorganic compound may be calcium carbonate, magnesium carbonate, magnesia, silica, alumina, mica and various types of glass. A selected inorganic compound may not react with the magnetic powder or binder polymer described above.
The average particle size of the inorganic compound is preferably smaller than that of the magnetic powder particles in consideration of providing good dispersion and iron core material characteristics and is preferably 20 μm or less.
The inorganic compound is preferably contained in the amount of 0.3 to 30% by volume based on the total volume of the composition. When the amount of the inorganic compound is less than 0.3% by volume, a desired effect cannot be obtained by addition of this compound. However, when the amount of the inorganic compound exceeds 30% by volume, the resultant iron core has a poor mechanical strength.
A method of manufacturing an iron core from the composition of the present invention will be described below.
First, a magnetic powder and a coupling agent are mixed together with or without dissolving the coupling agent in a suitable solvent thereof such as isopropanol, toluene, or xylene. Upon this step, the surface of the magnetic powder is covered with the coupling agent. Next, a binder polymer is added to the mixture and the resultant mixture is well stirred.
In the mixing step described above, three components i.e., the magnetic powder, the binder polymer and the coupling agent can be well mixed simultaneously. Also, the magnetic powder can be mixed with a mixture of the binder polymer and the coupling agent.
A mixture containing a powder of an electrically insulating inorganic compound can be prepared by various methods including a method of mixing a magnetic powder and a powder of an inorganic compound and then sequentially adding a coupling agent and a binder polymer to the mixture; a method of simultaneously adding all of a magnetic powder, a powder of an inorganic compound, a binder polymer, and a coupling agent; and a method of dispersing a powder of an inorganic compound in a binder polymer before mixing it with other components. Although any such method can be adopted, a better effect is obtained if a powder of an inorganic compound is dispersed in a binder polymer before mixing it with other components.
The resultant mixture is charged in a mold and compressed in accordance with a conventional method to prepare a formed body having a desired shape. The formed body is heat-treated for curing the polymer, as needed, thereby manufacturing an iron core.
EXAMPLES
Although the present invention will be described by way of examples below, it is to be understood that the present invention is not limited thereto.
EXAMPLES NOS. 1-25
A magnetic powder, a binder polymer, a Ti coupling agent, and when applicable, a powder of an inorganic compound were well mixed. The resultant mixture was charged into a mold and compressed at a pressure of 600 MPa. After the compressed body was released from the mold, it was heat-treated to prepare an iron core. In each case, the powder of the inorganic compound was dispersed in the binder polymer before mixing it with other components except for that of Example No. 24. In the iron core of Example No. 24, all the components were mixed simultaneously. The heat-treatment was performed at 160° to 200° C. for 0.5 to 2 hours for the iron cores which used an epoxy resin as a binder polymer and at 160° C. for 15 minutes for the iron cores which used a polyamide resin as a binder polymer.
The mixing ratios of the respective components used are shown in Tables 1 to 4 below.
Iron cores of Comparative Example Nos. 26 to 40 were prepared following the same procedures as those of Examples except that no coupling agent was contained or only a small amount of a coupling agent was contained in the compositions of these Comparative Examples.
Annular samples of the obtained iron cores were subjected to measurements of magnetic properties such as iron loss within a frequency range of 50 Hz to 200 kHz, magnetic permeability and effective permeability within a DC voltage frequency of up to 10 MHz and magnetic flux density.
Of the obtained measurement results, Tables 1 to 4 show only iron loss at 50 kHz and 100 kHz at a typical magnetic flux density: B=0.05 T.
The releasing force for releasing the formed body from the mold in a step of compressing a columnar iron core having a diameter and a height of 20 mm was also measured.
TABLE 1__________________________________________________________________________ Binder Inorganic compound Magnetic powder polymer Ti coupling agent powder Mixing Mixing Mixing Mixing Iron loss Average ratio ratio ratio Average ratio (W/kg); Composition particle (% by (% by (% by particle (% by B = 0.05T (% by diameter vol- vol- vol- diameter vol- 50 100 weight) (μm) ume) Type ume) Type ume) Type (μm) ume) kHz kHz__________________________________________________________________________ExampleNo. 1 3.5% Si--Fe 54 85.0 Epoxy 14.7 Tetraoctylbis- 0.3 -- -- -- 247 692 (ditridecylphos- phite)titanateNo. 2 3.5% Si--Fe 54 85.0 Epoxy 14.3 Tetraoctylbis- 0.7 -- -- -- 215 519 (ditridecylphos- phite)titanateNo. 3 3.5% Si--Fe 54 85.0 Epoxy 13.0 Tetraoctylbis- 2.0 -- -- -- 199 480 (ditridecylphos- phite)titanateNo. 4 3.5% Si--Fe 54 85.0 Epoxy 10.7 Tetraoctylbis- 0.3 CaCO.sub.3 2.8 4.0 235 662 (ditridecylphos- phite)titanateNo. 5 3.5% Si--Fe 54 85.0 Epoxy 9.5 Tetraoctylbis- 2.0 CaCO.sub.3 2.8 3.5 131 327 (ditridecylphos- phite)titanateNo. 6 3.5% Si--Fe 54 85.0 Epoxy 8.4 Tetraoctylbis- 3.5 CaCO.sub.3 2.8 3.1 123 309 (ditridecylphos- phite)titanateNo. 7 3.5% Si--Fe 54 85.0 Epoxy 6.9 Tetraoctylbis- 5.5 CaCO.sub.3 2.8 2.6 122 293 (ditridecylphos- phite)titanateComparativeExampleNo. 26 3.5% Si--Fe 54 85.0 Epoxy 14.9 Tetraoctylbis- 0.1 -- -- -- 338 986 (ditridecylphos- phite)titanateNo. 27 3.5% Si--Fe 54 85.0 Epoxy 10.8 Tetraoctylbis- 0.1 CaCO.sub.3 2.8 4.1 305 889 (ditridecylphos- phite)titanateNo. 28 3.5% Si--Fe 54 85.0 Epoxy 15.0 -- -- -- -- -- 368 1,127No. 29 3.5% Si--Fe 54 85.0 Epoxy 10.9 -- -- CaCO.sub.3 2.8 4.1 332 1,010__________________________________________________________________________ 3
TABLE 2__________________________________________________________________________ Binder Inorganic compound Magnetic powder polymer Ti coupling agent powder Mixing Mixing Mixing Mixing Iron loss Average ratio ratio ratio Average ratio (W/kg); Compostion particle (% by (% by (% by particle (% by B = 0.05T (% by diameter vol- vol- vol- diameter vol- 50 100 weight) (μm) ume) Type ume) Type ume) Type (μm) ume) kHz kHz__________________________________________________________________________ExampleNo. 8 Fe 88 98.4 Epoxy 1.3 Tetraoctylbis- 0.3 -- -- -- 242 613 (ditridecylphos- phite)titanateNo. 9 Fe 88 97.5 Epoxy 1.8 Tetraoctylbis- 0.7 -- -- -- 218 566 (ditridecylphos- phite)titanateNo. 10 3.5% Si--Fe 54 80.0 Epoxy 12.1 Tetraoctylbis- 2.0 CaCO.sub.3 2.8 4.9 147 322 (ditridecylphos- phite)titanateNo. 11 3.5% Si--Fe 54 75.0 Epoxy 23.0 Tetraoctylbis- 2.0 -- -- -- 184 382 (ditridecylphos- phite)titanateNo. 12 3.5% Si--Fe 54 75.0 Epoxy 16.7 Tetraoctylbis- 2.0 SiO.sub.2 5.0 6.3 168 350 (ditridecylphos- phite)titanateNo. 13 Fe 88 64.0 Epoxy 30.0 Tetraoctylbis- 4.0 -- -- -- 122 309 (ditridecylphos- phite)titanateNo. 14 Fe 88 55.0 Epoxy 41.0 Tetraoctylbis- 4.0 -- -- -- 109 262 (ditridecylphos- phite)titanateComparativeExampleNo. 30 Fe 88 98.4 Epoxy 1.6 -- -- -- -- -- 298 822No. 31 Fe 88 97.5 Epoxy 2.5 -- -- -- -- -- 258 710No. 32 3% Si--Fe 54 80.0 Epoxy 15.1 -- -- CaCO.sub.3 2.8 4.9 309 890No. 33 3% Si--Fe 54 75.0 Epoxy 25.1 -- -- -- -- -- 284 798No. 34 3% Si--Fe 54 75.0 Epoxy 18.7 -- -- SiO.sub.2 5.0 6.3 269 722No. 35 3% Si--Fe 54 64.0 Epoxy 36.0 -- -- -- -- -- 287 706__________________________________________________________________________
TABLE 3__________________________________________________________________________ Binder Inorganic compound Magnetic powder polymer Ti coupling agent powder Mixing Mixing Mixing Mixing Iron loss Average ratio ratio ratio Average ratio (W/kg); Composition particle (% by (% by (% by particle (% by B = 0.05T (% by diameter vol- vol- vol- diameter vol- 50 100 weight) (μm) ume) Type ume) Type ume) Type (μm) ume) kHz kHz__________________________________________________________________________ExampleNo. 15 45% Ni--Fe 54 85 Epoxy 9.5 Tetra(2,2-di- 2.0 CaCO.sub.3 2.8 3.5 136 281 allyloxymeth- yl-1-butyl)- bis(ditridecyl- phosphite)- titanateNo. 16 6.5% Si--Fe 54 85 Epoxy 9.5 Tetra(2,2-di- 2.0 CaCO.sub.3 2.8 3.5 197 395 allyloxymeth- yl-1-butyl)- bis(ditridecyl- phosphite)- titanateNo. 17 3.1% Al--Fe 54 85 Epoxy 9.5 Tetra(2,2-di- 2.0 CaCO.sub.3 2.8 3.5 129 279 allyloxymeth- yl-1-butyl)- bis(ditridecyl- phosphite)- titanateNo. 18 1.5% Si--Fe 54 85 Epoxy 9.5 Tetra(2,2-di- 2.0 CaCO.sub.3 2.8 3.5 112 287 allyloxymeth- yl-1-butyl)- bis(ditridecyl- phosphite)- titanateComparativeExampleNo. 36 45% Ni--Fe 54 85 Epoxy 11.5 -- -- CaCO.sub.3 2.8 3.5 155 405No. 37 6.5% Si--Fe 54 85 Epoxy 11.5 -- -- CaCO.sub.3 2.8 3.5 445 1,340No. 38 3.1% Al--Fe 54 85 Epoxy 11.5 -- -- CaCO.sub.3 2.8 3.5 259 682No. 39 1.5% Si--Fe 54 85 Epoxy 11.5 -- -- CaCO.sub.3 2.8 3.5 189 545__________________________________________________________________________
TABLE 4__________________________________________________________________________ Binder Inorganic compound Magnetic powder polymer Ti coupling agent powder Mixing Mixing Mixing Mixing Iron loss Average ratio ratio ratio Average ratio (W/kg); Composition particle (% by (% by (% by particle (% B = 0.05T (% by diameter vol- vol- vol- diameter vol- 50 100 weight) (μm) ume) Type ume) Type ume) Type (μm) ume) kHz kHz__________________________________________________________________________ExampleNo. 19 Fe 210 93.5 Epoxy 4.5 Tetraoctylbis- 2.0 -- -- -- 221 747 (ditridecylphos- phite)titanateNo. 20 Fe 180 93.5 Epoxy 4.5 Tetraoctylbis- 2.0 -- -- -- 219 700 (ditridecylphos- phite)titanateNo. 21 Fe 105 93.5 Epoxy 4.5 Tetraoctylbis- 2.0 -- -- -- 133 422 (ditridecylphos- phite)titanateNo. 22 Fe 88 93.5 Epoxy 4.5 Tetraoctylbis- 2.0 -- -- -- 116 318 (ditridecylphos- phite)titanateNo. 23 3.0% Si--Fe 54 85.0 Epoxy 9.5 Tetraoctylbis 2.0 Al.sub.2 O.sub.3 10 3.5 151 336 (ditridecylphos- phite)titanateNo. 24 3.0% Si--Fe 54 85.0 Epoxy 9.5 Tetraoctylbis- 2.0 Al.sub.2 O.sub.3 10 3.5 191 456 (ditridecylphos- phite)titanateNo. 25 1.5% Si--Fe 54 85.0 Poly- 13.0 Isopropyltri- 2.0 -- -- -- 115 342 amide (N--aminoethyl- aminoethyl)- titanateComparativeExampleNo. 40 1.5% Si--Fe 54 85.0 Poly- 15.0 -- -- -- -- -- 195 579 amide__________________________________________________________________________
(1) In Example Nos. 1-7 and Comparative Example Nos. 26 to 29, the iron loss was measured while the composition, the average diameter and the mixing ratio of the magnetic powder were kept the same but the mixing ratios of the binder polymer, the Ti coupling agent, and the powder of an inorganic compound (CaCO 3 ) were varied.
As a result of these measurements, there was no great difference in the iron loss at 50 Hz in a commercial frequency range. However, regarding the iron loss at 50 kHz and 100 kHz within a high-frequency range, as can be seen from Table 1 above, the iron cores of Example Nos. 1 to 7 in which the Ti coupling agent was added in the amounts of 0.3% or more had smaller iron losses than those of Comparative Example Nos. 26 to 29. At 200 kHz, the iron core of Example No. 3 had an iron loss of 1,170 W/kg,while that of Comparative Example No. 28 had an iron loss of 4,060 W/kg, revealing a greater difference. Note that the Example wherein a portion of the binder polymer was replaced with CaCO 3 had a still smaller iron loss.
The difference in the iron loss within a high-frequency range including 50 kHz and 100 kHz in the Example and Comparative Example is an eddy current loss difference and is attributable to the electrical insulation state between the magnetic powder particles. This reveals the fact that the iron cores of the present invention have an excellent electrical insulating property.
FIG. 3 shows the results obtained with the measurement of an effective permeability at respective frequencies (40 kHz to 1,000 kHz). Curve a in FIG. 3 corresponds to Example No. 3, while curve b corresponds to Comparative Example No. 28. The effective permeability of the iron core of Example No. 3 remained substantially the same over a wide frequency range of 40 kHz to 1,000 kHz. In contrast, to this, in the iron core of Comparative Example No. 28 which did not contain a Ti coupling agent, the effective permeability is significantly lowered in a high-frequency range. A similar tendency is seen between the iron core of Example No. 5 which contained CaCO 3 and the iron core of Comparative Example No. 29 which did not. Such a low eddy current means a low effective permeability within a high-frequency range.
Using the samples of the iron cores of Example No. 3 and Comparative Example No. 28, the releasing force from a mold for forming a formed body of the same shape and size was measured. The releasing force was 500 kg or less in Example No. 3 and was as high as 1,500 to 2,000 kg in Comparative Example No. 28. This fact revealed the facts that the addition of a Ti coupling agent can reduce the releasing force of a formed body from a mold to allow easy formation, and prevent damage to the formed body being released from the mold, thereby improving the manufacturing yield.
The iron core samples of Example Nos. 1 to 7 all had magnetic flux densities of 0.6 T or higher at a magnitizing force of 10,000 A/m.
(2) The iron loss was measured for the iron cores of Example Nos. 8 to 14 wherein the mixing ratio of the magnetic powder was varied within the range of 55.0 to 98.4% and a Ti coupling agent was added, and for those of Comparative Example Nos. 30 to 35 wherein the mixing ratio of the magnetic powder was also varied within a range of 64.0 to 98.4% and a Ti coupling agent was not used. The obtained results are shown in Table 2 above.
As can be seen from Table 2, when a comparison is made between the samples containing the same amount of magnetic powder, the iron cores of the Examples have a smaller iron loss, and a difference in iron loss between the Examples and Comparative Examples is enhanced at a frequency of 100 kHz. A particularly large difference in iron loss was seen between Example No. 10 and Comparative Example No. 32 in both of which a CaCO 3 powder was added as a powder of an inorganic compound and between Example No. 12 and Comparative Example No. 34 in both of which an SiO 2 powder was added as a powder of an inorganic compound.
The iron cores of these Examples exhibit magnetic flux densities of 0.5 T or higher at a magnetizing force of 10,000 A/m. However, in Example No. 14 in which the mixing ratio of the magnetic powder was less than 60%, although the iron loss was small, the magnetic flux density at a magnetizing force of 10,000 A/m was 0.4 T or less.
(3) The iron loss was measured for the iron cores of Examples 15 to 18 wherein the composition of the magnetic powder was varied and a Ti coupling agent was added, and for those of Comparative Examples 36 to 39 wherein the composition of the magnetic powder was similarly varied but a Ti coupling agent was not added. The obtained results are shown in Table 3. The iron cores of the Examples have smaller iron loss than the iron cores of the Comparative Examples at 50 kHz and 100 kHz. At 200 kHz, the iron core of Example No. 16 had an iron loss of 869 W/kg, that of Comparative Example No. 37 had an iron loss of 4,840 W/kg, that of Example No. 18 had an iron loss of 690 W/kg, and that of Comparative Example No. 39 had an iron loss larger than 1,400 W/kg.
FIG. 4 is a graph showing changes in effective permeability in a frequency range of 40 kHz to 1,000 kHz. Curve c in FIG. 4 corresponds to Example No. 16, and curve d corresponds to Comparative Example No. 37. Although the iron core of the Example experiences substantially no decrease in effective permeability in a high-frequency range, the iron core of the Comparative Example experiences a substantial decrease in effective permeability within a frequency higher than 100 kHz. This also applies to Example No. 15 and Comparative Example No. 36, Example No. 17 and Comparative Example No. 38, and Example No. 18 and Comparative Example No. 39.
The iron cores of Example Nos. 15 to 18 all had magnetic flux densities of 0.6 T or higher at a magnetizing force of 10,000 A/m.
(4) The iron loss was measured for the iron core of Example Nos. 19 to 22 wherein the average diameter of the magnetic powder was varied, those of Example Nos. 23 and 24 wherein Al 2 O 3 was used and was added in different orders, and for those of Example No. 25 and Comparative Example No. 40 wherein a polyamide resin was used as a binder polymer. The obtained results are shown in Table 4.
It is seen from the results obtained that the iron loss in a high-frequency range decreases with a decrease in an average diameter of the magnetic powder. However, the change in iron loss with changes in particle size was very small near a commercial frequency range. The iron loss of Example No. 23 wherein Al 2 O 3 was dispersed in an epoxy resin before mixing it with other components had smaller iron loss and better characteristics than those of the iron core of Example No. 24 wherein Al 2 O 3 , a magnetic powder, a Ti coupling agent, and an epoxy resin were mixed simultaneously.
When a polyamide resin was used as a binder polymer, the iron core of Example No. 25 in which a Ti coupling agent was added had a smaller iron loss than that of the iron core of Comparative Example No. 40 wherein no such Ti coupling agent was added.
The iron cores of these Examples had magnetic flux densities of 0.6 T or higher at a magnetizing force of 10,000 A/m.
EXAMPLE NOS. 41-60
Iron cores were prepared following the same procedures as those in Example Nos. 1 to 25 using the compositions shown in Tables 5 to 8 below.
Except for Example No. 59, the powder of an inorganic compound used was dispersed in a binder polymer before mixing it with other components. In Example No. 59, all the components were mixed simultaneously.
The heat-treatment conditions, and measurement conditions for the magnetic properties such as iron loss, effective permeability, or magnetic flux density and releasing force from a mold were performed under the same conditions as those in Examples Nos. 1 to 40 described above.
TABLE 5__________________________________________________________________________ Binder Inorganic compoundMagnetic powder polymer Silane coupling agent powder Mixing Mixing Mixing Mixing Iron loss Average ratio ratio ratio Average ratio (W/kg);Composition particle (% by (% by (% by particle (% by B = 0.05T(% by diameter vol- vol- vol- diameter vol- 50 100weight) (μm) ume) Type ume) Type ume) Type (μm) ume) kHz kHz__________________________________________________________________________ExampleNo. 413.5% Si--Fe 54 85.0 Epoxy 14.7 β-(3,4-epoxycyclo- 0.3 -- -- -- 260 728 hexyl)ethyltri- methoxysilaneNo. 423.5% Si--Fe 54 85.0 Epoxy 13.0 β -(3,4-epoxycyclo- 2.0 -- -- -- 202 549 hexyl)ethyltri- methoxysilaneNo. 433.5% Si--Fe 54 85.0 Epoxy 11.5 β-(3,4-epoxycyclo- 3.5 -- -- -- 208 562 hexyl)ethyltri- methoxysilaneNo. 443.5% Si--Fe 54 85.0 Epoxy 10.3 β-(3,4-epoxycyclo- 0.7 CaCO.sub.3 2.8 4.0 202 508 hexyl)ethyltri- methoxysilaneNo. 453.5% Si--Fe 54 85.0 Epoxy 8.4 β-(3,4-epoxycyclo- 3.5 CaCO.sub.3 2.8 3.1 151 377 hexyl)ethyltri- methoxysilaneCom-parativeExampleNo. 613.5% Si--Fe 54 85.0 Epoxy 14.9 β-(3,4-epoxycyclo- 0.1 -- -- -- 313 958 hexyl)ethyltri- methoxysilaneNo. 623.5% Si--Fe 54 85.0 Epoxy 10.8 β-(3,4-epoxycyclo- 0.1 CaCO.sub.3 2.8 4.1 289 879 hexyl)ethyltri- methoxysilaneNo. 633.5% Si--Fe 54 85.0 Epoxy 15.0 -- -- -- -- -- 368 1,127No. 643.5% Si--Fe 54 85.0 Epoxy 10.9 -- -- CaCO.sub.3 2.8 4.1 332 1,010__________________________________________________________________________ 4
TABLE 6__________________________________________________________________________ Binder Inorganic compoundMagnetic powder polymer Silane coupling agent powder Mixing Mixing Mixing Mixing Iron loss Average ratio ratio ratio Average ratio (W/kg);Composition particle (% by (% by (% by particle (% by B = 0.05T(% by diameter vol- vol- vol- diameter vol- 50 100weight) (μm) ume) Type ume) Type ume) Type (μm) ume) kHz kHz__________________________________________________________________________ExampleNo. 46Fe 88 98.4 Epoxy 1.3 γ-glycidoxypropyl- 0.3 -- -- -- 197 597 trimethoxysilaneNo. 47Fe 88 97.5 Epoxy 1.8 γ-glycidoxypropyl- 0.7 -- -- -- 177 537 trimethoxysilaneNo. 483.5% Si--Fe 54 75.0 Epoxy 23.0 γ-glycidoxypropyl- 2.0 -- -- -- 196 432 trimethoxysilaneNo. 493.5% Si--Fe 54 75.0 Epoxy 16.7 γ-glycidoxypropyl- 2.0 SiO.sub.2 5.0 6.3 186 388 trimethoxysilaneNo. 503.5% Si--Fe 54 64.0 Epoxy 22.9 γ-glycidoxypropyl- 4.0 CaCO.sub.3 2.8 9.1 190 389 trimethoxysilaneNo. 513.5% Si--Fe 54 55.0 Epoxy 30.1 γ-glycidoxypropyl- 4.0 CaCO.sub.3 2.8 10.9 211 430 trimethoxysilaneCom-parativeExampleNo. 65Fe 88 98.4 Epoxy 1.6 -- -- -- -- -- 298 822No. 66Fe 88 97.5 Epoxy 2.5 -- -- -- -- -- 258 710No. 673.5% Si--Fe 54 75.0 Epoxy 25.0 -- -- -- -- -- 284 798No. 683.5% Si--Fe 54 75.0 Epoxy 18.7 -- -- SiO.sub.2 5.0 6.3 269 722No. 693.5% Si--Fe 54 64.0 Epoxy 32.7 -- -- CaCO.sub.3 2.8 12.5 298 759__________________________________________________________________________
TABLE 7__________________________________________________________________________ Binder Inorganic compoundMagnetic powder polymer Silane coupling agent powder Mixing Mixing Mixing Mixing Iron loss Average ratio ratio ratio Average ratio (W/kg);Composition particle (% by (% by (% by particle (% by B = 0.05T(% by diameter vol- vol- vol- diameter vol- 50 100weight) (μm) ume) Type ume) Type ume) Type (μm) ume) kHz kHz__________________________________________________________________________ExampleNo. 5245% Ni--Fe 54 85.0 Epoxy 9.5 γ-glycidoxypropyl- 2.0 CaCO.sub.3 2.8 3.5 143 312 trimethoxysilaneNo. 536.5% Si--Fe 54 85.0 Epoxy 9.5 γ-glycidoxypropyl- 2.0 CaCO.sub.3 2.8 3.5 207 439 trimethoxysilaneNo. 543.1% Al--Fe 54 85.0 Epoxy 9.5 γ-glycidoxypropyl- 2.0 CaCO.sub.3 2.8 3.5 136 293 trimethoxysilaneCom-parativeExampleNo. 7045% Ni--Fe 54 85.0 Epoxy 11.5 -- -- CaCO.sub.3 2.8 3.5 155 405No. 716.5% Si--Fe 54 85.0 Epoxy 11.5 -- -- CaCO.sub.3 2.8 3.5 445 1,340No. 723.5% Al--Fe 54 85.0 Epoxy 11.5 -- -- CaCO.sub.3 2.8 3.5 259 682__________________________________________________________________________
TABLE 8__________________________________________________________________________ Binder Inorganic compoundMagnetic powder polymer Silane coupling agent powder Mixing Mixing Mixing Mixing Iron loss Average ratio ratio ratio Average ratio (W/kg);Composition particle (% by (% by (% by particle (% by B = 0.05T(% by diameter vol- vol- vol- diameter vol- 50 100weight) (μm) ume) Type ume) Type ume) Type (μm) ume) kHz kHz__________________________________________________________________________ExampleNo. 55Fe 180 93.5 Epoxy 4.5 γ-glycidoxypropyl- 2.0 -- -- -- 208 710 trimethoxysilaneNo. 56Fe 105 93.5 Epoxy 4.5 γ-glycidoxypropyl- 2.0 -- -- -- 160 460 trimethoxysilaneNo. 57Fe 88 93.5 Epoxy 4.5 γ-glycidoxypropyl- 2.0 -- -- -- 110 302 trimethoxysilaneNo. 583.5% Si--Fe 54 85.0 Epoxy 9.5 γ-glycidoxypropyl- 2.0 Al.sub.2 O.sub.3 10 3.5 159 373 trimethoxysilaneNo. 593.5% Si--Fe 54 85.0 Epoxy 9.5 γ-glycidoxypropyl- 2.0 Al.sub.2 O.sub.3 10 3.5 193 433 trimethoxysilaneNo. 601.5% Si--Fe 54 85.0 Poly- 13.0 γ-aminopropyltri- 2.0 -- -- -- 121 360 amide ethoxysilaneCom-parativeExampleNo. 731.5% Si--Fe 54 85.0 Poly- 15.0 -- -- -- -- -- 195 579 amide__________________________________________________________________________
(1) The iron loss was measured for the iron cores of Example Nos. 41 to 45 and Comparative Example Nos. 61 to 64 wherein the composition, average particle size, and mixing ratio of the magnetic powder were kept the same, while the mixing ratios of the binder polymer, the silane coupling agent, and the powder of the inorganic compound (CaCO 3 ) were varied. The obtained results are shown in Table 5.
Each sample had substantially the same iron loss at 50 Hz in a commercial frequency range. However, at 50 kHz and 100 kHz in a high-frequency range, the iron loss of Example Nos. 41 to 45 in which the silane coupling agent was added in the amounts of 0.3% or more was smaller than that of Comparative Example Nos. 61 to 64 wherein the silane coupling agent was added in amounts less than 0.3%. Particularly at 200 kHz, the iron core of Example No. 43 had an iron loss of 1,290 W/kg while that of Comparative Example No. 63 had an iron loss of 4,060 W/kg. Thus, the higher the frequency, the greater the difference in the iron loss of iron cores of the Example and Comparative Example. An iron core wherein a portion of the binder polymer is replaced with CaCO 3 had a still smaller iron loss.
FIG. 5 is a graph showing changes in effective permeability within a frequency range of 40 kHz to 1,000 kHz. Curve e in FIG. 5 corresponds to Example No. 43, while curve f corresponds to Comparative Example No. 63. As can be seen from this graph, the iron core of Example No. 43 experiences substantially no change in effective permeability within a wide frequency range. However, in the iron core of Comparative Example No. 63 wherein no silane coupling agent is used, the effective permeability significantly decreased within the high-frequency range. The effective permeability was measured up to a high-frequency range for the iron cores of Example No. 45 and Comparative Example No. 64 in both of which CaCO 3 was added. A similar tendency as that shown in FIG. 5 was also observed.
The releasing force of a formed body from the mold was measured for Example No. 43 and Comparative Example No. 63. The iron core of Example No. 43 required a releasing force of 700 kg or less, and that of Comparative Example No. 63 required a releasing force of 1,500 to 2,000 kg.
The iron cores of Example Nos. 41 to 45 had magnetic flux densities of 0.6 T or higher at a magnetizing force of 10,000 A/m.
(2) The iron loss was measured for the iron cores of Example Nos. 46 to 51 wherein the mixing ratio of the magnetic powder was varied within a range of 55.0 the 98.4% and a silane coupling agent was added, and for the iron cores of Comparative Example Nos. 65 to 69 wherein the mixing ratio of the magnetic powder was varied within a range of 64.0 to 98.4% and no silane coupling agent was added. The obtained results are shown in Table 6.
As can be seen from Table 6, when a comparison is made between iron cores having the same mixing ratio of the magnetic powder, iron cores of the Examples have a smaller iron loss than those of the Comparative Examples. The difference in iron loss is particularly enhanced at 100 kHz. With iron cores of the Examples containing an SiO 2 or CaCO 3 powder as a powder of an inorganic compound, they have considerably smaller iron loss than those of the Comparative Example having the same magnetic powder mixing ratio.
The iron cores of these Examples have magnetic flux densities of 0.5 T or higher at a magnetizing force of 10,000 A/m. However, in Example No. 51 wherein the mixing ratio of the magnetic powder is less than 60%, although the iron loss is small, the magnetic flux density at a magnetizing force of 10,000 A/m was 0.4 T or less.
(3) The iron loss was measured for the iron cores of Example Nos. 52 to 54 wherein the magnetic powder composition was varied amd a silane coupling agent was added, and for those of Comparative Example Nos. 70 to 72 wherein the composition of the magnetic powder was similarly changed but no silane coupling agent was added. The obtained results are shown in Table 7. As can be seen from this table, the iron cores of the present invention had smaller iron loss at 50 kHz and 100 kHz. In particular, the iron core of Example No. 53 had an iron loss of 1,010 W/kg at 200 kHz. However, at the same frequency, the iron core of Comparative Example No. 71 had an iron loss of 4,840 W/kg, providing a big difference from that of the Example.
FIG. 6 is a graph showing changes in effective permeability within a frequency range of 40 kHz to 1,000 kHz. Curve g in FIG. 6 corresponds to Example No. 53, and curve h corresponds to Comparative Example No. 71. The iron core of the present invention experienced substantially no decrease in effective permeability even within a high-frequency range. However, the iron core of the Comparative Example 71 underwent a significant decrease in effective permeability at frequencies about 100 kHz. This substantially applied to Example No. 52 and Comparative Example No. 70, and Example No. 54 and Comparative Example No. 72.
The iron cores of Example Nos. 52 to 54 had magnetic flux densities of 0.6 T or higher at a magnetizing force of 10,000 A/m.
(4) The iron loss was measured for the iron cores of Example Nos. 55 to 57 wherein the average diameter of the magnetic powder was varied, the iron cores of Example Nos. 58 and 59 wherein the addition timing of Al 2 O 3 was varied, and the iron cores of Example No. 60 and Comparative Example No. 73 wherein a polyamide resin was used as a binder polymer. The obtained results are shown in Table 8.
It is seen from the obtained results that a change in iron loss due to changes in particle diameter is small near a commercial frequency range, but the smaller the average diameter of the magnetic powder the smaller the iron loss in a high-frequency range.
As for the time to add a powder of an inorganic compound, the iron core of Example No. 58 wherein Al 2 O 3 was dispersed in the epoxy resin had a smaller iron loss than that of the iron core of Example No.59 wherein Al 2 O 3 , the magnetic powder, the silane coupling agent, and the epoxy resin were mixed together simultaneously.
When a polyamide resin is used as a binder polymer, the iron core of Example No. 60 in which a silane coupling agent was added had a smaller iron loss than that of Comparative Example No. 73 wherein no silane coupling agent was added.
The iron core of these Example had excellent magnetic flux densities of 0.6 T or higher at a magnetizing force of 10,000 A/m.
EXAMPLE NOS. 61-62
Iron cores were prepared following the same procedures as those in Example Nos. 1 to 25 and using the components shown in Table 9. The powder of an inorganic compound was dispersed in a binder polymer. The heat-treatment conditions, and measurement conditions for magnetic properties such as iron loss, effective permeability, and magnetic flux density, and a releasing force from a mold were the same as those in Example Nos. 1 to 25. The obtained results are shown in Table 9.
TABLE 9__________________________________________________________________________ Binder polymer Al coupling agent Inorganic compoundMagnetic powder Mixing Mixing powder Iron loss Average Mixing ratio ratio Average Mixing (W/kg);Composition particle ratio (% by (% by particle ratio B = 0.05TExam- (% by diameter (% by vol- vol- diameter (% by 50 100ple weight) (μm) volume) Type ume) Type ume) Type (μm) volume kHz kHz__________________________________________________________________________No. 61 3.5% Si--Fe 54 85.0 Epoxy 13.0 Ethyl acetoacetate 2.0 -- -- -- 249 659 aluminum diiso- propylateNo. 62 3.5% Si--Fe 54 85.0 Epoxy 8.4 Ethyl acetoacetate 3.5 CaCO.sub.3 2.8 3.1 181 452 aluminum diiso- propylate__________________________________________________________________________
A comparison was made between Example Nos. 61 and 62 and Comparative Example Nos. 63 and 64 shown in Table 5 above. As a result of such a comparison, the iron loss at 50 Hz was seen to be substantially the same for all these iron cores. However, at 50 kHz and 100 kHz in a high-frequency range, the iron core of Example No. 61 had a smaller iron loss than that of Comparative Example No. 63. The difference in iron loss between these iron cores is particularly notable at 100 kHz. The iron core of Example No. 62 wherein a powder of an inorganic compound was added had a still smaller iron loss.
FIG. 7 shows changes in effective permeability within a frequency range of 40 to 1,000 kHz. Curve i in FIG. 7 corresponds to Example No. 61, and curve f corresponds to Comparative Example No. 63 and is the same as the curve in FIG. 5. The iron core of Example No. 61 experiences substantially no change in effective permeability over a wide frequency range. The iron core of Example No. 62 in which CaCO 3 was added and that of Comparative Example No. 64 had the same tendencies as that in FIG. 7.
The releasing force of a formed body from a mold after formation was measured for the iron cores of Example No. 61 and Comparative Example No. 63. The iron core of Example No. 61 required a releasing force of only 700 kg or less, which was less than half that of Comparative Example No. 63.
The iron cores of Example Nos. 61 and 62 both had magnetic flux densities of 1.0 T or higher at a magnetizing force of 10,000 A/m.
In addition to the iron cores described above, another iron core was prepared using as a magnetic powder a powder of an Fe--Si--Al alloy called cendust having an average diameter of 73 μm, a polycarbonate resin as a binder polymer, and a Ti coupling agent. This iron core had an iron loss at 100 kHz of about 1/3 of an iron core prepared similarly but without addition of the Ti coupling agent.
Still another iron core was prepared in accordance with a conventional method using powders of an Fe--Co alloy and an Fe--Si--B amorphous alloy and mixing them with a binder polymer and a coupling agent. The resultant iron core had a very small iron loss within a high-frequency range of 50 kHz or higher, a small effective permeability within the high-frequency range, and a very low releasing force from a mold after compression and formation therein.
As can be seen from the above description, when a powder core is manufactured from a magnetic powder composition of the present invention, the surface of each magnetic powder particle is covered with the coupling agent. Owing to the lipophilic function of the coupling agent, the binder polymer has a good wettability, dispersibility and bindability with respect to the magnetic powder. Of iron loss, an eddy current loss component increases in proportion to a square of the frequency, and most of the iron loss in a high-frequency range is attributed to the eddy current loss. However, since the iron core of the present invention has an excellent electric insulating property due to the presence of the binder polymer between the adjacent magnetic powder particles, the iron loss due to an eddy current loss component can be reduced. Furthermore, since the iron core of the present invention has a small iron loss in a high-frequency range, heat generation is suppressed, a decrease in effective permeability is not experienced, and a high magnetic flux density can be maintained. In addition to these advantages, the releasing force from the mold after compression can be small, and the workability is improved.
|
A magnetic powder composition suitable for manufacturing a powder core used in a reactor or transformer connected to a semiconductor switching element, essentially consists of a powder of a soft magnetic metal or alloy or a mixture of these, an electrically insulating binder polymer for binding the powder, and a coupling agent of an organic metallic compound for coupling the powder and the binder polymer. The obtained powder core has excellent frequency characteristics of magnetic permeability, a high magnetic flux density, and a small iron loss at high frequencies.
| 8
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a ceramics joined body, particularly a joined body of a ceramic member made of an aluminum compound and another member made of a metal or a ceramics, and a method of joining the two members.
2. Related Art Statement
Heretofore, various methods of joining a ceramic member and a metal member with the aid of a brazing material have been provided for various uses. Particularly, for joining an alumina or aluminum nitride member to another member, the following methods are known.
(1) An active brazing metal is used for the joining.
(2) A paste of molybdenum-manganese is applied on a surface of aluminum nitride, and baked to form a baked layer, a nickel plating is provided on the baked layer, and brazing is effected on the nickel plating via an intervening brazing material.
However, in the above methods (1) and (2), an active metal, such as titanium or molybdenum, etc., remains in the joined portion. Thus, particularly when a plasma of a halogen series corrosive gas exists, an active metal, such as Ti or Zn, etc., existing in the joining portion or Mn, Mo or glass, etc., is likely corroded easily. In addition, when an active brazing metal is directly contacted with a surface of a ceramic member and melted in the method (1), wettability of alumina or aluminum nitride is often bad, so that there is still room left for improving in order to stably obtain a high joining strength.
The method (2) is for solving the problem of wettability of the brazing material to ceramics, and includes the steps of applying a paste containing a respective powder of molybdenum, manganese and glass on a surface of the ceramic member, and baking the paste thereon. At that time, the components of the glass are solidified on the surface of the ceramic member to form a glass layer, while a molybdenum-manganese layer is formed on the glass layer. In such a case, joining strength of the ceramic member and the glass layer is relatively high, and the molybdenum-manganese layer and the brazing metal are strongly bonded. In this way, since a direct strong bonding of a brazing metal on a surface of a ceramic member is difficult, a glass layer and a molybdenum-manganese layer are interposed therebetween to improve the joining strength therebetween. However, the layers intervening between the ceramic member and the another member were so many that the strength of the joining portion was not always stable. Moreover, in order to bake and fix such a glass-containing paste on the surface of the ceramic member, a high temperature of at least 800° C. is usually necessary, so that a residual stress resulting from difference between thermal expansions of the ceramic member and the metal member becomes large to likely a cause a destruction.
SUMMARY OF THE INVENTION
An objection of the present invention is to provide a novel method of joining a ceramic member containing aluminum and another member made of a metal or a ceramic.
Another object of the present invention is to improve the joining strength of the joined body.
A further object of the present invention is to provide a micro structure of the joined body having a high strength at the joined interface.
The present invention is a ceramics joined body including a ceramic first member made of an aluminum compound and a second member made of a ceramics or a metal, comprising a joining layer formed between the first member and the second member, and the joining layer having a continuous phase made of a metallic joining material and a dispersed phase made of an intermetallic compound formed among the continuous-phase.
The present invention is also a method of joining a ceramics including joining a ceramic first member made of an aluminum compound and a second member made of a ceramics or a metal forming a metal film on a surface to be joined of the first member such that the metal film contacts directly with the surface to be joined of the first member, interposing a metallic joining material made of a different material from the metal film between the metal film and the second member, and heating at least the metallic joining material and the metal film in the state that the metallic joining material intervenes between the metal film and the second material thereby to join the first member and the second member.
The inventors made studies in order to develop a method of firmly joining a ceramic member, such as aluminum nitride, etc., to another member at a lowest temperature as possible. In the process of the study, the inventors made tests of forming a nickel plating layer or a vapor deposited nickel layer on the surface of the ceramic member. In that step, the vapor deposited nickel layer or the nickel plating layer had a weak joining strength to the ceramic member and easily peeled off therefrom. However, the inventors have found out that if a brazing material was provided directly on the surface of the nickel plating layer or the vapor deposited nickel layer, and the brazing material was contacted to another metal or ceramic member and heat-treated under the contacted state, an unexpected firm joining can be attained between the ceramic member and the another member.
The thus obtained joined body was analyzed by inspecting the state of the joined interface thereof to find out that the vapor deposited nickel layer or the nickel plating layer was disappeared and nickel was reacted with the brazing material to form a dispersed layer made of an intermetallic compound. From this finding, the mechanism of joining was presumed as follows. In the process of heating the brazing material, at first the brazing aluminum is wetted by nickel, and then nickel is melted in the brazing material to form an intermetallic compound between nickel and aluminum. The reaction of forming the intermetallic compound between nickel and aluminum is an exothermic reaction, it is considered that a local temperature elevation occurred by the reaction heat, so that aluminum and aluminum nitride are wetted to afford the joining.
This point will further be explained. When a metal film made of nickel and a metallic joining material consisting mainly of aluminum are used for the joining, they are usually heated to 600° C. It is forecasted that at that time an aluminum-nickel intermetallic compound is formed under an exothermic reaction, so that local temperature elevations occur. Generally, ceramics and metals have improved wettability at high temperatures. Therefore it is considered that also this case, the wettabilities of the ceramics and the metal are improved by virtue of the exothermic reaction to afford the firm joining.
The thus obtained joined body according to the present invention includes a continuous layer made of a metallic joining material and a dispersed layer made of an intermetallic compound finely dispersed in the continuous layer. Usually, an intermetallic compound has a coefficient of thermal expansion which is smaller than that of a main component of the metallic joining material, and which is close to those of ceramics, particularly to those of nitride ceramics. By adopting the structure wherein such a dispersed layer is dispersed in the continuous layer of the metallic joining material, the residual stress after the joining could particularly be noticeably mitigated.
Particularly when the joined body of the present invention is used to use fields of being exposed to a halogen series corrosive gas, such as NF 3 or CF 4 , etc., permeation of the corrosive gas into the inside of the joining layer can be blocked at the place of the dispersed layer made of the intermetallic compound to prevent the invasion of corrosion. Therefore, the present invention is most suited to this use.
The inventors have found out that although the aforedescribed joining is most useful in joining an aluminum-nitride member to the another ceramic or metal member, it is also applicable in the case of joining an alumina member to another member.
As the material of the metallic joining member, use is made of a metallic brazing material. The metallic joining material may have any shape of sheet, powder or a mixed paste of powder and a binder. The above described expression "forming a metal film on a surface to be joined of the first member such that the metal film contacts directly with the surface to be joined of the first member" means that the metal film and the ceramic first member are joined without an intervening substance therebetween. If another substance is intervening between the metal film and the ceramic first member, a joining strength of the metallic joining material to the first member cannot be improved.
The clarify the above statement, the metal film can be formed on a surface of the first member by gas phase processes (chemical vapor deposition process, sputtering process, etc.), liquid phase processes (electrolytic plating process, electroless plating process, etc.). Particularly, according to the electroless plating process, the surface of the ceramic first member can easily be coated with the metal film. The metal layer preferably has a thickness of 0.1-20 μm.
A paste obtained by dispersing a powder of Ni or the like in an organic binder may be applied to a surface of the first member, the applied paste may be dried to dissipate the organic binder thereby to form the metal film. Alternatively, a metal foil may be contacted to a surface of the first member to form the metal film.
Among these methods, if the metal film was provided according to the gas phase processes, the liquid phase processes, or the paste-drying method, a satisfactory metal film could be obtained particularly with regard to the joining strength and the residual stress.
Next, in the state of the metallic joining material intervening between the metal film and the second member, heating is effected to heat at least the metallic joining material and the metal film. At the time of heating, preferably the metallic joining material is melted to perform the brazing. However, the whole of the metallic joining material needs not always be melted, and local melting of a portion thereof at least in the neighborhood of the interface between the metal film and the metallic joining material is sufficient. The expression "heating at least the metallic joining material and the metal film" comprises, in addition to the heat treating of all the joined body including these and the first and second members, the case of heat treating exclusively the regions having the metal film and the metallic joining material by a local heating means, such as, high frequency wave, laser beam, etc.
As the material of the metal film to be applied on the surface of the ceramic first member, use may be made of copper or aluminum, in addition to nickel.
BRIEF DESCRIPTION OF THE DRAWING
For a better understanding of the present invention, reference is made to the accompanying drawings, in which:
FIG. 1A is a schematic cross-sectional view showing a state of forming a metal film 52 on a surface 50a of a first member 50;
FIG. 1B is a schematic cross-sectional view showing a state of opposing and laminating the first member 50 and the second member 51;
FIG. 1c is a schematic cross-sectional view of a joined body obtained by joining the first and second members 50, 51;
FIG. 2A is a schematic cross-sectional view showing a state of forming metal films on the respective surface of the first and second members 50A, 50B;
FIG. 2B is a schematic cross-sectional view of the opposingly laminated first and second members 50A, 50B;
FIG. 2C is a schematic cross-sectional view of a joined body obtained by joining the first and second members 50A, 50B;
FIG. 3A is a schematic enlarged cross-sectional view of a joined interface of the first and second members 50, 51;
FIG. 3B is a schematic enlarged cross-sectional view of a joined interface of the first and second members 50A, 50B;
FIG. 4A is a plan view of an example of a plasma-generating electrodes apparatus accommodating therein high frequency electrodes showing an example of using the ceramics joining structure of the present invention;
FIG. 4B is a schematic cross-sectional view showing a joining portion of electric power supplying member in the plasma-generating apparatus shown in FIG. 4A;
FIG. 5 is a schematic enlarged cross-sectional view showing the neighborhood of the interface between a mesh electrode 12 and a joining layer 15 shown in FIG. 4B;
FIGS. 6A, 6B and 6C are schematic cross-sectional views respectively showing an embodiment of applying the present joining method and joined body to the joining portion of the mesh electrode and the electric power supplying member of the plasma-generating electrodes apparatus;
FIGS. 7A, 7B are schematic cross-sectional views respectively showing an embodiment of applying the present joining method and joined body to the joining portion of the mesh electrode and the electric power supplying member of the plasma-generating electrodes apparatus;
FIGS. 8A, 8B are schematic cross-sectional views respectively showing an embodiment of applying the present joining method and joined body to the joining portion of the mesh electrode and the electric power supplying member of the plasma-generating electrodes apparatus;
FIG. 9 is a schematic cross-sectional view showing a state of integrally joining a ceramic heater 62 to a flange portion 60 of a semiconductor producing apparatus;
FIG. 10 is a photograph taken by a survey type electron microscope showing a ceramics texture of a joining interface of a joined body corresponding to FIG. 3A; and
FIG. 11 is a photograph taken by a survey tape electron microscope showing a ceramics texture of a joining interface of a joined body corresponding to FIG. 3B.
Numbering in the drawings
1 . . . substrate
11 . . . hub
12 . . . mesh electrode
14 . . . electric power supplying member
15, 20 . . . joining layer
16, 21 . . . inserting member
19 . . . cap
44 . . . terminal of electric power supplying member
45 . . . electric power supplying member
50, 50A . . . ceramic first member made of an aluminum compound
50a . . . surface of the first member
50B, 51 . . . second member
52, 52A, 52B . . . metal film
53 . . . metallic joining material
54, 55 . . . joining layer
56, 58 . . . metallic joining material
57, 59A, 59B . . . dispersed phase made of intermetallic compound
60 . . . continuous phase made of intermetallic compound
71, 72 . . . region rich with intermetallic compound
Hereinafter, the present invention will be explained in more detailed with reference to the exemplified drawings.
Referring to FIGS. 1A-1C showing the processes of joining the first member 50 and the second member 51, the whole shapes of the members 50, 51 are not specifically limited. The first member 50 is a ceramics made of aluminum compound, and the second member 51 is made of a metal or ceramics other than the aluminum compound. As such a ceramics, aluminum nitride may be exemplified, and as such a metal, nickel, cooper, aluminum, and Kovar may be exemplified. A metal film 52 is formed on a surface 50a to be joined of the first member 50, as shown in FIG. 1A. Then, the first member 50 and the second member 51 are opposed with a metallic joining material 53 intervening between the metal film 52 of the first member 50 and the surface 51a to be joined of the second member 51, as shown in FIG. 1B. Thereafter, the first and second members 50, 51 are heat-treated to join the members 50, 51 with a joining layer 54 formed therebetween, as shown in FIG. 1C.
FIGS. 2A-2C are schematic cross-sectional views showing the processes of joining the first member 50A and the second member 50B. The first and second members 50A, 50B are ceramics respectively made of an aluminum compound. For that reason, a metal film 52A is formed on a surface 50a to be joined of the first member 50A, while a metal film 52B is formed on a surface 50b to be joined of the second member 50B, as shown in FIG. 2A. Then, the first and second members 50A, 50B are opposed with a metallic joining material 53 intervening between the metal films 52A, 52B, as shown in FIG. 2B. Thereafter, the first and second members 50A, 50B are heat treated to join the members 50A, 50B with a joining layer 55 formed therebetween, as shown in FIG. 2C.
As explained above with reference to FIGS. 1A-1C, if the second member made of a metal or ceramics other than the ceramics made of the aluminum compound is joined to the first member, the joining layer 54 is formed as shown in schematic cross-sectional view in FIG. 3A. The metal film 52 shown in FIG. 1A is disappeared in the joining layer 54, and particles 57 made of an intermetallic compound or a dispersed layer thereof were dispersed in the continuous layer 56 made of the metallic joining material. Namely, accompanying with the proceeding of the reaction of the metallic joining material with the material of the metal film, the components of the metal film were removed into the metallic joining material. In addition, particularly, a continuous layer 60 made of the intermetallic compound was occasionally formed on the surface of the second member 51 made of a metal. The continuous layer 60 occurred easily particularly when the second member was made of nickel. The continuous phase 60 is composed of a plural layers of intermetallic compounds of different composition or a single composition.
On the other hand, as explained above with reference to FIGS. 2A-2C, if the first and second members 50A, 50B both made of aluminum compounds are joined, the joining layer 55 is formed as shown in schematic cross-sectional view in FIG. 3B. That is, the metal films 52A, 52B shown in FIG. 2A are disappeared in the joining layer 55, and particles 59A, 59B made of intermetallic compounds, were formed along the surfaces 50a, 50a of the members 50A, 50B. This is considered due to starting of the solidification of the joining layer 55 from the vicinity of the respective surfaces 50a, 50a. The respective particles 59A, 59B were existing continuously along the respective interface to form regions 71, 72 which are rich with the intermetallic compound.
Next, preferable metallic joining materials which can be used in the present invention will be explained. The metallic joining material is not particularly limited to specific ones so far as it can form an intermetallic compound between the material of the metal film, and pure metals of copper, nickel, silver, aluminum or alloys thereof may be used. In order to reduce at the maximum the residual stress between the first member and the second member, a brazing material consisting mainly of aluminum is preferable, because it can perform the joining at low temperatures. In the present invention, a firm joining could be formed without particularly incorporating an active metal into the metallic joining material. This indicates that diffusion of active metal components into the ceramic members are not particularly necessary.
Therefore, an active metal needs not be incorporated into the brazing aluminum, however, 0.3-20 wt. % of Mg may be incorporated therein. Also, a third component of an amount of not more than 50 wt. % may be incorporated into the brazing aluminum. As the third component, at least one component selected from the group consisting Si and Cu may be used.
From a view point of durability to halogen series corrosive gases, metallic joining materials consisting mainly either of nickel, copper and aluminum are preferable. If Si is used as a component of the alloys, the amount of Si is desirably not more than 20 wt. % so as not to suffer from corrosive gases.
Hereinafter, preferable embodiments of various changes of the shapes of the first and second members will be explained in sequence. Referring to FIG. 4A showing an example of the structure of susceptor having high frequency electrodes and FIG. 4B showing a cross-sectional view of the susceptor of FIG. 4A along the line IVb--IVb, a high frequency electrode 12 is embedded in a disc-shaped substrate 1 which is a ceramics made of an aluminum compound. The high frequency electrode 12 is a mesh-shaped bulk material in this example. Reference numeral 2 is a flange made of alumina for attaching the substrate 1, reference numeral 4 is a joining portion of the electric power supplying member, reference numeral 5 is a joining portion of a thermocouple, and reference numeral 6 is a supporting portion for the substrate 1 of the susceptor and the alumina flange 2. Among these, detailed structure of the joining portion 4 of the electric power supplying member and the joining portion 5 of the thermocouple are shown in FIG. 4B.
The flange 2 is joined to a hub 11 made of aluminum nitride, and the hub 11 is joined to the rear surface 1b of the substrate 1. A high frequency electrode 12 is embedded in the substrate 1 at the vicinity of the surface 1a. The high frequency electrode 12 is preferably made of a high melting point metal, such as molybdenum, tungsten, etc. The substrate 1 is formed of a hole 13 opening at the rear surface 1b and exposing a mesh electrode 12 at the bottom. An elongated electric power supplying member 14 is accommodated within the inner space of the flange 2, and a distal end portion 14a of the member 14 is joined to the bottom 13a of the hole 13 via a joining layer 15 and an inserting member 16 for mitigating the residual stress. This constitutes the joining portion 4.
In the joining portion 4 for the electrode, the joining layer 15 is contacting with the bottom 13a of the hole 13 of the substrate 1, and the mesh electrode 12 is exposed at the bottom 13a, as exemplarily shown in FIG. 5. The joining portion 15 is joined to the mesh electrode 12 which is a metal exposed portion, and the joining portion 15 is joined to the substrate 1. If a mesh electrode 12 is particularly used as the metal exposed portion, the joining portion of the joining portion 15 and the mesh electrode 12 is existing in a mesh fashion, and the joining portion of the joining portion 15 and the substrate 1 is formed at the mesh. In this way, the joining portions of the mesh electrode and the brazing material and the joining portion of the substrate and the brazing material are existing alternately, so that a very strong joining can be achieved.
The substrate 1 has a hole 17 opening at the rear surface 1b. The hole 17 is shallower than the hole 13 and exposing the ceramics of the substrate 1 at the bottom. A hollow sheath 18 covering a thermocouple is accommodated within the flange 2, and a cap 19 of a high melting point metal for protecting the thermocouple is applied around a distal end 18a of the hollow sheath 18. The outer diameter of the cap 19 is slightly smaller than the inner diameter of the hole 17. The joining portion 5 of the thermocouple is constructed by joining the cap 19 to the bottom 17a of the hole 17 via the joining portion 20 and an inserting member 21.
Here, the present invention is applicable to joining of the alumina flange 2 and the aluminum nitride hub 11, and to joining of the hub 11 and the aluminum nitride substrate 1. In such cases, either one may be used as the first member and the other one may be used as the second member. The present invention is also applicable to the joining portion of the inserting member 16 and the substrate 1. In such a case, the substrate 1 exposing to the hole 13 is used as the first member, and the inserting member 16 is used as the second member.
FIG. 6A, 6B, 6C, 7A, 7B, 8A and 8B are respectively a schematic cross-sectional view showing the vicinity of an electric power supplying member in a plasma-generating electrode apparatus which is similar to the example shown in FIGS. 4A, 4B. Similar members as those shown in FIGS. 4A, 4B are allotted with same reference numerals and explanations thereof will be omitted sometimes.
In the example shown in FIG. 6A, a tubular terminal 41 having a through hole 41 at the center is accommodated in the hole 13. The terminal 41 is made of Ni or Al. The lower end surface of the terminal 41 is joined to the bottom 13a by the joining layer 15a, and the lower circumferential side surface of the terminal 41 is joined to the circumferential side surface of the hole 13 by the joining layer 15b. The joining layer 15b functions to prevent direct contact of the corrosive gas in the semiconductor producing apparatus to the mesh electrode 12.
In the example shown in FIG. 6B, a hole 57 is tapered and accommodates a tapered terminal 44 made of Ni or Al therein. The lower bottom surface of the terminal 44 and the bottom 57a of the hole 57 are joined via a joining layer 22a, and the circumferential side surface of the terminal 44 and the circumferential side surface 57b of the hole 57 are joined via a joining layer 22b. Thereafter, an electric power supplying member 45 made of Ni or Al is connected to the terminal 44 by melding.
In the example shown in FIG. 6B, by tapering the hole 57 and joining the circumferential side surface 57b of the hole 57 and the terminal 44 according to the present invention, a larger joining surface bay be obtained and a more gas tight structure for the bottom 57a can be obtained. In addition, by inserting the terminal 44 in the hole 57, the heating of the metallic joining material can be allowed, while pressing the circumferential side surface of the hole 57 along the tapered surface of the terminal 44.
The joining structure shown in FIG. 6C has further a stress-mitigating member 24 made of aluminum nitride and accommodated in the through hole 41a in addition to the joining structure shown in FIG. 6A. The lower bottom surface of the stress-mitigating member 24 and the bottom 13a of the hole 13 are joined according to the present invention. Namely, the joining portion and its neighboring portion are exposed to temperature elevation and processing, and in such cases thermal stress is exerted on the joining interface between the joining layers 15a, 15b and the ceramics caused by difference of thermal expansion between the metal and the ceramics. However, by adopting the structure of sandwiching the terminal 41 by means of the stress-mitigating ceramic member 24, the stress acting on the joining layers from the terminal 41 is dispersed and mitigated. The ceramic member 24 is particularly effective in mitigating the stress at the interface between the joining layer 15a and the ceramics. In FIGS. 6A, 6B and 6C, the substrate 1 exposing to the hole 13 is used as the first member, and the terminals 41, 44 made of a corrosion resistant metal to be joined thereto are used as the second member.
In the example shown in FIG. 7A, a through hole 46 is provided at the center of a tapered bush 58. An enlarged pressing portion 45a is formed at the outermost end of the electric power supplying member 45. The member 45 is inserted in the through hole 46 and heating is effected while pushing the metallic joining material toward the direction of the bottom 57a of a hole 57. The heating is also effected while pushing the metallic joining material toward the circumferential side surface 57b of the hole 57 by means of the bush 58.
In this example, when the joining is effected to the bottom 57a of the hole 57, the pressing portion 45a can exert a pressure on the joining portion, so that the joining strength of the joining portion can further be improved along the bottom 57a. In this embodiment, the substrate 1 is used as the first member, and the pressing portion 45a and the corrosion-resistant metallic bush 58 to be joined therewith are used as the second member.
In the example shown in FIG. 7B, a thin disc 47 made of Ni or Al having substantially the same shape and inner diameter with those of the hole 13 is joined to the bottom 13a of the hole 13 via the joining layer 15 according to the present invention. Then, the Ni or Al thin disc 47 is connected to the electric power supplying member 45 made of Ni or Al by welding to make integral therewith. In this embodiment, the thermal stresses generated in the production step and during the use can further be decreased by the use of the disc 47. In this embodiment, the substrate 1 is used as the first member, and the disc 47 to be joined therewith is used as the second member.
In the example shown in FIG. 8A, an end surface of an aluminum nitride ring-shaped intermediate member 48 and an end surface of an electric power supplying member 45 made of Ni or Al is joined in the hole 13 to the bottom 13a via the joining portion 15. In this embodiment, the aluminum nitride intermediate member 48 and the practically electric power supplying member 45 are simultaneously joined to the bottom 13a, so that the thermal stresses can further be decreased. In this embodiment, the substrate 1 is used as the first member, and the electric power supplying member 45 and the intermediate member 48 are used as the second member.
In the example shown in FIG. 8B, several portions of the mesh electrode 12 are severed and the remaining portions of the mesh electrode 12 are extended toward the rear surface 1b of the substrate 1, and the substrate 1 at this state was sintered integrally. By this operation, the severed portions 58 are extending from the mesh electrode 12 toward the direction of the rear surface 1b, and the end surfaces of thin wires 58 which constitute the severed portions are exposed on the rear surface 1b. The electric power supplying member 45 is joined to the rear surface 1b of the substrate 1 via the joining member 15, and the electric power supplying member 45 is connected to the wires 58. In this embodiment, the substrate 1 is used as the first member, and the electric power supplying member 45 is used as the second member. In the embodiment shown in FIG. 8B, the processes of forming the holes 13, 57 are not necessary on the mesh portion 12 which is difficult to process.
FIG. 9 is a schematic cross-sectional view of a structure joining a metal flange 60 and a ceramics heater 62 of a semiconductor producing apparatus. The metal flange 60 is provided with an attaching portion 60a for attaching the flange 60 to the chamber of the semiconductor producing apparatus, and an elongated portion 60b extending in the interior of the apparatus. A space 61 separated from the inner atmosphere of the apparatus is formed within the elongated portion 60b. To an end surface 60c of the elongated portion 60b is joined a rear surface 66b of a ceramics substrate 66 of a ceramic heater 62 via a joining member 70 according to the present invention. A heat-generating resistive member 63 is embedded in the substrate 66 and the ends of the heat-generating resistive member 63 are connected to terminals 64. The terminals 64 are exposed on the rear surface 66b of the substrate 66 and connected respectively to rod members 67 for supplying an electric power. The substrate 66 has a recess 65 at the rear surface 66b, which accommodates therein an end heat contacting portion of a thermocouple 68.
The temperature of a wafer-heating surface 66a is controlled by adjusting the electric power to be supplied to the heat-generating resistive member 63, while measuring the temperature of the substrate 66 by means of the thermocouple 68. The method for measuring the temperatures, the structure of the heat-generating resistive member and the structure of connecting the terminals are of course not specifically limited. By this arrangement, a heating apparatus can be provided which prevent the easily corrodable thermocouple and the terminals of the ceramics heater from exposing to the interior of the semiconductor producing apparatus.
In the example shown in FIG. 9, a functional member, such as an electrostatic chuck electrode or a high frequency electrode can be embedded in the substrate 66 to which the flange 60 is to be joined. At that time, the respective functional member and the terminal for supplying an electric power thereto can be prevented from exposing to the space 61 thereby from exposing to the interior of the semiconductor producing apparatus.
In the embodiments shown in FIGS. 4-8, the mesh electrode which is the high frequency electrode may be a punched metal or non-woven fabric. Also, an electrostatic chuck electrode or a heat-generating resistive member as shown in FIG. 9 may be embedded in the substrate instead of the high frequency electrode.
DESCRIPTION OF PREFERRED EMBODIMENTS
Herein after, the present invention will be explained in more detail with reference to Preparation Examples.
Preparation Example 1
Joined bodies were prepared according to the method shown in FIG. 2. As the first and second members, respectively a plate-shaped aluminum nitride ceramics member was prepared having a size of 8 mm×40 mm×20 mm. In the Preparation Examples 1-1-1-4 shown in the following Table 1, a surface 50a of the respective member was plated by contacting with a nickel plating solution for a determined time. A brazing material sheet 53 having a ratio of components as shown in Table 1 was sandwiched between the two members to prepare an assembled body to be treated. The assembled body was put in an electric furnace and heated to a temperature of not less than the melting point of the brazing material and then cooled to room temperature to prepare a respective joined body. The sheet 53 had a size of 8 mm×40 mm×0.12 mm. When effecting the heating, a pressure of 70 g/cm 2 was applied to the sheet in the vertical direction. In comparative Examples 1-1, 1-2, the surface treating of the respective member was not performed.
A test piece for four points bending strength test was cut off from the respective joined body and measured for four points bending strength according to the method of JIS Z2204. Also, the respective joined body was exposed to a CF 4 plasma at 400° C. for 192 hrs. and the exposed joined body was measured for four points bending strength in the same manner as described above. Also, discoloration of the joined interface of the respective joined body was examined and a length of the discolored portion from the surface was measured considering the discolored portion as an invaded portion. The length of the discolored portion was expressed as the invaded distance.
TABLE 1__________________________________________________________________________ Four Points Components Ratio Initial Four Points Bending Strength InvasionPreparation in Brazing Surface Bending Strength, After Corrodec, DistanceExample Material Treating MPa MPa μm__________________________________________________________________________Example Al--10Si--1.5Mg Ni plating on 288 250 1501-1 the member surface for 5 min.Example Al--10Si--1.5Mg Ni plating on 272 255 1451-2 the member surface for 10 min.Example Al--12Si--3Cu Ni plating on 270 250 1451-3 the member surface for 10 min.Example 99Al Ni plating on 245 220 801-4 the member surface for 10 min.Comparative Al--10Si--1.5Mg Not treated 110 65 200Example1-1Comparative Ag--35Cu--2.25Ti Not treated 270 0 >1500Example1-2__________________________________________________________________________
As shown in Table 1, a joined body having a high four points bending strength and a high corrosion resistant property to halogen series corrosive gases and the like corrosive gases can be provided according to the present invention, and the joining can be performed easily by means of a brazing material made of various aluminum alloy or pure aluminum.
Meanwhile, the joined body of Comparative Example 1-1 had a relatively work joining strength and an inferior corrosion resistant property. This is considered presumably due to a low wettability of the brazing material to aluminum nitride. In Comparative Example 1-2, a method was adopted of largely increasing the content of the active metal in the brazing material to improve the wettability of the brazing material to aluminum nitride. As a result, the thus obtained joined body had a large initial joining strength, however, corrosion of the joined body was extremely progressed when exposed to a corrosive gas.
A photograph of the joining interface of the joined body of Preparation Example 1-1 was taken by a survey type electron microscope as shown in FIG. 10. As seen from FIG. 10, along the interfaces of the both sides of the joining layer made of the brazing material, particles of another substance were formed in rows. The respective portion of the joining layer was elementary analyzed by EDAX to find dispersed layers made of an aluminum-nickel intermetallic compound of a composition of Al 3 Ni remaining on the both sides of the layer made of the brazing material.
Preparation Example 2
Joined bodies were prepared according to the method shown in FIG. 1. Namely, two sheets of first member made of aluminum nitride were prepared, and a sheet of second member made of a metal was prepared. The sheet of the first member was sandwiched and joined between the two sheets of the second member. The material of the second member was varied as shown in the following Table 2. The size of the first member was 8 mm×40 mm×20 mm, and the size of the second member was 8 mm×40 mm×2 mm.
In the Preparation Examples 2-1-2-7 shown in Table 2, a surface 50a of the first member 50 was contacted with a nickel plating solution for a determined time to perform a nickel plating. A brazing material sheet 53 having a ratio of components as shown in Table 2 was sandwiched between the first and second members 50, 51 to prepare an assembled body to be treated. The assembled body was put in an electric furnace and heated to a temperature of not less than the melting point of the brazing material and then cooled to room temperature to prepare a respective joined body. The sheet 53 had a size of 8 mm×40 mm×0.12 mm. When the heating is effected, a pressure of 70 g/cm 2 was applied to the sheet in the vertical direction. In Comparative Examples 2-1-2-4, the surface treating of the respective member was not performed.
A test piece for four points bending strength test was cut off from the respective joined body and measured for four points bending strength according to the method of JIS Z2204.
TABLE 2______________________________________Components Four PointsRatio in Kind of BendingPreparation Brazing Surface Second strengthExample Material Treating Member MPa______________________________________Example 2-1 Al--10Si--1.5Mg Ni plating on Ni 200 the member surface for 10 min.Example 2-2 Al--10Si--1.5Mg Ni plating on A1 212 the member surface for 10 min.Example 2-3 Al--10Si--1.5Mg Ni plating on Co 195 the member surface for 10 min.Example 2-4 Al--10Si--1.5Mg Ni plating on Mo 180 the member surface for 10 min.Example 2-5 Al--10Si--1.5Mg Ni plating on Kovar 205 the member surface for 10 min.Example 2-6 Al--12Si--3Cu Ni plating on Ni 195 the member surface for 10 min.Example 2-7 99Al Ni plating on Ni 190 the member surface for 10 min.Comparative Al--10Si--1.5Mg Not treated Ni 95Example 2-1Comparative Al--10Si--1.5Mg Not treated Mo 80Example 2-2Comparative Ag--25Cu--2.25Ti Not treated Ni 120Example 2-3Comparative Cu--2.25Ti Not treated Ni 90Example 2-4______________________________________
As seen from Table 2, a joined body having a high four points bending strength can be provided according to the present invention, and the joining can be performed easily by means of a brazing material made of various aluminum nitride alloy or pure aluminum. A high joining strength was obtained also when either of nickel, molybdenum, copper, Kovar or aluminum was used as the material of the second member.
Meanwhile, the joined bodies of Comparative Examples 2-1, 2-2 had a relatively weak joining strength. This is considered presumably due to a low wettability of the brazing material to aluminum nitride. In Comparative Example 2-3, a method was adopted of largely increasing the content of the active metal in the brazing material to improve the wettability of the brazing material to aluminum nitride. However, in such a case, the temperature required for the joining was 600°-670° C. for Al series brazing materials, whereas it was 850° C. for the Comparative Example 2-3, and 1,050° C. for the Comparative Example 2-4, so that the joining strength of the Comparative Examples 2-3, 2-4 were low for the sake of remarkable thermal stress caused by difference of thermal expansion between the first member which is a ceramics and the second member which is a metal.
A photograph of the joining interface of the joined body of Preparation Example 2-1 was taken by a survey type electron microscope as shown in FIG. 11. As seen from FIG. 11, particles of another substance were existing at everywhere in the joining layer made of the brazing material. Therefore, the respective portion of the joining layer was elementary analyzed by EDAX to find a large number of aluminum-nickel intermetallic compound particles of a composition of Al 3 Ni were formed in the continuous layer of the brazing material.
A continuous phase of a nickel-aluminum inter-metallic compound was found extending in a layer fashion along the interface between the joining layer and the nickel member. Among the continuous phase, Al 3 Ni was mainly formed in the region remote from the nickel member and Al 3 Ni 2 was mainly formed in the region near the nickel member.
As described above, according to the present invention, a novel method of joining a ceramics containing aluminum to another member made of a metal or a ceramics whereby the joining of the ceramics containing aluminum to the another member can be facilitated and the joining strength can be improved. Therefore, the joined body according to the present invention can be satisfactorily applied to ceramic heaters, electrostatic chucks, susceptors having high frequency electrodes as well as to various semiconductor producing apparatuses and semiconductor devices.
Although the present invention has been explained with specific examples and numeral values, it is of course apparent to those skilled in the art that various changes and modifications thereof are possible without departing from the broad spirit and aspect of the present invention as defined in the appended claims.
|
Novel method of joining ceramics containing aluminum nitride and another member made of a metal or a ceramic is provided having an improved joining strength and a corrosion-resistant property by joining a first member made of a ceramics consisting of an aluminum compound. The second member is made of a ceramics or a metal, forming a metal film directly on a surface to be joined of the first member interposing a metallic joining material which is made of a different material from the metal film. The metallic joining material is between the metal film and the second member, and by heating at least the metallic joining material and the metal film in such an interposed state to form a joining layer made of the metallic joining material and an intermetallic compound between the first and second members, so as to join the two members.
| 2
|
CROSS-REFERENCE TO RELATED APPLICATION
This application is a Continuation, based on and claiming priority to U.S. patent application entitled “Systems and Methods for Storing Items with Containers,” having Ser. No. 10/262,314, filed on Oct. 1, 2002, now U.S. Pat. No. 6,698,231, which is a Continuation-in-Part Application based on and claiming priority to U.S. patent application entitled, “Systems and Methods for Storing Items with Containers,” having Ser. No. 10/236,764, filed on Sep. 5, 2002, now U.S. Pat. No. 6,557,370, issued on May 6, 2003, which is a Continuation-in-Part Application based on and claiming priority to U.S. patent application entitled “Systems and Methods for Storing Items with Containers,” having Ser. No. 10/135,606, filed on Apr. 30, 2002, now U.S. Pat. No. 6,502,417, issued on Jan. 7, 2003, which is a Continuation-in-Part Application based on and claiming priority to U.S. patent application entitled, “Transport Container,” having Ser. No. 09/817,680, filed on Mar. 26, 2001, now U.S. Pat. No. 6,401,484, issued on Jun. 11, 2002, which is a Continuation-in-Part Application based on and claiming priority to U.S. patent application entitled, “Re-Freezable Beverage Cooler,” having Ser. No. 09/409,319, filed Sep. 30, 1999, now U.S. Pat. No. 6,216,487, issued on Apr. 17, 2001, each of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention generally relates to containers and, in particular, to systems and methods that utilize containers for storing items so that the temperature of the items may be maintained, raised and/or cooled as desired.
2. Description of the Related Art
Oftentimes, it is desirable to transport items, such as beverages, for example, in a portable container or cooler so that convenient access to the beverages is provided, such as while playing golf, attending sporting events, going to a beach, etc. Hereinbefore, such a container typically has been formed of either insulating material, for maintaining the temperature of previously chilled beverages, or a combination of insulating material and cooling material, such as blue ice, for instance, whereby the cooling material chills a beverage stored within the container and the insulating material tends to maintain the temperature of both the cooling material and the chilled beverages.
For example, U.S. Pat. No. 4,741,176, issued to Johnson, et al., discloses a beverage cooler, which includes a cylindrical freezer-pack insert to be placed into a cup, and a cover. In an embodiment of the Johnson device, the cylindrical freezer-pack insert includes removable sections to change its size, and removable plugs for putting coolant fluid into the removable sections. Since, however, the Johnson device is adapted for inserting within an individual cup, the device is limited for use in cooling one beverage at a time.
As another example, U.S. Pat. No. 4,295,345, issued to Atkinson, discloses a cooling container for canned beverages. The Atkinson device includes a reusable concave container for carrying and cooling canned beverages having a bottom section containing a plurality of cylindrical compartments, a top section containing corresponding compartments having a slow warming cooling gel in the upper end thereof, and a shoulder strap for carrying the container. While it is apparent that the Atkinson device addresses the problem of cooling multiple beverages simultaneously, it does not, however, provide for increased cooling efficiency of the beverages stored therein, as the cooling gel is stored only in the upper end of the container.
It also may be desirable to transport other items in a portable container. By way of example, various items, such as fluids, organs and/or other medical-related items, may require transport. Heretofore, these items typically have been transported within containers that are not specifically adapted for these items. This inadequacy also is prevalent in fields other than the medical industry.
Therefore, there is a need for improved coolers which address these and/or other shortcomings of the prior art.
BRIEF SUMMARY OF THE INVENTION
Briefly stated, the present invention is directed to systems and methods that utilize containers for storing and/or transporting items. In this regard, one such method includes: A method for storing items, said method comprising: providing a container, the container having: an outer shell defining an interior and having a lid, the outer shell having at least one opening for providing access to the interior, the lid being movable between an open position and a closed position, in the closed position the outer shell encasing the interior, in the open position the lid providing access to the interior, the outer shell comprising cardboard; a storage chamber formed within the interior and communicating with the opening, the storage chamber being adapted to receive at least one item; insulating material disposed within the interior between the storage chamber and the outer shell; and temperature-maintaining material disposed within the interior, the temperature-maintaining material comprising a super-absorbent.
An embodiment of a container in accordance with the invention comprises: an outer shell defining an interior and having a lid, the outer shell having at least one opening for providing access to the interior, the lid being movable between an open position and a closed position, in the closed position the outer shell encasing the interior, in the open position the lid providing access to the interior, the outer shell comprising cardboard; a storage chamber formed within the interior and communicating with the opening, the storage chamber being adapted to receive at least one item; insulating material disposed within the interior between the storage chamber and the outer shell; and temperature-maintaining material disposed within the interior, the temperature-maintaining material comprising a super-absorbent.
Another embodiment of a container in accordance with the invention comprises: an outer shell defining an interior; an insulating material disposed at least partially within the interior, the insulating material comprising soyoyl polyol; and a temperature-maintaining material disposed within the interior, the temperature-maintaining material comprising an acrylate-based super-absorbent.
Another embodiment of a container in accordance with the invention comprises an outer shell defining an interior, the outer shell defining an interior, the outer shell comprising at least one of a ceramic-containing material and an epoxy; insulating material disposed at least partially within the interior, the insulating material comprising at least one of soyoyl polyol foam, urethane foam and polystyrene foam; and a temperature maintaining material disposed within the interior, the temperature-maintaining material comprising a super-absorbent.
Other systems, methods, features, and advantages of the present invention will be or become apparent to one with skill in the art upon examination of the following drawings and detailed description. It is intended that all such additional systems, methods, features, and advantages be included within this description, be within the scope of the present invention, and be protected by the accompanying claims.
DESCRIPTION OF THE SEVERAL VIEW OF THE DRAWINGS
The invention can be better understood with reference to the following drawings. The components in the drawings are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles of the present invention. In the drawings, like reference numerals designate corresponding parts throughout the several views.
FIG. 1 is a partially cut-away perspective view of a preferred embodiment of the present invention with representative beverage containers shown in phantom lines.
FIG. 2 is a partially cut-away, perspective view of an alternative embodiment of the present invention with representative beverage containers shown in phantom lines.
FIG. 3 is a partially cut-away, perspective view of an alternative embodiment of the present invention with representative beverage containers shown in phantom lines.
FIG. 4 is a partially cut-away, perspective view of an alternative embodiment of the present invention with representative beverage containers shown in phantom lines.
FIG. 5 is a partially cut-away, perspective view of an alternative embodiment of the present invention with representative beverage containers shown in phantom lines.
FIG. 6 is a perspective view of an alternative embodiment of the present invention.
FIG. 7 is a partially-exploded, cut-away, side view of the embodiment depicted in FIG. 6 .
FIG. 8 is a perspective view of the embodiment depicted in FIGS. 6 and 7, showing the lid in an open position.
FIG. 9 is a preferred embodiment of the item retainer, which may be utilized in the container of FIGS. 6-8.
FIG. 10 is a partially-exploded, schematic view of another embodiment of a container of the present invention.
FIG. 11 is a partially-exploded, schematic view of another embodiment of a container of the present invention.
FIG. 12 is a partially-exploded, schematic, cut-away view of the embodiment of FIG. 10 .
FIG. 13 is a schematic, cut-away view of a sidewall of an alternative embodiment of a container of the present invention, showing insertion of temperature-maintaining material within a temperature-maintaining material chamber.
FIG. 14 is a schematic, cut-away view of a representative sidewall of an alternative embodiment of a container of the present invention.
FIG. 15 is a schematic, cut-away view of a representative sidewall of an alternative embodiment of a container of the present invention.
FIG. 16 is a schematic, plan view of an embodiment of the present invention in an unassembled or unfolded configuration.
FIG. 17 is a schematic, plan view of an alternative embodiment of the present invention in an unassembled or unfolded configuration.
FIG. 18 is a schematic side view representative of both the embodiment of FIG. 15, as viewed from line A—A, and the embodiment of FIG. 16, as viewed along line B—B.
FIG. 19 is a schematic side view showing a stacking arrangement of containers of the invention.
FIG. 20 is a schematic side view showing another stacking arrangement of containers of the invention.
FIG. 21 is a partially cut-away, schematic view showing assembly detail of sidewalls of an embodiment of the present invention.
FIG. 22 is a schematic, cut-away view of an alternative embodiment of the container of the present invention.
FIG. 23 is a flowchart depicting functionality of a method in accordance with the present invention.
FIG. 24 is a flowchart depicting functionality in accordance with another method of the present invention.
FIG. 25 is a flowchart depicting functionality in accordance with still another method of the present invention.
FIGS. 26-33 are graphs depicting time versus temperature involving storage of items in various embodiments of the present invention.
DETAILED DESCRIPTION
Reference will now be made in detail to the drawings, wherein like reference numerals indicate like parts throughout the several views. As shown in FIG. 1, a preferred embodiment of the cooler 100 of the present invention incorporates an outer shell 20 , preferably formed of a durable material, such as molded plastic, or other suitable materials, and which defines an interior. Preferably, one or more storage chambers 70 are provided within the interior. Storage chambers 70 preferably are adapted to receive one or more beverage containers 90 , such as conventional cans or bottles, with the cooler being constructed so as to chill the beverages containers 90 , and/or maintain the beverages of the containers 90 at a suitable chilled temperature, as described hereinafter.
Access to the storage chamber(s) 70 , such as for the insertion and/or removal of beverage containers 90 , preferably is facilitated by one or more caps 80 which removably engage the shell 20 . For example, in the preferred embodiment depicted in FIG. 1, a plurality of caps 80 are provided along a lower surface of the shell 20 , with each of the caps being constructed as a “screw-off” cap so that engagement of each of the caps with the shell is facilitated by rotating the cap relative to the shell. However, in other embodiments, engagement of the cap and shell may be facilitated by a friction fit, or other suitable means.
Preferably, storage chamber(s) 70 are defined by inner walls of a re-freezable material chamber 50 which is adapted to receive and retain a quantity of re-freezable material 30 . Preferably, the re-freezable material chamber 50 is adapted to conform to the exterior surface of a beverage container 90 and, therefore, fills the interstices formed between the various containers. Preferably, in embodiments which are adapted for receiving one beverage container within each storage chamber, each beverage container is surrounded and engaged by the inner wall of the re-freezable material chamber, i.e., on all of its sides and its top.
An insulation chamber 40 preferably is provided between the re-freezable material chamber 50 and the shell 20 . Preferably, insulation chamber 40 is filled with an efficient insulating material 60 , such as polyurethane foam or other suitable material. So configured, each beverage container inserted within a storage chamber 70 is encased by a layer of re-freezable material, as well as within a layer of insulation for maintaining the temperature of the re-freezable material at a suitable temperature.
Additionally, cooler 100 may be provided with a handle 10 so that the cooler is easily transportable. The handle may be formed of numerous suitable materials, such as plastic or leather, for instance, and may be fastened to the cooler in any conventional manner so that the weight of the cooler and any beverage container stored therein does not cause the handle to separate and detach from the shell 20 .
As depicted in FIGS. 2-5, various numbers and arrangements of storage containers 70 may be provided for storing and cooling various numbers of beverage containers 90 .
Reference will now be made to FIGS. 6-9, which depict a representative alternative embodiment of the cooler of the present invention. As shown in FIG. 6, cooler 100 includes an outer shell 110 and a lid assembly 120 . As described in greater detail hereinafter, shell 110 and lid 120 cooperate to form a protective enclosure for transporting and/or storing items placed within an interior of the container. Preferably, shell 110 is formed of a substantially rigid material that is adapted for protecting items placed within the container. Additionally, lid 120 preferably is formed, at least partially, of substantially rigid material.
As shown in FIG. 6, lid 120 incorporates a cap or door 130 that is adapted to alternately provide and deny user access to the interior of the container. In the embodiment depicted in FIG. 6, door 130 includes a recess 140 that is adapted to receive the fingers of a user so that the user may urge the door from its closed to its open position.
Referring now to FIG. 7, assembly of the container 100 will be described in greater detail. As shown in FIG. 7, a layer(s) of insulation 150 preferably is disposed within the interior of the container. In some embodiments, insulation 150 is provided adjacent an interior surface of the outer shell. An insert 160 is adapted to be received within the interior. The insert defines a storage chamber 170 , which is adapted to receive one or more items. Re-freezable material 180 preferably is disposed between an exterior surface of the insert and the layer(s) of insulation 150 . Engagement of the insert with the outer shell also may tend to retain the insulation 150 and re-freezable material 180 in position within the interior.
As shown in greater detail in FIG. 7, lid 120 includes a top 190 as well as door 130 . Top 190 is adapted to engage the outer shell so as to provide a mounting platform for the door. In some embodiments, a gasket 200 is provided between the top and the insert.
Insulation also may be provided within the door. More specifically, the door may be formed with an insulation-receiving recess 210 that is sized and shaped for receiving a layer(s) of insulation 220 . In order to maintain the insulation 220 in position relative to the door, a door insulation retainer 230 may be provided that is adapted to securely engage the door.
In order to facilitate moving the door from its closed position (depicted in FIG. 6) to its open position (depicted in FIG. 8 ), pivots 240 of the door are received within orifices 245 so as to enable pivoting of the door about the pivots. In some embodiments, a spring 250 is provided for securing the door in the closed position. In particular, spring 250 urges a latch 255 of the door toward engagement with a recess 265 . Thus, when the latch and recess are aligned, the latch forms an interference fit, thereby tending to maintain the door in its closed position.
As shown in FIG. 7, a handle assembly may be provided for facilitating transport of the container. Preferably, handle assembly 270 includes a strap portion 275 . Each end of the strap portion preferably is adapted to engage a strap guide 280 of the container, which may be formed on the lid, for example. In some embodiments, a handle may be provided at an intermediate portion of the handle assembly. In these embodiments, the handle 285 preferably is formed of a substantially rigid material and is mounted to the strap so as to provide a portion of the handle assembly that is readily suited for grasping by the hand of a user. In the embodiment depicted in FIG. 7, ends of the strap are secured to the strap guides by hook and loop material 290 although, in other embodiments, various other mechanisms for securing the strap to the container may be utilized.
As shown in FIGS. 8 and 9, the container 100 may be configured with an item-receiving retainer 300 . Item-receiving retainer 300 defines one or more item-receiving cavities 310 that may be specifically sized and shaped to conform to an exterior surface of an item to be received therein. For example, the item-receiving cavities 310 depicted in FIG. 8 are each specifically configured to receive a test tube or vile 320 . Preferably, an exterior surface of the item-receiving retainer is adapted to engage an interior surface of the insert and is configured so that cooperation of the lid and the outer shell maintains the item-receiving retainer within the storage chamber.
In addition to substantially maintaining relative positions of items stored within the container, the material of the item-receiving retainer may be suitably selected so as to provide shock absorbing. In these embodiments, such as those embodiments formed of a foamed material, for example, the item-receiving retainer may reduce the tendency of an item to break within the container.
In some embodiments, various configurations of item-receiving retainers may be provided. More specifically, multiple item-receiving retainers may be provide with a given container, with each item-receiving retainer being adapted to receive various configurations of items for storage within the container. So provided, the container may be adapted so as to specifically accommodate transporting and cooling of particularly sized and shaped items.
Another embodiment of a container in accordance with the present invention is depicted schematically in FIG. 10 . As shown in FIG. 10, container 100 includes an outer shell 321 that is sized and shaped to receive an insert 322 . When insert 322 is received by shell 321 , a gap 323 is formed. Insulation (not shown) can be placed in gap 323 between the outer shell and the insert.
Container 100 of FIG. 10 also includes a storage chamber 324 that is defined by an inner shell 325 . Inner shell 325 is received by insert 322 so that a second gap 326 is formed. Gap 326 is adapted to receive temperature-maintaining material (not shown) so that the temperature-maintaining material is located about the sides and/or bottom of an item placed within the storage chamber.
Access to the storage chamber is provided by a removable lid 327 . Lid 327 can optionally house insulation and/or temperature-maintaining material. In the embodiment of FIG. 10, the lid includes a nozzle 328 that allows liquid to be drawn from the storage chamber when in an open position. So configured, the container can be used to store various types of items, such as liquids (which can be accessed via the nozzle) and beverage cans (which can be accessed by opening the lid).
Note, the outer shell, insert and inner shell can be held in an assembled configuration by various techniques. For instance, when a foam-type insulation is used, the foam can be injected into gap 323 so that a portion of the foam contacts the inner shell. This enables the insulation to perform as an adhesive for bonding the inner shell to the outer shell and insert.
Reference will now be made to FIGS. 11 and 12, which depict another embodiment of a container 100 in accordance with the present invention. As shown in FIG. 11, container 100 includes multiple side surfaces that extend upwardly from a base (shown more clearly in FIG. 12 ). In particular, container 100 includes sidewalls 330 , 332 , 334 and 336 , each of which extends upwardly from base 340 . The sidewalls and the base define an interior storage chamber 342 that can be enclosed when a lid 344 , e.g., a removable lid, is used to engage the sidewalls.
As shown in FIG. 12, the base, sidewalls and lid are shaped to interlock with each other so that temperature-maintaining material 350 surrounds the storage chamber. More specifically, each of the base, sidewalls and lid includes a temperature-maintaining material chamber, e.g., chambers 352 , 354 , 356 and 358 , that retains temperature-maintaining material. By way of example, the temperature-maintaining material can be a refreezable material.
Preferably, each of the base, sidewalls and lid, in addition to incorporating a temperature-maintaining material chamber and associated temperature-maintaining material, includes an insulation chamber ( 360 , 362 , 364 , 366 ) with insulation 370 arranged therein. Note, the various chambers can be defined by a substantially rigid material that also can be used to form the exterior shell 372 of the container.
Attachment of the base, sidewalls and lid to each other can be accomplished in numerous manners. By way of example, one or more of the sidewalls could be hingedly attached to the base. Hinged attachment can be facilitated by hinge mechanisms (not shown) or by a portion of the material of the exterior shell (not shown), for example, that is adapted to flex or bend to accommodate movement of the sidewall with respect to the base. Note, several different attachment configurations will be described later.
As shown in FIG. 13, a container of the invention can include one or more temperature-maintaining material chambers that are adapted to permit removal of the temperature-maintaining material. As shown in FIG. 13, this can be accommodated by a sidewall 374 including an opening 376 . The opening 376 is sized and shaped so that the temperature-maintaining material 350 can be removed, such as for freezing, and then re-inserted into the chamber through the opening for use. Note, depending upon the type of temperature-maintaining method used, the material may be packaged so that it does not break apart.
Various insulation and temperature-maintaining materials can be used. For example, polyurethane foam can be used as the insulation, and a gel-forming polymer such as polyacrylate/polyalcohol copolymers can be used as the temperature-maintaining material. Clearly, various other materials could be used depending upon characteristics such as the intended operating temperature range, desired weight of the container, and stability/compatibility within the item(s) stored, among others. The selection of the particular materials is considered within the knowledge of one of skill in the art.
Clearly, various other arrangements can be used for providing the outer shell, insulation, and temperature-maintaining material so that an item placed within the storage chamber of the container can be protected and/or have its temperature maintained. Cut-away views of additional configurations are depicted in FIGS. 14 and 15.
As shown in FIG. 14, insulation 370 and temperature-maintaining material 350 are arranged between an outer wall 380 and an inner wall 382 of a container. Of particular interest, a gas chamber 384 is provided between the insulation and temperature-maintaining material. The gas chamber is adapted to receive gas 386 , such as an inert gas, or other gas that is considered suitable for increasing the insulating properties of the container. Depending upon the particular properties of the insulation and temperature-maintaining material, these materials may be adequate for defining the gas chamber and maintaining the gas therebetween.
Another embodiment that includes a gas chamber is depicted in FIG. 15 . As shown in FIG. 15, the gas chamber 388 , which is located between the insulation 370 and the temperature-maintaining material 350 , is defined by an inner wall 390 of the insulation chamber 392 and an outer wall 394 of the temperature-maintaining material chamber 396 . Thus, this embodiment uses additional structural elements for maintaining the location of the gas.
As shown in FIG. 16, the base 400 and sidewalls 402 , 404 , 406 and 408 of a container 100 are depicted in a disassembled or unfolded configuration. In this configuration, the sidewalls and base exhibit a generally flattened structure. Note, the lid 410 is not attached to the base-sidewall assembly 412 . Note, hinge mechanisms 414 , 416 , 418 and 420 attach the sidewalls to the base. The embodiment of FIG. 16 also includes a hanging component 422 , which in this case is a ring that can be used for hanging the container during storage, for example. For instance, the ring could attach the container to a hook suspended within a freezer.
FIG. 17 also depicts an embodiment of a storage container 100 in its disassembled or unfolded configuration. In particular, sidewalls 430 , 432 , 434 and 436 are attached to base 400 . Compared to the embodiment of FIG. 16, however, the embodiment of FIG. 17 includes a lid 442 that is hingedly attached to the unfolded structure. In particular, the lid is attached to sidewall 436 .
In those embodiments that are configured to unfold into a generally flattened structure, it is shown that the space taken up by the structure is somewhat less than that used when the sidewalls and lid are assembled, such as depicted in FIG. 11 . This unfolded configuration is considered advantageous, in that less volume is required within which to place the container. By way of example, when multiple containers are to be placed within a freezer so that the temperature-maintaining material can be frozen, more containers can be placed within the freezer in the unfolded configuration than would otherwise be able to be placed in the freezer when the containers are assembled.
As shown in the schematic side view of FIG. 18, the lid 450 , base 452 , and/or one or more of the sidewalls 454 of a container 100 can include protrusions 456 that extend outwardly from an exterior surface 458 of the container 100 . These protrusions can be used to form air flow channels 460 between the containers and the surface 462 upon which it is placed. Clearly, the number and arrangement of protrusions can vary among embodiments. Preferably, the protrusions are arranged in rows that are spaced parallel from each other.
In FIG. 19, two containers ( 100 A, 100 B) are shown stacked one upon the other. In this arrangement, air (depicted by arrows) is able to flow between the containers, as well as between the lowermost container and surface 462 .
As shown in FIG. 20, embodiments of containers 100 also can incorporate recesses 470 , which are complimentary shaped with respect to the protrusions 456 . Thus, the containers ( 100 C, 100 D) can nest within each other. Stacking the containers in a nested configuration enables the containers to take up less space, such as during shipping when they are not in use.
As depicted in FIG. 21, the sidewalls can incorporate mating components that are adapted to mate with each other to form a more rigid assembly and/or complete seal about the storage chamber. As shown in FIG. 21, sidewall 480 includes a protruding member 482 , while sidewall 484 includes a complimentary shaped recess 486 . The protruding member is received by the recess as the sidewalls are assembled, such as by moving sidewall 484 in the direction indicated by the arrow receiving the protruding member. In some embodiments, the protruding member and recess can include surfaces for forming an interference fit when the protruding member is inserted within the recess. Thus, by inserting the protruding member within the recess and forming the interference fit, a tendency for the sidewalls to separate from each other during use can be reduced.
Another embodiment of a storage container 100 is depicted schematically in FIG. 22 . As shown in FIG. 22, storage container 100 defines an interior 488 within which items (not shown) can be placed. Temperature-maintaining material can be placed at various locations of the storage container. In the embodiment depicted in FIG. 22, temperature-maintaining material 490 is located at a bottom of the container, temperature-maintaining material 491 is located at the top of the container, temperature-maintaining material 492 is located at a first side of the container and temperature-maintaining 493 is located at a second side of the container. Also depicted in FIG. 22 is temperature-maintaining material 494 that is placed within the interior 488 and which, preferably, is not secured to the container. In particular, temperature-maintaining material 494 is stored within a container 495 that can be a bag or other structure that substantially retains the temperature-maintaining material. Typically, the container 495 is enabled to be moved about the interior although, in some embodiments, the container may be adapted to be maintained in a particular position within the interior.
Clearly, in other embodiments, temperature-maintaining material can be placed in one or more of the positions identified in FIG. 22 . Note, the shape, size and/or thickness of the temperature-maintaining material can differ between embodiments.
Various materials can be used for forming embodiments of containers in accordance with the invention. By way of example, insulation that is incorporated into and/or forms the walls, top and/or bottom of a container can be formed, at least partially, of urethane and/or soyoyl polyol. Of particular interest is the use of soyoyl polyol, as this material is biodegradable. Thus, biodegradable containers that are suitable for one-time use can be provided. In some of these embodiments, an outer shell can be used. For instance, a biodegradable material such as cardboard could be used as an outer shell that protects the insulation.
Typically, embodiments of containers in accordance with the invention include multiple material layers. Various materials and/or combinations of materials can be used to form each of the layers, with each of the layers performing one or more of the following functions: providing structural support for the container, insulating the container and protecting the container.
With respect to supporting the container structurally, various materials can be used. By way of example, soyoyl polyol foam, urethane foam, polystyrene and cardboard are considered useful as these materials are relatively light in weight, are relatively rigid and suited for the application of coatings (described later). Additionally, soyoyl polyol, urethane and polystyrene offer improved insulating properties and, thus, can enhance the insulative characteristics of the containers in which they are incorporated.
Various materials can be used to insulate the containers. In some embodiments, insulating properties of the containers are enhanced by one or more material layers in addition to the material(s), used to provide structural support for the container (described before). For example, one or more layers of soyoyl polyol, urethane foam and/or polystyrene can be used. Additionally or alternatively, other materials, such as those applied as coatings, can be used. By way of example, coatings that incorporate ceramics, such as SUPERTHERM™ manufactured by Superior Products International of Shawnee, Kans. can be used. Materials such as SUPERTHERM™ can be applied to the interior and/or exterior of the containers. Specifically, the material can be applied to the material that provides structural support to the container. Additionally or alternatively, such a material can be applied to another material that is used to insulate the container.
Various materials also can be used to form an outer shell of a container. Such an outer shell can be used to protect the inner material layers of the container and, thereby, improves the durability of the container. This can allow the container to be used more than once. Various durable materials such as ureas, e.g., urea polymers and/or copolymers, cardboard, coatings that incorporate ceramics, such as SUPERTHERM™, epoxies, such as EPOXOTHERM™, and enamels, such polyurethane enamels, e.g., ENAMOGRIP™, can be used. Clearly, various other materials can be used to form an outer shell. Note, the material forming the outer shell also can provide enhancements in insulating characteristics of the container.
In some embodiments, the material used to form the insulation of a container also can be used to form an outer shell. In particular, various materials that form outer skins or hardened layers can be used. By way of example, ureas, e.g., urea polymers and/or copolymers, can be used to form insulated structures that incorporate hardened outer surfaces. Also, materials configured as foams can be used to form insulated structures with hardened outer surfaces. These hardened outer surfaces or skins typically form as the material contacts the form into which the material is placed.
Various types of temperature-maintaining materials also can be used. By way of example, acrylate-based superabsorbents can be used. For instance, polacrylate/polyalcohol polymers and/or copolymers, such as AP85-38 manufactured by Emerging Technologies, Inc. of Greensboro, N.C. Norsocryl D-60, LiquiBlock, AT-03S, LiquiBlock 88, LiquiBlock 75, LiquiBlock 44-0C, among others can be used.
As described before, temperature-maintaining material can be incorporated into a container in various manners, such as by disposing the material between adjacent walls of the container and/or providing the temperature-maintaining materials in a package that can be placed within the interior of the container. Note, in use, the polymers/copolymers are allowed to absorb liquid, such as water, and the temperature of the temperature-maintaining materials can be adjusted as desired.
As mentioned before, containers of the invention can be used for storing items, while maintaining, increasing or decreasing the temperature of the items stored in the containers. The various functions associated with the containers of the invention will now be described with respect to several flowcharts. In this regard, FIG. 23 is a flowchart depicting a method in accordance with the invention.
As shown in FIG. 23, the method may be construed as beginning at block 502 , where an embodiment of a container of the invention is provided. In block 504 , an item is placed in the container. In block 506 , the container with the item inserted therein can be transported.
Various items can be stored and/or transported within containers of the invention. For instance, food products, beverages, pharmaceutical products, and biological matter, such as plants, tissues, organs, and blood can be stored and/or transported within the containers. Clearly, various other items could be used with embodiments of the invention, particularly those items that may require their respective temperatures to be maintained, reduced and/or increased for a period of time, such as during transport.
As depicted in FIG. 24, another method in accordance with the invention may be construed beginning at block 522 , where a container is provided. In block 524 , the temperature-maintaining material of the container is adjusted to exhibit a selected temperature. By way of example, when the temperature-maintaining material is a refreezable material, the material can be frozen. In block 526 , an item is placed within the container and, thereafter (block 528 ), the container with the item stored therein is transported. In block 530 , the item is removed from the container, such as by accessing the storage chamber and removing the item from the storage chamber. Based upon the configuration of the container and the time the item has been stored within the container, the item preferably exhibits desired temperature characteristics.
Another method of the invention is depicted in FIG. 25 . As shown in FIG. 25, the method may be construed as beginning at block 540 , where a container in accordance with the invention is provided in a disassembled or unfolded configuration. In block 542 , the temperature of the temperature-maintaining material of the container is adjusted. In block 544 , the container is assembled and, such as depicted in block 548 , an item is placed within a storage chamber of the assembled container. In block 550 , the container with the item inserted therein is transported to an intended destination and, in block 552 , the item is removed from the container.
Several prototype containers were constructed in accordance with the invention and were subjected to testing. Results from the tests conducted will now be described.
EXAMPLE 1
In this example, a container was formed as a 6″×6″×6″ box with 1.5″ thick polyurethane insulation. The insulating material surrounded temperature-maintaining material in the form of a gel-forming polymer. Approximately 24 ounces of gel-forming polymer was located at the base of the container, 16 ounces of the polymer was located at the lid or top of the container. The item placed in the storage chamber was 0.74 lbs. of steak, which was placed into the storage chamber after the steak and the container were allowed to cool to a temperature of 4.9° F. The container with the item stored therein was then placed in an ambient environment which was approximately 75° F. The results of this example are depicted in FIG. 26 .
EXAMPLE 2
In this example, another container (8.5″×8.5″×8.25″) was formed with 1.5″ polyurethane insulation. Twenty-four ounces of gel-forming polymer was located at the base, 16 ounces of gel-forming polymer was located at each of the sidewalls, 16 ounces of gel-forming polymer was located at the lid, and 4 ounces of gel-forming polymer was located at each of the 4 corners of the container. Ground beef, (1.87 lbs.) was inserted into the storage chamber, which was then cooled to 35.8° F. After cooling, the container was placed in an ambient environment of approximately 75° F. As depicted in FIG. 27, the ground beef was maintained at or below 40° F. for approximately 127 hours.
EXAMPLE 3
In this example, a cylindrical container (see FIG. 10) was formed with 6 oz. of foam-type insulation. Five ounces of gel-forming polymer was located in a gap formed between the inner shell and the insert. The outer shell, insert and inner shell were formed of plastic.
The container was placed in a freezer, which was maintained at 1.5° F. Two cans of Bud Light® were placed in a refrigerator, which was maintained at 33.1° F. After removing the container from the freezer, the cans were placed inside the container. The container with the stored can were then placed in a room with an ambient temperature of 75.5° F. Results are depicted in FIG. 28 .
EXAMPLE 4
The container used in example 3 was used again in this example. This time, the container was placed in a freezer, which was maintained at 3.6° F. Two cans of Bud Light® were placed in a refrigerator, which was maintained at 33.7° F. After removing the container from the freezer, the cans were placed inside the container, which was placed in a room with an ambient temperature of 75.5° F. Results are depicted in FIG. 29 .
EXAMPLE 5
The container used in examples 3 and 4 was used again in this example. Two cans of Diet Coke® were inserted in the container with the container exhibiting a temperature of 4.3° F. at start, with each of the cans exhibiting a start temperature of 37.5° F. The container with the stored cans was then placed in an ambient environment of 70° F.
As depicted in FIG. 30, the beverages were maintained at temperatures of less than 37° F. for approximately two hours. Due to the large number of data points, the curve shown represents a moving average of the data point values. Note, the temperature of the beverages dropped for approximately 30 minutes to 34° F. and stabilized for approximately 90 minutes. The temperature began to rise and reached approximately 37° F. at approximately 150 minutes, then continued to rise to 40° F. at approximately 190 minutes.
EXAMPLE 6
In this example, a container in a box-type configuration was used. Approximate dimensions of the container are 1.25′×1.25′×1.25′. Ten pouches of gel-forming polymer, weighing a total of 7.8 lbs., were used. The polymer was cooled to approximately 4° F. and inserted into the storage chamber of the container. In particular, the bags were placed on the bottom, sides, corners and top of the storage chamber. Hamburger meat (3″×8″×4″) weighing approximately 7.8 lbs. and exhibiting an initial temperature of 23.4° F. was then placed in the container.
FIG. 31 shows the temperature profile which indicates that the meat climbed to a temperature of 32° F. within one hour. The temperature at the gel/meat interface remained constant at 34° F. for approximately 110 hours, then began a very slow increase to 39° F. over the next 50 hours. After 166 hours, the container was opened and the meat was removed. Approximately one inch of the meat against the gel packs appeared brown in color, while the center of the meat was natural red in color.
EXAMPLE 7
In this example, the container of example 6 was used to determine the viability of antifreeze/gel-forming polymer-based refreezable material to maintain the temperature of items. In particular, one pint vanilla Haggendas® ice cream was placed in the container.
A 75:25 mixture of antifreeze (ethylene glycol) and water was mixed with 2.5 teaspoons of a dry polymer gel. Approximately 2.03 lbs. of the mixture was then dispensed into 6 Ziplock® bags and frozen in liquid nitrogen. The frozen bags and the ice cream, which had an initial temperature of 11° F., were placed in the storage chamber. The container was maintained at room temperature (72-74° F.) for 68 hours. The results are depicted in the graph of FIGS. 31 and 32.
The foregoing description has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Modifications or variations are possible in light of the above teachings. The embodiment or embodiments discussed, however, were chosen and described to provide the best illustration of the principles of the invention and its practical application to thereby enable one of ordinary skill in the art to utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. All such modifications and variations, are within the scope of the invention as determined by the appended claims when interpreted in accordance with the breadth to which they are fairly and legally entitled.
|
Containers are provided. A representative container comprises: an outer shell defining an interior and having a lid, the outer shell having at least one opening for providing access to the interior, the lid being movable between an open position and a closed position, in the closed position the outer shell encasing the interior, in the open position the lid providing access to the interior, the outer shell comprising cardboard; a storage chamber formed within the interior and communicating with the opening, the storage chamber being adapted to receive at least one item; insulating material disposed within the interior between the storage chamber and the outer shell; and temperature-maintaining material disposed within the interior, the temperature-maintaining material comprising a super-absorbent.
| 5
|
TECHNICAL FIELD
[0001] The present invention relates to a field of preparation of flame retardant masterbatch material, and more specifically, relates to an efficient halogen-free flame retardant masterbatch for polypropylene, a preparation method and use thereof.
BACKGROUND
[0002] Flame retardant masterbatch, known as fire retardant masterbatch and fireproof masterbatch, is also known as “concentrate” abroad which means a concentrate of the flame retardant. The flame retardant masterbatch has been generated for a few decades, which firstly is mainly to solve the problem of uneven dispersion and severe dust pollution in the process of using flame retardant powder. After several years of development, by considerable applications of scientific means and new technologies, people investigating flame retardant masterbatch are not restricted to general problems such as dispersion and prevention of pollution. It has been formed as an independent discipline and developed into an independent industry. By plenty of technical research and application, the flame retardant masterbatch has become a high-tech product or a product of high-technology.
[0003] The existing flame retardant technology provides polyolefin with flame retardancy by means of direct addition of flame retardant. Nowadays, the common halogen-free flame retardant mainly includes inorganic flame retardant and phosphorus-nitrogen type intumescent flame retardant. However, due to the poor consistency with polyolefin resin and the low flame retardant efficiency, inorganic flame retardant presents a certain flame retardant effect only when a large amount of filling. This will seriously damage the mechanical property and processing property of polyolefin. In order to overcome the deficiency of inorganic type flame retardant in low flame retardant efficiency, a phosphorus-nitrogen type halogen-free flame retardant with high flame retardant efficiency is utilized generally in polyolefin resin. When heated, such flame retardant can form a layer of compact carbon foam layer on the surface, which can isolate heat as well as oxygen, inhibit smoke and prevent molten drop, and also provides good flame retardancy. In addition, such flame retardant is halogen-free and low-toxic when it is burnt, and no corrosive gas produces. It belongs to an environmental friendly type flame retardant, and therefore, has developed very fast.
[0004] Since these phosphorus-nitrogen type flame retardants are generally formed as powder with fineness thereof generally being 400 meshes or more, a large amount of dust pollution can be easily generated during weighing, mixing and pelletizing. This would worsen the production environment, do great harm to human health, and make wear on processing equipment at a certain extent. Moreover, phosphorus-nitrogen type flame retardants have problems of relatively strong hygroscopicity, low thermal stability and poor consistency with polyolefin resin, which result in that the flame retardant materials are sensitive to moisture, easy to be foamed and easy to be degraded, result in the weakness such as poor dispersibility of flame retardant in the resin and a certain extent of damage to processing properties and mechanical properties of the materials.
SUMMARY OF THE INVENTION
[0005] According to the deficiency of existing flame retardant masterbatch material, the present invention provides an efficient halogen-free flame retardant masterbatch for polypropylene.
[0006] Another object of the present invention is to provide a preparation method and use of the above-mentioned efficient halogen-free flame retardant masterbatch for polypropylene.
[0007] The present invention enables a prepared halogen-free flame retardant masterbatch to have advantages such as dust-free, easy to disperse, high flame retardant efficiency, low cost and strong processing adaptability by means of selecting and utilizing an environmental friendly, efficient and halogen-free flame retardant and a continuous production process of high speed stirring, crushing and extruding, and therefore dust pollution may be reduced and the production environment may be improved.
[0008] The technical objects of the present invention can be realized by following technical solutions:
[0009] The present invention provides an efficient halogen-free flame retardant masterbatch for polypropylene, said masterbatch comprising following raw materials in percentage by weight:
ammonium polyphosphate 30˜40% pentaerythritol phosphate 10˜20% melamine 15˜25% bisphenol A bis(diphenyl phosphate) 5˜15% microporous polypropylene 10˜30% pentaerythritol stearate 0.1˜1% antioxidant 1010 0.1˜0.5% antioxidant 168 0.1˜0.5%;
[0018] said microporous polypropylene is particles with a size of 3˜5 mm, cell size on a surface of the particle is 10˜100 μm, and cell density is more than 10 5 cells/cm 3 .
[0019] In particular, microporous polypropylene serves as an adsorbent for a liquid flame retardant (bisphenol A bis(diphenyl phosphate)) and as a carrier for such flame retardant masterbatch. A main function of the microporous polypropylene is to adsorb bisphenol A bis(diphenyl phosphate) into micropores and to combine phosphorus-nitrogen type halogen-free flame retardant powders together, in order to achieve a granular halogen-free flame retardant masterbatch. Ammonium polyphosphate, pentaerythritol phosphate and melamine respectively serve as acid resource, carbon resource and gas resource, constituting an intumescent type flame retardant system, and they cooperate with each other to achieve the object of efficient flame retardancy. As an efficient phosphorus flame retardant, bisphenol A bis(diphenyl phosphate) can provide phosphorus-nitrogen synergistic flame retardant effect with melamine. As a lubricant with low melting point, pentaerythritol stearate, on one hand, can reduce wear between material and equipment; on the other hand, pentaerythritol stearate can enhance a dispersion effect of halogen-free flame retardant on the carrier. Function of antioxidant 1010 and antioxidant 168 is to improve the thermal processing stability and the ability of anti-thermo-oxidative aging of the material.
[0020] Preferably, said masterbatch comprises following raw materials in percentage by weight:
ammonium polyphosphate 32˜38% pentaerythritol phosphate 13˜17% melamine 18˜22% bisphenol A bis(diphenyl phosphate) 8˜10% microporous polypropylene 15˜25% pentaerythritol stearate 0.5˜1% antioxidant 1010 0.2˜0.5% antioxidant 168 0.2˜0.5%.
[0029] Preferably, said microporous polypropylene is prepared by following preparation method:
[0030] stirring a mixture of high melt-strength co-polypropylene, foaming agent, antioxidant 1010, antioxidant 168 and calcium stearate; melt-blending and extruding the mixture; after pelletizing and drying, said microporous polypropylene can be obtained.
[0031] More preferably, said microporous polypropylene comprises following raw materials in percentage by weight:
high melt-strength co-polypropylene 80˜90% foaming agent 5˜12% antioxidant 1010 0.1˜0.5% antioxidant 168 0.1˜0.5% calcium stearate 0.5˜1%.
[0037] Preferably, said ammonium polyphosphate has a mean particle size of 8˜10 μm.
[0038] More preferably, said ammonium polyphosphate is HT-208 purchased from Jinan Taixing Fine Chemicals Co. Ltd or APP high molecular ammonium polyphosphate (n>1000) from Shandong Shian Chemical Co., Ltd.
[0039] Preferably, said pentaerythritol phosphate has a purity of more than 99%, a moisture content of less than 0.2%, and a mean particle size of 5˜8 μm.
[0040] More preferably, said pentaerythritol phosphate is pentaerythritol phosphate (PEPA) purchased from Jiangsu Victory Chemical Co., Ltd.
[0041] Preferably, said melamine has a purity of more than 99%.
[0042] More preferably, said melamine is high-class product melamine purchased from Chengdu Yulong Chemical Co., Ltd or Tianfu brand melamine (with a purity of more than 99.8%) from Sichuan Chemical Company Limited.
[0043] Preferably, said bisphenol A bis(diphenyl phosphate) has a viscosity of 1800˜2600 mPa·s at 40° C. and a color of less than 80.
[0044] More preferably, said bisphenol A bis(diphenyl phosphate) is WSFR-BDP purchased from Zhejiang Wansheng Co., Ltd.
[0045] The present invention also provides a preparation method of said efficient halogen-free flame retardant masterbatch for polypropylene, including following steps:
[0046] S1. preparation of microporous polypropylene: stirring a mixture of high melt-strength co-polypropylene, foaming agent, antioxidant 1010, antioxidant 168 and calcium stearate; melt-blending and extruding the mixture; after pelletizing and drying, said microporous polypropylene can be obtained;
[0047] S2. mixing the microporous polypropylene obtained from S1 and bisphenol A bis(diphenyl phosphate) evenly, then let it stand for later use;
[0048] S3. melt-blending pentaerythritol stearate, antioxidant 1010, antioxidant 168 and the mixture obtained from S2, then adding ammonium polyphosphate, pentaerythritol phosphate and melamine for blending, after internal mixing, extruding and pelletizing, said efficient halogen-free flame retardant masterbatch for polypropylene can be obtained.
[0049] Preferably, the microporous polypropylene prepared from said S1 is particles with a size of 3˜5 mm, cell size on a surface of the particle is 10˜100 and cell density is more than 10 5 cells/cm 3 .
[0050] Preferably, an extruder has an aspect ratio of 20˜40; barrel temperature of the extruder is 150˜180° C.; and rotating speed of a main engine of the extruder is 300˜700 r/min.
[0051] The efficient halogen-free flame retardant masterbatch for polypropylene prepared by the invention has several characteristics of easy dispersing, easy processing, high flame retardant efficiency and low production cost, and it can be widely used in the production of flame retardant polypropylene materials for extrusion, injection molding and membrane blowing.
[0052] Compared with the prior art, the present invention has following beneficial effects:
[0053] The notable effect of the present invention is that using self-prepared microporous polypropylene to serve as both an adsorbent and a carrier of masterbatch, by adsorbing all liquid flame retardant (bisphenol A bis(diphenyl phosphate)) into the micropores, problems caused by the direct addition of liquid flame retardant are thus avoided, such as difficulty in processing, uneven dispersion and easy wearing.
[0054] In the present invention, a synergistic flame retardant effect is generated by an efficient phosphorus-nitrogen halogen-free intumescent flame retardant system which is formed by optimized ammonium polyphosphate, pentaerythritol phosphate and melamine, and thereby the addition amount of flame retardant can be reduced and the influence of flame retardant on the physical and mechanical properties of materials can be reduced.
[0055] In the present invention, adopting liquid efficient flame retardant (bisphenol A bis(diphenyl phosphate)) to be compounded with solid intumescent flame retardant system, on one hand, can generate synergistic flame retardant effect and reduce the addition amount of flame retardant, and on the other hand, can effectively avoid the difficulty of carrier covering caused by additional flame retardant powder, thereby improving the processing efficiency.
[0056] Since the efficient halogen-free flame retardant masterbatch for polypropylene prepared by the invention is granular, and is basically in accordance with a particle size of a basic resin, the materials can therefore be blended evenly so that it can prevent a situation of unstable quality of materials caused by the uneven blending of powder and pellets.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0057] The present invention will be specifically described below by way of embodiments. It is necessary to indicate that the embodiments are only used to further described the present invention and they could not be interpreted as limitation of the scope of protection of the invention. Those skilled in the art can make some unessential improvements and adjustments according to above contents of the present invention.
[0058] Unless otherwise specified, reagents, methods and equipments used in the present invention are conventional reagents, methods and equipments in the present technical field.
[0059] The microporous polypropylene described in the embodiments and the comparative examples below is prepared by following steps:
[0060] Matching materials in percentage by weight as below: 89% of high melt-strength co-polypropylene (PP-WFW4, Mitsubishi Chemical Corporation, Japan), 10% of foaming agent (MJ Addifoam 43™, Beijing Plaschem Trading Co., Ltd), 0.2% of antioxidant (SONOX 1010, Shandong Linyi Sunny Wealth Chemical Co., Ltd), 0.3% of antioxidant (SONOX 168, Shandong Linyi Sunny Wealth Chemical Co., Ltd) and 0.5% of lubricant (calcium stearate 3818, BELIKE Chemical Co., Ltd). After above-mentioned materials are weighed, they are mixed evenly and added into a main feed hopper of a single screw extruder with an aspect ratio of 40:1. Temperature of each section from the hopper to a die-head in the single screw extruder is respectively set as 180° C., 190° C., 200° C., 190° C., 190° C., 190° C., 200° C., 210° C. and 220° C. The screw speed of a main engine is 450 r/min and the frequency of a feed screw of the main feed hopper is 13 Hz. The materials are melt-blended and extruded. A strip from a die of the single screw extruder is under water ring pelletizing and drying, and microporous polypropylene is then obtained.
Embodiment 1
[0061] Following materials were matched in percentage by weight as below:
[0062] 32% of ammonium polyphosphate (HT-208, Jinan Taixing Fine Chemicals Co. Ltd), 17% of pentaerythritol phosphate (produced by Jiangsu Victory Chemical Co., Ltd), 22% of melamine (high-class product, produced by Chengdu Yulong Chemical Co., Ltd), 8% of bisphenol A bis(diphenyl phosphate) (WSFR-BDP, Zhejiang Wansheng Co., Ltd), 19.8% of microporous polypropylene (self-prepared, the preparation method is described above), 0.5% of pentaerythritol stearate (GLYCOLUBE® P(ETS), American Lonza Chemical Inc.), 0.5% of antioxidant 1010 (SONOX 1010, Shandong Linyi Sunny Wealth Chemical Co., Ltd) and 0.2% of antioxidant 168 (SONOX 168, Shandong Linyi Sunny Wealth Chemical Co., Ltd).
[0063] Each component in above-described formula was weighed accurately. Bisphenol A bis(diphenyl phosphate) was mixed with microporous polypropylene into uniformity and then let the mixture stand for 5 hours. Then such mixture, together with pentaerythritol stearate, antioxidant 1010 and antioxidant 168, were added into a pressurized inverse internal mixer. Temperature in an internal mixer chamber was controlled at 160° C., the rotor speed was 50 r/min and the time of internal mixing was 6 minutes. After the materials melted, ammonium polyphosphate, pentaerythritol phosphate and melamine powder were added into the internal mixer by twice with 4 minutes between each addition. All materials were internal mixed for another 8 minutes after they were all added into the internal mixer.
[0064] Above-described plastic block after being internal mixed was transported to a hopper of a single screw extruder by a conveyer belt, and was chopped into pieces by a cutter in the hopper. Temperature of each section of a barrel was controlled at 170° C. and the rotor speed of a main engine was 500 r/min. After melting, being mixed and being extruded by the single screw, and then being wind-cooled, grinded surface and pelletized, the efficient halogen-free flame retardant masterbatch for polypropylene was made.
Embodiment 2
[0065] Following materials were matched in percentage by weight as below:
[0066] 35.7% of ammonium polyphosphate (HT-208, Jinan Taixing Fine Chemicals Co. Ltd), 15% of pentaerythritol phosphate (produced by Jiangsu Victory Chemical Co., Ltd), 20% of melamine (Sichuan Chemical Co., Ltd), 8% of bisphenol A bis(diphenyl phosphate) (WSFR-BDP, Zhejiang Wansheng Co., Ltd), 20% of microporous polypropylene (self-prepared, the preparation method is described above), 0.6% of pentaerythritol stearate (GLYCOLUBE® P(ETS), American Lonza Chemical Inc.), 0.4% of antioxidant 1010 (SONOX 1010, Shandong Linyi Sunny Wealth Chemical Co., Ltd) and 0.3% of antioxidant 168 (SONOX 168, Shandong Linyi Sunny Wealth Chemical Co., Ltd).
[0067] Each component in above-described formula was weighed accurately. Bisphenol A bis(diphenyl phosphate) was mixed with microporous polypropylene into uniformity and then let the mixture stand for 5 hours. Then such mixture, together with pentaerythritol stearate, antioxidant 1010 and antioxidant 168, were added into the pressurized inverse internal mixer. The temperature in the internal mixer chamber was controlled at 160° C., the rotor speed was 50 r/min and the time of internal mixing was 6 minutes. After the materials melted, ammonium polyphosphate, pentaerythritol phosphate and melamine powder were added into the internal mixer by twice with 4 minutes between each addition. All materials were internal mixed for another 8 minutes after they were all added into the internal mixer.
[0068] Above-described plastic block after being internal mixed was transported to the hopper of the single screw extruder by the conveyer belt, and was chopped into pieces by the cutter in the hopper. Temperature of each section of the barrel was controlled at 170° C. and the rotor speed of the main engine was 500 r/min. After melting, being mixed and being extruded by the single screw, and then being wind-cooled, grinded surface and pelletized, the efficient halogen-free flame retardant masterbatch for polypropylene was made.
Embodiment 3
[0069] Following materials were matched in percentage by weight as below:
[0070] 38% of ammonium polyphosphate (HT-208, Jinan Taixing Fine Chemicals Co. Ltd), 16.5% of pentaerythritol phosphate (produced by Jiangsu Victory Chemical Co., Ltd), 20% of melamine (high-class product, produced by Chengdu Yulong Chemical Co., Ltd), 9% of bisphenol A bis(diphenyl phosphate) (WSFR-BDP, Zhejiang Wansheng Co., Ltd), 15% of microporous polypropylene (self-prepared, the preparation method is described above), 0.8% of pentaerythritol stearate (GLYCOLUBE® P(ETS), American Lonza Chemical Inc.), 0.3% of antioxidant 1010 (SONOX 1010, Shandong Linyi Sunny Wealth Chemical Co., Ltd) and 0.4% of antioxidant 168 (SONOX 168, Shandong Linyi Sunny Wealth Chemical Co., Ltd).
[0071] Each component in above-described formula was weighed accurately. Bisphenol A bis(diphenyl phosphate) was mixed with microporous polypropylene into uniformity and then let the mixture stand for 6 hours. Then such mixture, together with pentaerythritol stearate, antioxidant 1010 and antioxidant 168, were added into the pressurized inverse internal mixer. The temperature in the internal mixer chamber was controlled at 160° C., the rotor speed was 50 r/min and the time of internal mixing was 6 minutes. After the materials melted, ammonium polyphosphate, pentaerythritol phosphate and melamine powder were added into the internal mixer by twice with 4 minutes between each addition. All materials were internal mixed for another 8 minutes after they were all added into the internal mixer.
[0072] Above-described plastic block after being internal mixed was transported to the hopper of the single screw extruder by the conveyer belt, and was chopped into pieces by the cutter in the hopper. Temperature of each section of the barrel was controlled at 170° C. and the rotor speed of the main engine was 500 r/min. After melting, being mixed and being extruded by the single screw, and then being wind-cooled, grinded surface and pelletized, the efficient halogen-free flame retardant masterbatch for polypropylene was made.
Embodiment 4
[0073] Following materials were matched in percentage by weight as below:
[0074] 32.3% of ammonium polyphosphate (APP high molecular ammonium polyphosphate, Shandong Shian Chemical Co., Ltd), 13% of pentaerythritol phosphate (produced by Jiangsu Victory Chemical Co., Ltd), 18% of melamine (Sichuan Chemical Co., Ltd), 10% of bisphenol A bis(diphenyl phosphate) (WSFR-BDP, Zhejiang Wansheng Co., Ltd), 25% of microporous polypropylene (self-prepared, the preparation method is described above), 1% of pentaerythritol stearate (GLYCOLUBE® P(ETS), American Lonza Chemical Inc.), 0.2% of antioxidant 1010 (SONOX 1010, Shandong Linyi Sunny Wealth Chemical Co., Ltd) and 0.5% of antioxidant 168 (SONOX 168, Shandong Linyi Sunny Wealth Chemical Co., Ltd).
[0075] Each component in above-described formula was weighed accurately. Bisphenol A bis(diphenyl phosphate) was mixed with microporous polypropylene into uniformity and then let the mixture stand for 7 hours. Then such mixture, together with pentaerythritol stearate, antioxidant 1010 and antioxidant 168, were added into the pressurized inverse internal mixer. The temperature in the internal mixer chamber was controlled at 160° C., the rotor speed was 50 r/min and the time of internal mixing was 6 minutes. After the materials melted, ammonium polyphosphate, pentaerythritol phosphate and melamine powder were added into the internal mixer by twice with 4 minutes between each addition. All materials were internal mixed for another 8 minutes after they were all added into the internal mixer.
[0076] Above-described plastic block after being internal mixed was transported to the hopper of the single screw extruder by the conveyer belt, and was chopped into pieces by the cutter in the hopper. Temperature of each section of the barrel was controlled at 170° C. and the rotor speed of the main engine was 500 r/min. After melting, being mixed and being extruded by the single screw, and then being wind-cooled, grinded surface and pelletized, the efficient halogen-free flame retardant masterbatch for polypropylene was made.
Comparative Example 1
[0077] Following materials were matched in percentage by weight as below:
[0078] 45% of ammonium polyphosphate (HT-208, Jinan Taixing Fine Chemicals Co. Ltd), 25% of pentaerythritol phosphate (produced by Jiangsu Victory Chemical Co., Ltd), 4.5% of melamine (high-class product, produced by Chengdu Yulong Chemical Co., Ltd), 9% of bisphenol A bis(diphenyl phosphate) (WSFR-BDP, Zhejiang Wansheng Co., Ltd), 15% of microporous polypropylene (self-prepared, the preparation method is described above), 0.8% of pentaerythritol stearate (GLYCOLUBE® P(ETS), American Lonza Chemical Inc.), 0.3% of antioxidant 1010 (SONOX 1010, Shandong Linyi Sunny Wealth Chemical Co., Ltd) and 0.4% of antioxidant 168 (SONOX 168, Shandong Linyi Sunny Wealth Chemical Co., Ltd).
[0079] Each component in above-described formula was weighed accurately. Bisphenol A bis(diphenyl phosphate) was mixed with microporous polypropylene into uniformity and then let the mixture stand for 6 hours. Then such mixture, together with pentaerythritol stearate, antioxidant 1010 and antioxidant 168, were added into the pressurized inverse internal mixer. The temperature in the internal mixer chamber was controlled at 160° C., the rotor speed was 50 r/min and the time of internal mixing was 6 minutes. After the materials melted, ammonium polyphosphate, pentaerythritol phosphate and melamine powder were added into the internal mixer by twice with 4 minutes between each addition. All materials were internal mixed for another 8 minutes after they were all added into the internal mixer.
[0080] Above-described plastic block after being internal mixed was transported to the hopper of the single screw extruder by the conveyer belt, and was chopped into pieces by the cutter in the hopper. Temperature of each section of the barrel was controlled at 170° C. and the rotor speed of the main engine was 500 r/min. After melting, being mixed and being extruded by the single screw, and then being wind-cooled, grinded surface and pelletized, the efficient halogen-free flame retardant masterbatch for polypropylene was made.
Comparative Example 2
[0081] Following materials were matched in percentage by weight as below:
[0082] 32.3% of ammonium polyphosphate (APP high molecular ammonium polyphosphate, Shandong Shian Chemical Co., Ltd), 13% of pentaerythritol phosphate (produced by Jiangsu Victory Chemical Co., Ltd), 18% of melamine (Sichuan Chemical Co., Ltd), 10% of bisphenol A bis(diphenyl phosphate) (WSFR-BDP, Zhejiang Wansheng Co., Ltd), 25% of polypropylene copolymer (EP548R, CNOOC and Shell Petrochemicals Co., Ltd), 1% of pentaerythritol stearate (GLYCOLUBE® P(ETS), American Lonza Chemical Inc.), 0.2% of antioxidant 1010 (SONOX 1010, Shandong Linyi Sunny Wealth Chemical Co., Ltd) and 0.5% of antioxidant 168 (SONOX 168, Shandong Linyi Sunny Wealth Chemical Co., Ltd).
[0083] Each component in above-described formula was weighed accurately. Bisphenol A bis(diphenyl phosphate) was mixed with microporous polypropylene into uniformity and then let the mixture stand for 7 hours. Then such mixture, together with pentaerythritol stearate, antioxidant 1010 and antioxidant 168, were added into the pressurized inverse internal mixer. The temperature in the internal mixer chamber was controlled at 160° C., the rotor speed was 50 r/min and the time of internal mixing was 6 minutes. After the materials melted, ammonium polyphosphate, pentaerythritol phosphate and melamine powder were added into the internal mixer by twice with 4 minutes between each addition. All materials were internal mixed for another 8 minutes after they were all added into the internal mixer.
[0084] Above-described plastic block after being internal mixed was transported to the hopper of the single screw extruder by the conveyer belt, and was chopped into pieces by the cutter in the hopper. Temperature of each section of the barrel was controlled at 170° C. and the rotor speed of the main engine was 500 r/min. After melting, being mixed and being extruded by the single screw, and then being wind-cooled, grinded surface and pelletized, the efficient halogen-free flame retardant masterbatch for polypropylene was made.
Comparative Example 3
[0085] Following materials were matched in percentage by weight as below:
[0086] 38% of ammonium polyphosphate (HT-208, Jinan Taixing Fine Chemicals Co. Ltd), 16.5% of pentaerythritol phosphate (produced by Jiangsu Victory Chemical Co., Ltd), 20% of melamine (high-class product, produced by Chengdu Yulong Chemical Co., Ltd), 24% of microporous polypropylene (self-prepared, the preparation method is described above), 0.8% of pentaerythritol stearate (GLYCOLUBE® P(ETS), American Lonza Chemical Inc.), 0.3% of antioxidant 1010 (SONOX 1010, Shandong Linyi Sunny Wealth Chemical Co., Ltd) and 0.4% of antioxidant 168 (SONOX 168, Shandong Linyi Sunny Wealth Chemical Co., Ltd).
[0087] Each component in above-described formula was weighed accurately. Microporous polypropylene, pentaerythritol stearate, antioxidant 1010 and antioxidant 168 were added into the pressurized inverse internal mixer. The temperature in the internal mixer chamber was controlled at 160° C., the rotor speed was 50 r/min and the time of internal mixing was 6 minutes. After the materials melted, ammonium polyphosphate, pentaerythritol phosphate and melamine powder were added into the internal mixer by twice with 4 minutes between each addition. All materials were internal mixed for another 8 minutes after they were all added into the internal mixer.
[0088] Above-described plastic block after being internal mixed was transported to the hopper of the single screw extruder by conveyer belt, and was chopped into pieces by the cutter in the hopper. Temperature of each section of the barrel was controlled at 170° C. and the rotor speed of the main engine was 500 r/min. After melting, being mixed and being extruded by the single screw, and then being wind-cooled, grinded surface and pelletized, the efficient halogen-free flame retardant masterbatch for polypropylene was made.
Comparative Example 4
[0089] Following materials were matched in percentage by weight as below:
[0090] 38% of ammonium polyphosphate (HT-208, Jinan Taixing Fine Chemicals Co. Ltd), 16.5% of pentaerythritol phosphate (produced by Jiangsu Victory Chemical. Co., Ltd), 20% of melamine (high-class product, produced by Chengdu Yulong Chemical Co., Ltd), 9% of bisphenol A bis(diphenyl phosphate) (WSFR-BDP, Zhejiang Wansheng Co., Ltd), 15% of microporous polypropylene (self-prepared, the preparation method is described above), 0.8% of pentaerythritol stearate (GLYCOLUBE® P(ETS), American Lonza Chemical Inc.), 0.3% of antioxidant 1010 (SONOX 1010, Shandong Linyi Sunny Wealth Chemical Co., Ltd) and 0.4% of antioxidant 168 (SONOX 168, Shandong Linyi Sunny Wealth Chemical Co., Ltd).
[0091] Each component in above-described formula was weighed accurately. Bisphenol A bis(diphenyl phosphate), microporous polypropylene, pentaerythritol stearate, antioxidant 1010 and antioxidant 168 were added into the pressurized inverse internal mixer. The temperature in the internal mixer chamber was controlled at 160° C., the rotor speed was 50 r/min and the time of internal mixing was 6 minutes. After the materials melted, ammonium polyphosphate, pentaerythritol phosphate and melamine powder were added into the internal mixer by twice with 4 minutes between each addition. All materials were internal mixed for another 8 minutes after they were all added into the internal mixer.
[0092] Above-described plastic block after being internal mixed was transported to the hopper of the single screw extruder by conveyer belt, and was chopped into pieces by the cutter in the hopper. Temperature of each section of the barrel was controlled at 170° C. and the rotor speed of the main engine was 500 r/min. After melting, being mixed and being extruded by the single screw, and then being wind-cooled, grinded surface and pelletized, the efficient halogen-free flame retardant masterbatch for polypropylene was made.
Comparative Example 5
[0093] The preparation method is as same as that in Embodiment 3. The difference is that the adopted microporous polypropylene (XP100, Shenzhen Kunstek Corporation) has an average cell diameter of 8 μm and a cell density of 10 4 cells/cm 3 .
Comparative Example 6
[0094] The preparation method is as same as that in Embodiment 3. The difference is that the adopted acid resource is melamine pyrophosphate (MPP, produced by Shandong Shian Chemical Co., Ltd).
Comparative Example 7
[0095] The preparation method is as same as that in Embodiment 3. The difference is that the adopted liquid flame retardant is resorcinol bis(diphenyl phosphate) (produced by Zhejiang Wansheng Co., Ltd).
[0096] The efficient halogen-free flame retardant masterbatch for polypropylene prepared by the present invention was mixed with polypropylene resin according to formulas from Table 1 in order to prepare flame retardant polypropylene. The masterbatches prepared by comparative examples 1˜4 were mixed with the polypropylene resin according to the formulas from Table 2 in order to prepare flame retardant polypropylene. The test result of performance of above-mentioned flame retardant polypropylene is shown as Table 3.
[0097] The performances of efficient halogen-free flame retardant masterbatch for polypropylene prepared by the present invention were tested by following experiments:
[0000]
TABLE 1
Formulas of Embodiments
Embodiment number
Embodi-
Embodi-
Embodi-
Embodi-
ment 1
ment 2
ment 3
ment 4
Content of
65%
65%
65%
65%
polypropylene
resin (PPZ30S)
Category and
Content of
Content of
Content of
Content of
content of
masterbatch
masterbatch
masterbatch
masterbatch
efficient
obtained
obtained
obtained
obtained
halogen-free
from
from
from
from
flame retardant
Embodi-
Embodi-
Embodi-
Embodi-
masterbatch for
ment 1
ment 2
ment 3
ment 4
polypropylene
is 32%
is 32%
is 32%
is 32%
Content of
3%
3%
3%
3%
other
processing
agents
[0000]
TABLE 2
Formulas of Comparative Examples
Comparative example number
Comparative
Comparative
Comparative
Comparative
Comparative
Comparative
Comparative
example 1
example 2
example 3
example 4
example 5
example 6
example 7
Content of
65%
65%
65%
65%
65%
65%
65%
polypropylene
resin
(PPZ30S)
Category and
Content
Content
Content
Content
Content
Content
Content
content of
of
of
of
of
of
of
of
efficient
masterbatch
masterbatch
masterbatch
masterbatch
masterbatch
masterbatch
masterbatch
halogen-free
obtained
obtained
obtained
obtained
obtained
obtained
obtained
flame
from
from
from
from
from
from
from
retardant
Comparative
Comparative
Comparative
Comparative
Comparative
Comparative
Comparative
masterbatch
example
example
example
example
example
example
example
for
1 is 32%
2 is 32%
3 is 32%
4 is 32%
5 is 32%
6 is 32%
7 is 32%
polypropylene
Content of
3%
3%
3%
3%
3%
3%
3%
other
processing
agents
[0000]
TABLE 3
Test result of performance of flame retardant PP material
Item
Notch impact
Tensile
Bending
Flexural
strength
yield
strength
modulus
Flame
23° C.
strength
(23° C.)
(23° C.)
retardancy
Unit
KJ/m 2
MPa
MPa
MPa
Test standard
GB/T1843-
GB/T1040-
GB/T9341-
GB/T9341-
1996
2006
2000
2000
UL94
Embodiment 1
3.9
25
34
1950
2.0 mmV0
Embodiment 2
3.8
24
34
1945
2.0 mmV0
Embodiment 3
4.2
23
36
1976
1.5 mmV0
Embodiment 4
4.5
25
35
2010
3.2 mmV0
Comparative
3.2
21
38
2230
3.2 mmV0
example 1
Comparative
4.1
24
35
1988
3.2 mmHB
example 2
Comparative
4.4
24
35
1936
3.2 mmV0
example 3
Comparative
3.8
21
34
1866
2.5 mmV0
example 4
Comparative
4.1
22
34
1926
2.5 mmV0
example 5
Comparative
4.0
22
36
1943
3.2 mmV0
example 6
Comparative
4.1
23
35
1902
3.2 mmV0
example 7
[0098] It can be seen from the above data that, comparing the masterbatch prepared by Embodiment 3 with that prepared by comparative example 1, after altering ratio of ammonium polyphosphate to pentaerythritol phosphate to melamine in the flame retardant, the flame retardancy of the material decreased from 1.5 mm V0 to 3.2 mm V0. It illustrates that the synergetic effect between the flame retardants decreased, resulting in that the flame retardancy decreased. Comparing the masterbatch prepared by Embodiment 4 with that prepared by comparative example 2, when using general polypropylene copolymer instead as a carrier in processing, the flame retardancy of the material decreased and the physical and mechanical properties decreased also.
[0099] Comparing comparative example 3 with Embodiment 3, the flame retardancy of flame retardant masterbatch prepared without addition of liquid flame retardant bisphenol A bis(diphenyl phosphate), decreased greatly from 1.5 mm V0 to 3.2 mm V0. It indicates that the liquid flame retardant bisphenol A bis(diphenyl phosphate) adopted in the present invention and the solid flame retardants which are ammonium polyphosphate, pentaerythritol phosphate and melamine adopted in the present invention, generate an inflaming retarding synergistic effect together.
[0100] Comparing comparative example 4 with Embodiment 3, the liquid flame retardant wasn't adsorbed by the microporous polypropylene. Instead, it was added by direct addition. The flame retardant effect of the masterbatch prepared by comparative example 4 reduced, and the physical and mechanical properties of the material decreased either. It indicates that only after the liquid flame retardant is adsorbed by the microporous polypropylene in advance and then is loaded with the solid flame retardant, can we achieve a better mixing effect.
[0101] Comparing comparative example 5 with Embodiment 3, when microporous polypropylene with smaller cell diameter and less cell density was used instead, due to the decline of its adsorption capacity for the liquid flame retardant, the flame retardant effect of flame retardant masterbatch prepared by comparative example 5 was worse.
[0102] Compared with comparative example 3, in comparative example 6 and comparative example 7, melamine pyrophosphate was used as an acid resource flame retardant instead and resorcinol bis(diphenyl phosphate) was used as the liquid flame retardant instead respectively. Because the types of flame retardant are different, the synergetic flame retardant effect between the flame retardants decreased and flame retardant efficiency of flame retardant masterbatch decreased greatly. It indicates from the corresponding data in Table 3 that, only after the solid flame retardants which are ammonium polyphosphate, pentaerythritol phosphate and melamine, and the liquid flame retardant which is bisphenol A bis(diphenyl phosphate) were adopted in the present invention and were adsorbed and loaded by the microporous polypropylene prepared in the present invention, can we achieve optimal flame retardancy under the precondition of not influencing the processability and the physical and mechanical properties of the material.
|
The present invention provides an efficient halogen-free flame retardant masterbatch for polypropylene, which comprises following raw materials in percentage by weight: 30˜40% of ammonium polyphosphate; 10˜20% of pentaerythritol phosphate; 15˜25% of melamine; 5˜15% of bisphenol A bis(diphenyl phosphate); 10˜30% of microporous polypropylene; 0.1˜1% of pentaerythritol stearate; 0.1˜0.5% of antioxidant 1010; and 0.1˜0.5% of antioxidant 168. Said microporous polypropylene is particles with a size of 3˜5 mm, cell size on a surface of the particle is 10˜100 μm, and cell density is more than 10 5 cells/cm 3 . The efficient halogen-free flame retardant masterbatch for polypropylene prepared by the invention has several characteristics of easy dispersing, easy processing, high flame retardant efficiency and low production cost, and it can be widely used in the production of flame retardant polypropylene materials for extrusion, injection molding and membrane blowing.
| 2
|
BACKGROUND OF THE INVENTION
This invention relates to a method and apparatus for changing dies on a moving bolster for a press, particularly a large press. More particularly, this invention relates to a hydraulic control circuit for the moving bolster to decelerate the moving bolster to a smooth stop within the press. Still more particularly, this invention relates to a rotary valve for use in a circuit of the type described for controlling the movement of a moving bolster during die changing.
Large presses are well known for making large items such as automobile body parts by pressing a metal blank. Typically, such presses include a press body and a pressing apparatus for pressing a metallic blank inserted intermediate the pressing apparatus and a die positioned in a bolster. It is a continuing problem in this art to provide a means for changing dies on a bolster to facilitate die changes within the press.
A typical arrangement utilizes a moving bolster. For a die change, the bolster containing the existing die, for forming automobile side panels for example, is withdrawn from the press. Then, the automobile side panel die is removed from the bolster and another die, such as a hood die, is secured to the bolster. Thereafter, the bolster with the hood die attached is moved into position within the press and secured at that point. The art of presses, moving bolsters, and securing dies to the moving bolster is well-developed.
However, it remains a problem in this art to expedite die changes. In addition to minimizing production interruption for a die change in normal circumstances, it is desired to minimize inventory of a particular part for cost reasons. Thus, while large numbers of a particular part might be pressed before changing to another part because of the long time needed to change the dies, now it is a significant desire in the art to produce fewer parts before a die change. This requires therefore that die changes be expedited and completed in a short time.
Such presses are massive with capacities up to hundreds of tons of pressure to be exerted on dies which can weigh in the order of 40 or 50 tons. Accordingly, the bolsters and the dies are able to withstand such pressures in the pressing operation, largely through their size and structure. It is a problem, however, when undergoing expedited die changing of the type described, to move such massive parts in a way which satisfactorily controls movement and momentum of the combination, both in withdrawing the die/bolster combination from the press, but particularly in inserting the new die/bolster combination into the press. It is of course desirable to move the die and bolster as promptly as possible, but a risk of damage to the equipment for failure to stop adequately must be avoided given the masses involved.
Accordingly, it is a problem in this art to provide a control circuit, such as pneumatic control circuit compatible with typical control circuits for moving such equipment, which can control acceleration, deceleration, and stopping of such equipment.
It is another problem in this art to automate such stopping particularly within the press, since operator judgment if faulty can cause significant damage for failure of the equipment to stop precisely within the press. Thus, it is desired to provide a circuit which is responsive to a ramp on the track of travel to initiate deceleration and stoppage.
It is another problem in this art to provide a control valve responsive to the ramp for use in the hydraulic circuit of the invention to control deceleration and stoppage of the die and bolster at a predetermined time, with a desired hold and subsequent release of the pneumatic braking.
These and other objects of the invention will be apparent from a detailed description of the invention which follows.
BRIEF SUMMARY OF THE INVENTION
Directed to achieving the foregoing objectives, one aspect of the invention relates to a pneumatic circuit for controlling deceleration of a moving bolster to achieve a controlled stop for a die and bolster combination. The circuit includes an air supply in circuit with a pilot operating 4-way 2-position valve for providing air to a pair of quick exhaust, directional valves for providing air to a deceleration valve according to the invention. The deceleration valve permits forward movement of the air motor through a control valve until its cam-operated member is actuated by contact with a ramp on the track for the bolster at a predetermined location near or within the press. The location is determined so that the deceleration valve and circuit can operate to provide a controlled stop to the equipment. When the cam-actuated member is operated, the forward air supply is interrupted, while permitting the bolster to move to a stop, either by its own momentum or by the use of a reverse air supply initiated to provide reverse air for the motor under the control of a cam operated valve or both. In any case, the cam also sets the circuit to a reverse mode, so that the bolster and die can be withdrawn on its next cycle. Thereupon, the die/bolster combination decelerates to a controlled stop within the press.
A significant advantage of the invention is that it permits significant increases in the speed of movement of the bolsters since the deceleration and stoppage of the bolster is controlled. Speeds of 30 to 35 feet per minute are possible as compared to an average speed for the bolsters before modification of about 10 to 15 feet/min.
The deceleration valve according to the invention is mounted to the bolster and is activated by a cam mounted on the press bed. The main air lines running to the motor are then rerouted through the deceleration valve which in turn reduces the volume of air to the motor when activated by the cam causing the motor to slow down. It is a feature of the valve according to the invention to provide a controlled clearance, such as 0.010 in. clearance between the spool and the valve body, thus allowing an internal by-pass of air to the motor after the valve is closed by the cam. The by-pass air is used to bleed down air trapped in the circuit after controlled stop. The deceleration valve also causes the bolster to idle onto its stop at about 2 ft/min by its structure in combination with the control circuit.
It is another feature of the invention that, when the bolster is on its stop, the main air supply is shut off. A column of air is trapped between the motor and the deceleration valve which allows he bolster to maintain a load on the stop while the bolster is lowered onto the press bed. The column of air is bled off to atmosphere through a small air jet with a short blow-down time of about 20 seconds.
These and other features of the invention will become apparent from a detailed description of the invention which follows taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is a schematic view of the major components of a conventional controlled moving bolster arrangement for a press;
FIG. 2 is a top view of a portion of FIG. 1 showing the moving bolster, with a camming ramp located at a predetermined position along the bolster path;
FIG. 3 is a pneumatic circuit according to the invention for controlling the deceleration of a moving bolster in a press;
FIG. 4 is a side plan view of a deceleration valve preferably used in the circuit of FIG. 3 showing its cam-actuated operator for contacting the ramp of FIG. 2;
FIG. 5 is a frontal view of the deceleration valve of FIG. 4;
FIG. 6 is a cross-sectional view taken along line 6--6 of FIG. 4; and
FIG. 7 is a side view of the camming ramp mounted on the rails as shown in FIG. 2 for actuating the deceleration valve of FIGS. 4 to 6 in the circuit of FIG. 3.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
In FIGS. 1 and 2, a schematic view is shown of a press, such as a large panel transfer press used in the automobile industry, designed by the reference numeral 10. The press 10 is conventionally equipped with a moving bolster shown generally at the reference numeral 12 on which a die 13 and gripper rail assemblies 14 are mounted in one of the ways known to the art. Such moving bolster arrangements are well known for assisting die changes in the press 10. Conventionally, a combination of a first die 13 on a moving bolster 12 is in production in the press 10 while a second set of a die and a moving bolster rests outside the press 10 and is prepared for the next production run. Thus, in this way, production runs for particular parts made from a particular die can be shortened if the down time from the die change is rapid and economical. Prior to the development of such moving bolster arrangements, die changes were costly so extended production runs were usually the norm rather than the exception. With the advent of moving bolsters of the type generally depicted in FIGS. 1 and 2, production runs could be more limited.
In such arrangements, a die 13 is clamped to the bolster 14 by die clamps generally shown at the reference number 17. The bolster includes sufficient pneumatic, electric, or hydraulic circuitry or components to permit the equipment to traverse laterally from the at-rest position to a production position within the press 10 for receiving the stamping anvil 11 of the press 10 in a mating relationship. The bolster also includes sufficient gripper rail assemblies (not shown) for gripping the rails 16 for movement as described. Usually, such circuits are pneumatic, so the invention is here discussed as a pneumatic circuit in its preferred embodiment.
The apparatus of FIGS. 1 and 2 is conventionally controlled by a programmable control 18 for automatically executing the total changeover process. The control 18 contains the data for the respective die sets, as well as data for the changeover of destackers and racking/stacking devices for finished parts. The steps in a die change, which are controlled automatically, include unclamping of the dies on the slide, uncoupling of gripper rail connections, raising and moving out the exchanged moving bolster and dies, moving in, lowering, centering and reclamping, as well as the changes of parts nests. All pressure, travel and speed parameters related to the new die set are called-up from memory and entered by the electronic control as set values.
A die change operation can be accomplished in about 10 minutes or less. For ease of monitoring, the individual phases of the changeover procedure are displayed locally and centrally on CRT's. Against this background of conventional equipment, the invention of this application relates to a deceleration valve and pneumatic circuit for application to this system.
A deceleration valve 30, shown in detail in FIGS. 4 to 6, and referred to in the pneumatic circuit of FIG. 3, is mounted on the bolster 12, as seen in FIG. 2. The deceleration valve 30 is activated by contact between its cam roller 29 and a cam 90 shown in FIG. 7 mounted on the press bed adjacent to a rail 16. By the action of the deceleration valve 30, the main air lines running to an air motor 32 (seen in FIG. 3) are effectively rerouted through the deceleration valve 30 which in turn reduces the volume of air to the motor 32 when activated by the cam 90 causing the motor 32 to slow down. A feature of the deceleration valve 30, which will be discussed in greater detail, is that the valve has a limited clearance between the valve body 33 and the spool 34, such as about 0.010", thus allowing an internal by-pass of air to the motor 32 after the valve 30 is closed by the cam 90. The by-pass air may be used to idle the bolster 12 onto a stop 19 (FIG. 1) at a controlled rate of speed such as about 2 ft./min. The invention thus provides a significant improvement in the average speed of travel for a bolster 12 thus decreasing the time needed for a die change. Conventionally, the average speed of bolsters before modification according to the invention was about 10 to 15 ft./min., while the average speed after modification is about 30 to 35 ft./min.
Another significant feature of the invention as shown in the pneumatic circuit of FIG. 3 is that after the bolster 12 is on the stop 19, the main air supply 35 is shut off. A column of air is trapped between the motor 32 and the deceleration valve 30 which allows the bolster 12 to maintain a load on the stop 19 while the bolster 12 is lowered onto the press bed. The column of air is bled off to the atmosphere through a small air jet with a blow down time of about 20 seconds.
The pneumatic circuit for the invention is shown in FIG. 3 and is designated generally by the reference numeral 37. The circuit 37 includes an air supply source 35 such as a central air supply at the factory, connected by air hoses to the moving bolster 12. The air supply source 35 is connected through a manual or power actuated valve 38 to a 4-way, 2-position valve 39, having an actuator 40 for controlling a forward or a reverse direction for the air motor 32 and thus for the moving bolster 12. Assume first that the actuator 40 is positioned to control forward travel.
In that case, the air from the air supply 35 is channeled through the conduit 41 to a pair of directional valves 42a and 42b having a quick exhaust. When the valve 42a is open as determined by the presence of air from the line 41, air from the air supply 35 is provided through the conduit 43 through each of the valves 42a and 42b to the deceleration valve 30 through the conduits 44 and 45 respectively.
When the deceleration valve 30 is open, i.e. when the cam actuator 29 is not operative or in contact with the cam 90, air is supplied from the deceleration valve 30 to the forward port F of each of the air motors 32a and 32b through the quick exhaust valves 46a and 46b respectively.
Similarly, when the pilot-operated valve 39 is actuated to be in its reverse direction controlling position, air is supplied through the conduit 51 to a pair of directional valves 52a and 52b having a quick exhaust. When the valve 52a is open as determined by the presence of air from the valve 51, air from the air supply 35 is provided through the conduit 53 through each of the valves 52a and 52b to the 32a and 32b through the conduits 54 and 55 respectively.
A cam-operated valve 50 is positioned in the conduit 53 and is cam-actuated at the same time as the deceleration valve 30 to coordinate forward and reverse operations of the circuit. The circuit of FIG. 3 and its operation can be understood by those skilled in the art so further detailed discussion is not believed to be necessary.
In operation, the bolster 12 is thus caused to travel in a forward or a reverse direction according to the operation of the air motors 32a and 32b. Assuming that the forward direction is equivalent to withdrawal of the bolster 12 from the press 10, it can be noted that when the cam-actuator 29 for the deceleration valve 30 rides over the cam surface 91 of FIGS. 2 and 7 in the forward direction, the deceleration valve 30 is closed this stopping forward motion of the air motors 32a, 32b. At the same time, the valve 50 is also actuated, thus supplying air through the valve 50 to the valves 52a and 52b, thus reversing the drive on the air motor to stop the bolster 12 at a predetermined position. That predetermined position is at the stop 19; thus the position of the cam surface 91 of FIGS. 2 and 7 is located at a site which causes the bolster 12 to stop at the stop 19 given its momentum as determined by its mass and its velocity at the location of the stop, with the aid of the reversal of the motors 32a, 32b.
When the air to the motors 32a, 32b is in a reverse mode, as described, after actuation of the values 30, 50 by the cam 91, a release path for the air from the motors 32a, 46b is defined. The gap between the spool 34 and the valve body thus controls the exit of air in the reverse mode to cause the motors to idle onto the stop 19. Once positioned, the air further blows down through the pilot hole 70. The spool 34 is biased open by a spring 71.
The cam roller 29 includes a pair of wheels 72 rotatably secured to an assembly 73 at the lowermost end of the spool 34. When the wheels contact the ramp 91, the spool 34 is forced upwardly, causing its through openings 74, 75 to deregister from the input ports 44a, 45a connected to the lines 44, 45.
FIG. 7 shows a side view of the cam surface 90 secured to the press bed as in FIGS. 1 and 2. As explained above, the cam surface 91 actuates the deceleration valve 30 and the valve 50 as shown and discussed in connection with FIGS. 3 to 6. As shown, the ramp surface 91 is in the shape of a gentle curve so that when the cam-actuators 29 contact the cam surface 91, the movement of the spool 34 is smooth and free. The surface 91 could also be arranged to assume alternate shapes to provide desired and predetermined opening and closing characteristics for the deceleration valve when controlling the operation of the air motor.
While this invention has been described as having a preferred design, it will be understood that it is capable of further modification within the spirit of the invention. This application is, therefore, intended to cover any variations, uses, or adaptation of the invention following the general principles thereof and including such departures from the present disclose as come within know or customary practice in the art to which this invention pertains and fall within the limits of the appended claims.
|
A method and apparatus for changing dies on a moving bolster for a press including a control circuit in combination with a cam-actuated deceleration valve. A ramp is located at a predetermined location along a path for the moving bolster. Upon reaching the ramp location when the bolster is moving toward the press, the deceleration valve is actuated to inhibit and shut off a flow of air to air-operated motors on the bolster. Thereupon, the moves to a stop at a predetermined location relative to the press.
| 8
|
CLAIM FOR PRIORITY
This application is a division of U.S. application Ser. No. 11/451,057 filed Jun. 12, 2006, now U.S. Pat. No. 7,419,462, issued on Sep. 2, 2008, which claims the benefit of U.S. Provisional Application Ser. No. 60/689,818, filed Jun. 13, 2005. The priorities of the foregoing applications are hereby claimed and the entirety of their disclosures incorporated herein by reference.
TECHNICAL FIELD
The present invention relates to improved apparatus for making paperboard pressware such as paper plates, bowls, platters and the like from paperboard blanks. In connection with the present invention, paperboard blanks are pneumatically propelled into the forming cavity of a pressware die set.
BACKGROUND
Disposable paper plates and similar containers are generally made from either pressed paperboard or molded pulp. Molded pulp containers, after drying, are strong and rigid but generally have rough surface characteristics. They are not usually coated and are susceptible to penetration by water, oil and other liquids. Pressed paperboard containers, on the other hand, can be decorated and coated with a liquid-resistant coating before being pressed by the forming dies into the desired shape.
General background with respect to pressed paperboard containers is seen in U.S. Pat. Nos. 5,203,491 entitled “Bake-In Press-Formed Container” of R. P. Marx et al.; 4,721,500 entitled “Method of Forming a Rigid Paper-Board Container” of G. J. Van Handel et al.; 4,721,499 entitled “Method of Producing a Rigid Paperboard Container” of R. P. Marx et al.; 4,609,140 entitled “Rigid Paperboard Container and Method and Apparatus for Producing Same” of G. J. Van Handel et al.; and 4,606,496 entitled “Rigid Paperboard Container” of R. P. Marx et al., all of which are incorporated herein by reference.
The following commonly-assigned patents and co-pending patent applications contain further information as to pressware materials, processing techniques and equipment and are also incorporated herein by reference: U.S. application Ser. No. 10/963,686, entitled “Pressed Paperboard Servingware with Improved Rigidity and Rim Stiffness” (Publication No. US2006-0208054A1); U.S. Pat. No. 7,337,943, entitled “Disposable Servingware Containers with Flange Tabs”; U.S. Pat. No. 7,048,176, entitled “Deep Dish Disposable Pressed Paperboard Container”; U.S. Pat. No. 6,893,693, entitled “High Gloss Disposable Pressware”; U.S. Pat. No. 6,733,852, entitled “Disposable Serving Plate With Sidewall-Engaged Sealing Cover”; U.S. Pat. No. 6,715,630, entitled “Disposable Food Container With A Linear Sidewall Profile and an Arcuate Outer Flange”; U.S. Pat. No. 6,592,357, entitled “Rotating Inertial Pin Blank Stops for Pressware Die Sets”; U.S. Pat. No. 6,589,043, entitled “Punch Stripper Ring Knock-Out for Pressware Die Sets”; U.S. Pat. No. 6,585,506, entitled “Side Mounted Temperature Probe for Pressware Die Sets”; and U.S. Pat. No. 6,474,497, entitled “Smooth Profiled Food Service Articles”.
Equipment and methods for making paperboard containers are also disclosed in U.S. Pat. Nos. 5,249,946 entitled “Plate Forming Die Set” of R. P. Marx et al.; 4,832,676 entitled “Method and Apparatus for Forming Paperboard Containers” of A. D. Johns et al.; and 4,781,566 entitled “Apparatus and Related Method for Aligning Irregular Blanks Relative to a Die Half” of A. F. Rossi et al. In addition, applicant's co-pending U.S. patent application Ser. No. 11/057,959, entitled “Apparatus for Making Paperboard Pressware with Controlled Blank Feed” (Publication No. US2005-0192171A1), discusses use of a variable speed blank feeder that includes a pervious feed belt, vacuum source and drive means.
The forming section of pressware apparatus may typically include a plurality of reciprocating upper die halves opposing, in facing relationship, a plurality of lower die halves. The upper die halves are mounted for reciprocating movement in a direction that is generally oblique or inclined with respect to the horizontal or vertical plane. The paperboard blanks, after cutting, are gravity fed to the inclined lower die halves in the forming section. The construction of the die halves and the equipment on which they are mounted may be substantially conventional; for example, as utilized on presses manufactured by the Peerless Machine & Tool Corporation, Marion, Ind. U.S. Pat. No. 4,435,143 entitled “Small Blank Feed and Tray Former” to Dempsey describes such apparatus. See also, U.S. Pat. No. 4,242,293 to Dowd. Optionally included are hydraulic controls as described in U.S. Pat. No. 4,588,539 to Rossi et al.
For paperboard plate stock of conventional thicknesses, i.e., in the range of from about 0.010 to about 0.040 inches, it is preferred that the spacing between the upper die surface and the lower die surface is as taught in U.S. Pat. Nos. 4,721,499 and 4,721,500. Note also the following patents of general interest with respect to forming paperboard containers: U.S. Pat. No. 6,527,687 to Fortney et al. which discloses a cut-in-place forming system with a draw ring and ejection means comprising air jets; U.S. Pat. No. 3,305,434 to Bernier et al. which discloses a paperboard forming apparatus; U.S. Pat. No. 2,832,522 to Schlanger which discloses another paperboard forming apparatus; and U.S. Pat. No. 2,595,046 to Amberg which discloses yet another paperboard forming apparatus.
It is conventional in the manufacture of pressed paperboard containers to feed paperboard blanks to a die set by way of gravity, that is, by passive means. “Active” feed techniques, where paperboard webs or blanks are supplied to the die set by means other than gravity, such as by belt or chain driven conveyors, are not generally employed due to their relative complexity and the need for close synchronization with the press. Pneumatic assist for pressing paperboard articles has heretofore generally been limited to assisting in product ejection, de-nesting or stripping from the mold, or in reducing friction during conveying from one processing station to another, and these functions have been accomplished with relatively simple air nozzles and the like. For example, in connection with ejection, de-nesting or stripping of pressed paperboard articles from a mold, the following patents are noted: U.S. Pat. No. 1,793,089 entitled “Paper Utensil Forming Die” to Heyes; U.S. Pat. No. 2,332,937 entitled “Molding Press” to Schmidberger; and U.S. Pat. No. 4,755,128 entitled “Apparatus for Releasing a Press-Formed Article From a Die Set” to Alexander et al. Pneumatic assists for ejection and de-nesting of other manufactured articles are found in U.S. Pat. No. 5,364,583 entitled “Method and Device for Removing an Injection-Molded Piece From a Mold” of Hayashi, and U.S. Pat. No. 5,693,346 entitled “Automatic Molded Hardboard Unnesting System” to Dull.
In connection with air cushioning or conveying of pressed paperboard articles previously cited U.S. Pat. Nos. 4,435,143 and 4,755,128 are noted. Air cushioning in connection with production of other types of articles are found in U.S. Pat. No. 4,741,196 entitled “Air Conveyor and Method for Removing Parts from a High Speed Forming Press” to Stewart, et al.; U.S. Pat. No. 5,017,052 entitled “Cup Conveyor” to Bartylla; U.S. Pat. No. 5,634,636 entitled “Flexible Object Handling System Using Feedback Controlled Air Jets” to Jackson et al.; U.S. Pat. No. 6,042,107 entitled “Device for Contact-Free Sheet Guidance in a Sheet-Fed Printing Press” to Stephan; and U.S. Pat. No. 6,585,259 entitled “Delivery of a Machine for Processing Flat Printing Materials” to Kerpe et al.
As to conveying equipment utilized in manufacturing operations generally, the following patents are noted: U.S. Pat. Nos. 5,945,137 to Mizuno et al.; 5,816,994 to Hill et al.; 5,163,891 to Goldsborough et al.; 5,074,539 to Wells et al.; 5,026,040 to Gibert; 4,748,792 to Jeffrey; 4,494,745 to Ward, Sr. et al.; 4,359,214 to Eldridge; and 3,228,066 to Rippstein.
It has been found in accordance with the present invention that paperboard blanks can be pneumatically propelled into a forming die by selective use of laminar air flow air knives to increase speed and reliability of the pressing operation. Air knives heretofore have been used in industrial processes primarily for drying applications. The apparatus and method of the invention eliminates moving parts as opposed to mechanical options for active blank feeding and thus requires less maintenance and capital investment as will be appreciated especially from the appended drawings.
SUMMARY OF THE INVENTION
A typical apparatus of the invention includes an inclined die set with a punch and a die adapted for reciprocal motion with respect to each other, configured to cooperate in order to form a shaped product from a substantially planar paperboard blank upon pressing thereof, as well as an inclined feed station for positioning a paperboard blank for insertion into the die set along an inclined feed path. A first air knife is upwardly disposed with respect to the feed station and has a pneumatic outlet directed toward the feed path; while a second air knife is downwardly disposed with respect to the feed station and also has a pneumatic outlet directed toward the feed path. The first and second air knives are selected and positioned so as to cooperate to propel the paperboard blank into the die set.
Further features and advantages of the present invention will become apparent from the discussion which follows.
BRIEF DESCRIPTION OF DRAWINGS
The invention is described in detail below in connection with the appended drawings wherein like numerals designate like parts and wherein:
FIG. 1 is a perspective view of a pressed paperboard plate representative of the articles produced in connection with the present invention;
FIG. 2 is a view in partial section illustrating the profile of the plate of FIG. 1 ;
FIG. 3 is a schematic view in perspective of the die portion of a segmented die set of the class used to make pressware containers;
FIG. 4 is a partial perspective view of the feed section of an improved apparatus of the invention;
FIG. 5 is a schematic diagram of an apparatus of the invention;
FIG. 6 is a diagram illustrating angles and operation of the apparatus of FIGS. 4 and 5 ;
FIG. 7 is a schematic top view illustrating a plurality of die sets and associated feeding stations as would be arranged on a press;
FIG. 8 is a schematic diagram illustrating the flow pattern of an air knife used with the present invention; and
FIG. 9 is a timing diagram illustrating a 360° forming cycle of a pressware die set.
DETAILED DESCRIPTION
The invention is described in detail below with reference to numerous embodiments for purposes of exemplification and illustration only. Modifications to particular embodiments within the spirit and scope of the present invention, set forth in the appended claims, will be readily apparent to those of skill in the art.
As used herein, terminology is given its ordinary meaning unless a more specific definition is given or the context indicates otherwise. “Mil”, “mils” and like terminology refers to thousandths of an inch and dimensions are given in inches unless otherwise specified. Caliper is the thickness of material and is expressed in mils. “FPM” or “fpm” refers to feet per minute. “PSI” or “psi” refers to pounds per square inch gauge pressure unless otherwise stated.
An “air knife” is a pneumatic device for generating a fluid jet, characterized by an elongated slot with a slot axis generally perpendicular to the path of the fluid jet which issues from the air knife. The fluid jet extends over the length of the slot, suitably in many cases resulting in a generally controlled laminar air flow with a pre-defined dispersal pattern. See FIG. 8 . It has been found that a suitable air knife used in connection with the present invention for paperboard blanks will have a 3 inch slot, but other slot lengths may be used. Air knives typically have means to receive, control and filter fluid input and adjust fluid output characteristics, such as flow velocity, pressure, and dispersal patterns. Some air knives have the additional ability to reduce static electricity by introducing positive and negative ions into the fluid jet.
Pressed articles prepared by way of the invention include disposable servingware containers such as paperboard containers in the form of plates, both compartmented and non-compartmented, as well as bowls, trays, and platters. The products are typically round or oval in shape but can also be hexagonal, octagonal, or multi-sided. The containers produced by way of the invention generally include a plurality of radially extending, circumferentially spaced pleats, preferably formed of rebonded paperboard lamellae as is known in the art.
The present invention is typically practiced in connection with segmented dies generally as are known and further discussed herein. Manufacture from coated paperboard is preferred. Clay coated paperboard is typically printed, coated with a functional grease/water resistant barrier and moistened prior to blanking and forming. The printed, coated and moistened paperboard roll is then transferred to a web feed blanking press where the blanks are cut in a straight across, staggered, or nested pattern (to minimize scrap). The blanks are transferred via inclined transfer chutes to an inclined feed station immediately adjacent to the pressware die set. The transfer chutes and feed station may be integral with each other and typically will consist of parallel, slotted rails or guides adjustable to fit the dimensions of the blank. The feed station will temporarily hold and position the blank prior to the blank being fed into the die set.
During the feed step, blanks will commonly hit against forward blank stops at the forward portion of the die set (rigid or pin stops that can rotate) for final positioning prior to forming. The stop heights and locations are chosen to accurately locate the blank and allow the formed product to be removed from the tooling without interference. Typically the inner portions of the blank stops or inner blank stops are lower in height since the formed product must pass over them.
Instead of web forming, blanks may be rotary cut or reciprocally cut off-line in a separate operation. Such pre-cut blanks are typically transferred to the feed station via transfer chutes of the type described above. The overall productivity of such pre-cut blank feed style presses is typically lower than a web feed style press since the stacks of blanks must be repeatedly inserted into the feed station, the presses are commonly narrower in width with fewer forming positions available, and the forming speeds are commonly less since fluid hydraulics are typically used versus mechanical cams and gears.
As noted, the blank is typically positioned by rigid or rotating pin stops as well as by side edge guides that contact the blank diameter. The punch pressure ring contacts the blank, clamping it against the lower draw ring and optional relief area to provide initial pleating control. The upper punch and lower die knock-outs (that may have compartment ribs machined into them) then contact the paperboard holding the blank on center. The upper knock-out is sometimes an articulated style having spring pre-load and full loads and 0.030 inch to 0.120 inch articulation stroke during the formation. The pressure ring may have the outer product profile machined into it and provides further pleating control by clamping the blank between its profile area and die outer profile during the formation. The draw ring and pressure ring springs typically are chosen in the manner to allow full movement of the draw ring prior to pressure ring movement (i.e., full spring force of draw ring is less than or equal to the pre-load of the pressure ring springs).
The invention is advantageously practiced in connection with a heated matched pressware die set utilizing inertial rotating pin blank stops as described in co-pending application U.S. Ser. No. 09/653,577, filed Aug. 31, 2000, now U.S. Pat. No. 6,592,357. For paperboard plate stock of conventional thicknesses in the range of from about 0.010 to about 0.040 inches, the springs upon which the lower die half is mounted are typically constructed such that the full stroke of the upper die results in a force applied between the dies of from about 6,000 to 10,000 pounds or higher. Similar forming pressures and control thereof may likewise be accomplished using hydraulics as will be appreciated by one of skill in the art. The paperboard which is formed into the blanks is conventionally produced by a wet laid papermaking process and is typically available in the form of a continuous web on a roll. The paperboard stock is preferred to have a basis weight in the range of from about 100 pounds to about 400 pounds per 3000 square foot ream and a thickness or caliper in the range of from about 0.010 to about 0.040 inches as noted above. Lower basis weight paperboard is preferred for ease of forming and to save on feedstock costs. Paperboard stock utilized for forming paper plates is typically formed from bleached pulp fiber and is usually double clay coated on one side. Such paperboard stock commonly has a moisture (water content) varying from about 4.0 to about 8.0 percent by weight.
In a pressware apparatus for making pressed paperboard articles, the present invention provides the combination of: (a) a die set including a punch and a die adapted for reciprocal motion with respect to each other and configured to cooperate in order to form a shaped product from a substantially planar paperboard blank upon pressing thereof, (b) a feed station for positioning a paperboard blank for insertion into said die set; and (c) means for pneumatically propelling the paperboard blank from the feed station into the die set.
The means for pneumatically propelling the paperboard blank include means for providing a first fluid jet, the means for providing the first jet being upwardly disposed at a predetermined distance and orientation with respect to a paperboard blank in the feed station such that the first jet is downwardly directed at an oblique angle with respect to a production direction and incident upon a paperboard blank in the feed station, the angle, distance, flow rate, fluid pressure, and fluid dispersal pattern of the first jet being selected so as to be operative to accelerate the paperboard blank into the die set.
The means for pneumatically propelling the paperboard blank typically also include means for providing a second fluid jet, the means for providing the second jet being downwardly disposed with respect to the feed station at a predetermined distance and orientation with respect to a paperboard blank in the feed station such that the second jet is upwardly directed at an oblique angle with respect to a production direction and incident upon a paperboard blank in the feed station, the angle, distance, flow rate, fluid pressure, and fluid dispersal pattern of the second jet being selected so as to promote propelling the paperboard blank into the die set.
The fluid jets are suitably nozzles or air knives. Perhaps the most convenient fluid is compressed air at pressures of from about 10 psi to about 100 psi. From about 15 psi to about 50 psi is sufficient in many cases. Conventional means may be used to supply the fluid, such as readily available commercial air compressors. Suitable air knives have a characteristic jet height spread of about 6 inches or less at 1 foot and exhibit a characteristic pneumatic force of at least about 0.05 lbs. Typically and preferably, the first upper jet makes an oblique angle with the production direction of from about 1° to about 35° while the second jet makes an angle with the production direction of from about 5° to about 60°. Other angles may be used.
The die set and the production direction are generally inclined at an angle of from about 30° to about 60° with respect to horizontal. Optionally included are stop means for retaining a paperboard blank in the feed station such that the blank is stationary while a container is formed from another blank. The stop means may be a pin or any suitable clamp. There is typically provided control means for synchronizing the means for pneumatically propelling the paperboard blank into the die set with the reciprocal motion of the die set, wherein the means for pneumatically propelling the blank are active during feeding of a blank to the die set and inactive during formation of a container.
A method of making a pressed paperboard container in accordance with the invention includes: (a) positioning a substantially planar paperboard blank in a feed station such that the paperboard blank is substantially stationary; (b) pneumatically propelling the blank into a die set including a punch and a die adapted for reciprocal motion with respect to each other and configured to cooperate in order to form a shaped product from the substantially planar paperboard blank upon pressing thereof, and (c) forming the container in the die set. The step of pneumatically propelling the blank into the die set is carried out in a feed step with a pulsed jet, the pulsed jet being synchronized with the feed step and forming step such that the jet is on during at least a portion of the feed step and off during forming of the related container.
Generally, the paperboard blank is pneumatically propelled into the die set at a peak velocity of at least about 1000 fpm; typically at a peak velocity at least about 750 fpm up to about 3000 fpm or more. The paperboard blank has a caliper from about 10 to about 25 mils in preferred embodiments, and in any event a caliper of at least about 5 mils. Likewise, the paperboard blank is made from paperboard having a basis weight of from about 150 to about 250 lbs per 3000 square foot ream and is a scored paperboard blank.
Suitably, the process is operated at a production rate or frequency of at least about 40 cycles per minute.
It is thought that advantages of the invention are or may be: increased press productivity; reduction in blank misfeeds; reduction in or removal of air turbulence and static electricity (if present) created by friction in reciprocal operation of the die set; evacuation of moisture from the die set; and the ability to inject release agents and/or additives, such as fragrances and deodorizers, directly into the die set.
Referring now to FIGS. 1 and 2 , there is illustrated a plate 10 made from a substantially planar paperboard blank. Plate 10 includes a planar bottom 12 , a first transition 14 , a sidewall 16 , a second transition 18 and an arcuate outer flange portion 20 . Optionally provided is an outer evert 22 which provides additional strength to the container. Pressed paperboard containers such as plate 10 typically include a plurality of pleats such as pleats 24 , 26 , 28 and so forth because of the excess paperboard located in a circumferential direction when a flat blank is formed into the shaped product, as will be appreciated by one skilled in the art.
Referring to FIG. 3 , a container such as plate 10 is typically formed in an automated pressware apparatus which includes a plurality of die sets, each including a punch and a die such as die 30 . Die 30 is mounted on a mounting plate 32 and is optionally a segmented die including a draw ring 34 , a knock-out 36 and a pair of forward blank stops 38 , 40 as is shown. A flat paperboard blank is generally passively fed to die 30 by gravity, guided along a production direction 42 by blank guides 44 , 46 . The die set is typically inclined with respect to horizontal at an angle between 30° and 60° such as 45° so that blanks and product are advanced by gravity along an inclined feed path in plane 42 as is well known. However, pursuant to this invention, instead of relying solely upon a passive gravity feed system, it has been found that higher blank feeding speeds and more reliable press operation are achieved by pneumatically propelling the blank into the die set as is illustrated in FIGS. 4 , 5 , 6 and 7 .
As shown in FIGS. 4 and 5 , the improved apparatus includes generally a pressware die set 52 including a punch 54 driven by a forming ram 56 , as well as a die 30 and a blank feeding station 60 . Punch 54 includes a knock-out 62 , a pressure ring 64 , and a punch base 66 . The knock-out is optionally spring biased as shown. Die 30 has draw ring 34 , knock-out 36 as well as base 68 which defines a contour transferred to the blank in order to form the container.
As shown in FIG. 5 , included in the blank feeding station 60 are optional stop pins such as an optional stop pin 70 , as well as an optional damper plate 74 along with a pair of air knives 80 , 82 . Optional damper plate 74 may be positioned either before or after air knives 80 , 82 . As shown in FIGS. 4 and 6 , air knives 80 , 82 are adjustably mounted on respective supports 84 , 86 such that their outputs form angles 88 , 90 , respectively ( FIG. 6 ) with respect to production direction 42 which is parallel with the inclined plane of the feed station indicated at 92 in FIG. 6 .
As shown in FIG. 6 , plane 92 is typically and conventionally inclined with respect to a horizontal indicated at 94 such that blank 100 are gravity fed to pressware die set 52 . The angle of inclination 96 may be anywhere from about 30 to about 60°; typically at an angle of about 45° with respect to horizontal. Angle 88 is suitably about 5°, or in other words, the output of upper air knife 80 makes an angle of about 50° with a horizontal when the feed path is inclined 45°. Angle 90 is suitably about 30° such that the output of lower air knife 82 makes an angle of about 15° with respect to a horizontal (75° to vertical) when the feed path is inclined to 45°. It will be appreciated that the angles of incidence on the paperboard blank can be selected for different paperboard weights, angles of inclination, operating speeds or equipment. The angle of incidence from the jet below the feed path is typically greater than the angle of incidence from the jet above the feed path; that is to say, angle 90 is suitably larger than angle 88 . Angle 90 may in some cases be quite high if significant lift is needed in connection with propelling the blank into the die set.
An inclined feed path in the plane indicated at 92 extends in production direction 42 as indicated in FIG. 6 . The inclined feed path extends in between air knives 80 , 82 and has on upper side 112 where knife 80 is located on the same side of the plane as the punch and a lower side 114 where knife 82 is located on the same side of the plane as the die. Angle 88 is thus defined as an oblique angle of incidence which may be from 1° to 35° such as from 2° to 10° or from 3° to 7° with respect to the inclined feed path. Angle 90 is likewise an angle of incidence which may be from 5° to 60° such as from 10° to 50° or from 20° to 40° with respect to the inclined feed path. The angles are measured or adjusted using a digital protractor, for example, on the air knife casing which is parallel with the central axis of the issuing jet.
FIG. 7 shows a plurality of feed stations 60 , each holding blanks 100 , and each having upper air knives 80 to propel blanks 100 into pressware die set 52 . The axes of the slots of the air knives 80 and 82 (not shown) extend in direction 43 substantially perpendicular to the production direction 42 .
Referring again to FIGS. 4 , 5 and 6 , in operation, paperboard blank 100 is gravity-fed or mechanically fed to feed station 60 where it is optionally stopped with a pin such as pin 70 mounted on the forming ram. Damper plate 74 helps limit bounce-back of blank 100 when it is stopped in feed station 60 at feed plane 92 in anticipation of the feed step.
The feed step begins after the previous container has been formed and removed. During the feed step, air knives 80 , 82 are activated and supply air blasts incident on blank 100 as shown schematically in FIG. 7 . The air blasts are at angles 88 , 90 with respect to direction 42 and feed plane 92 and operate to accelerate the blank and propel it into die set 52 , where the blank is formed into a container such as that shown in FIG. 1 . As will be readily recognized, it may be possible to use a single air knife 80 or 82 above or below feed plane 92 to implement the invention, and multiple air knives in combination may be positioned above or below feed plane 92 . In addition, the air knives preferably will be provided with means to adjust and control jet velocity, direction, and flow pattern to take into account the configuration of feed station 60 and blank guides 46 , and the dimensions of blank 100 , such as blank shape, width, thickness, surface friction, and weight.
A suitable air knife for upper or lower application is an Exair® Super Air Knife manufactured by EXAIR Corporation, Cincinnati, Ohio. Such an air knife is typically operated with an input air pressure of from about 40 to 80 psig. Other pressures are also suitable. Further information may be found at http://www.exair.com/airknife/sak_page.htm, Jun. 6, 2006, the disclosure of which is incorporated herein by reference. In one mode of operation air knife 80 is operated at 40 psi while air knife 82 is operated at 20 psi. The air knife may have the flow pattern shown in FIG. 8 , where the jet issuing from the knife has a “spread” or a characteristic jet height of about 5″ at one foot, although other spreads may be used. The jet velocity will typically be in excess of 10,000 fpm, and preferably 14,000 fpm, when the air knife is operated with an input air pressure of 40 psig. A 3″ Super Air Knife is especially suitable for paperboard blanks having a diameter from about 6 to about 10 inches. This air knife has a characteristic force (measured on a 12 inch by 12 inch surface perpendicular to the jet flow path) of about 0.161 lbs. The force of the jet on the surface does not substantially change as the surface is moved away from the air knife at distances between 1″ and 12″. Suitably, the characteristic force is measured at 6″ from the air knife.
In practical applications, the invention may be utilized in a five station press 110 as is shown in FIG. 7 . In FIG. 7 , there are provided five die sets 52 adjacent five blank feed stations 60 , each of which has a pair of air knives as described above.
Simultaneously with propelling blank 100 , air knives shown in FIGS. 3 through 8 may also, optionally, be used to reduce, remove or clear air turbulence created by reciprocal operation of pressware die set 52 thereby facilitating insertion of blank 100 ; to evacuate heat and moisture from die set 52 to better control the pressing environment; and to inject lubricants, coolants and other chemicals or substances in aerosol form into the die set to facilitate or enhance pressing or to impart desired characteristics to the pressed article; provided, however, all additives selected do not cause mold build-up or other operational difficulties.
The invention is still further illustrated in FIG. 9 which is a schematic timing diagram illustrating operation of the invention apparatus, it being appreciated that air knives, such as air knives 80 , 82 are controlled using a solenoid valve controller as indicated in FIG. 6 in order to synchronize the air knives with operation of the forming press. Any suitable controller may be used. In FIG. 9 , a forming cycle is represented in time by degrees of the operating cycle. At 0° the die set is fully open; at 135° the press hydraulic pressure is applied; at 180° the die set is fully closed for forming; at 225° the hydraulic pressure is released; and at about 265° the air knives are turned on, that is, the output jets are activated. The lower air knife remains on until about 295°, while the upper air knife remains on until about 305°. At 360° the die set is again fully open. Suitable ranges are also as follows:
TABLE 1
Air Knife On/Off Cycle Position
ON AT
OFF AT
Upper Air Knife
250°-280°
290°-320°
255°-275°
295°-315°
Lower Air knife
250°-280°
280°-310°
255°-275°
285°-305°
The knives remain active within the interval between on and off times selected from Table 1.
While the invention has been described in connection with several examples, modifications to those examples within the spirit and scope of the invention will be readily apparent to those of skill in the art. In view of the foregoing discussion, relevant knowledge in the art and references including co-pending applications discussed above in connection with the Claim for Priority, Background and Detailed Description, further description is deemed unnecessary.
|
An improved apparatus for making disposable pressware features a pneumatic feeding system which accelerates a paperboard blank into a forming die. In a typical embodiment, a pair of adjustable air knives propel a paperboard blank into the forming cavity.
| 1
|
TECHNICAL FIELD
The present invention relates to molded plastic chambers for receiving and dispersing water in soil or other granular media, in particular to end closures for such.
BACKGROUND
Buried leaching chambers are most commonly used for dispersing wastewaters beneath the surface of ground. Such type chambers may also be used for draining earth or other media. Buried stormwater chambers are used for receiving water, typically from storm, retaining the waters, and then dispersing them, usually by percolation. Commercially popular chambers of such types are made of molded thermoplastic, most commonly by injection molding. Typically they have arch shape cross sections and are coupled end to end at joints to form a string or row of chambers. The ends of the first and last chambers of a string or row have to be closed by end plates or end caps, to keep the surrounding media from entering the chambers.
Water is typically flowed into the chamber at the first end of the string; and thus it is common to have a provision in the end plate for receiving one or more influent flow pipes, which may approach at no particular angle. At times, it is necessary to connect one chamber string to another spaced apart string, where the second string which might run parallel, perpendicular, or at some other angle to the first string. That connection between such chamber strings is frequently made by means of drainpipes penetrating the endplates.
For instance, U.S. Pat. No. 5,839,844 for a leaching chamber endplate and U.S. Pat. No. 5,017,041, for a leaching chamber, both to Nichols et al., show different kinds of flat endplates, which attach to the end of the chamber. As shown by the patents, in the prior art, provisions have been made in endplates, such as a cutout hole, or an embossing for a hole-cut, with the expectation that a pipe will lie substantially parallel to the axis as the chamber. In the prior art, when the drain pipe does not lie close to the extension of the lengthwise axis of the chamber, then plumbing fittings in the drain pipe are used, to make the connection. Particularly in leaching chamber applications, where the wastewater tends to carry solids, it is desirable to minimize any sharp bends in the drain line. It is desirable, for reason of labor and material costs to avoid plumbing work at the job site and to speed installation.
SUMMARY
An object of the invention is to provide an end cap for an arch shape cross section chamber which enables easy connection of pipe lines coming toward the chamber at varying angles, and which thus minimizes the number of fittings necessary in the drain line. A further object is to provide such an end cap in a form which is structurally strong, is adapted to economical plastic molding, and which can be nested for economic shipment.
In accord with the invention, an end cap for an arch shape cross section leaching chamber or storm water chamber, has an end flange for engaging the end cap with a chamber; a base flange for supporting the end cap on soil; a shell, preferably a convex exterior surface shape dome, connecting the base flange with the end flange; and at least one buttress, preferably a multiplicity of buttresses, extending outwardly from the exterior of the dome shape surface, and running upwardly from the base flange. Each buttress has a surface portion, preferably an essentially planar surface portion, which is adapted for receiving a pipe through which water may be flowed to or from the interior of the end cap.
Preferably, the end cap is comprised of five buttresses. There are first and a second buttress having planar surfaces facing in opposing y axis directions, and a third buttress having a planar surface facing in the x axis direction, i.e., of the lengthwise axis of the end cap, which corresponds with the lengthwise axis of a chamber to which the end cap attaches. Fourth and fifth buttresses are interspersed between the first, second and third buttresses. They face at angles intermediate to the other buttresses, preferably at nominally 45 degrees angles to the x axis in the x-y plane of the base flange of the end cap.
Preferably, the buttresses run down to the base flange, and at least one of the buttresses has a step formed by slightly displaced planes running along the face of the buttress. The step forms a saddle for supporting a pipe inserted in a hole in said planar face. And a sub-saddle bisects the saddle, to support a pipe having a substantially smaller diameter than the pipe which is supportable by the saddle. Preferably, at least one buttress has three slightly displaced planes, to form two steps therebetween and two saddles, one for supporting a pipe at a high elevation near the top, and one for supporting a pipe near the base flange. Preferably, the planar face of the buttress has an embossed seal with a pull-tab, so a circular piece can be torn out of the face, to create a hole for a pipe. Preferably, the base flange of the end cap, in front of a planar face of a buttress, has perforations for receiving the tabs of a splash plate which projects into the interior of the end cap.
The foregoing and other objects, features and advantages of the invention will become more apparent from the following description of preferred embodiments and accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows an end cap in isometric view along with associated orthogonal reference axes.
FIG. 2 is a longitudinal vertical centerline cross section through the end cap of FIG. 1 .
FIG. 3 shows a portion of a buttress, with a seal that can accommodate different diameters of pipes.
FIG. 4 shows a splash plate, which optionally may be connected to the base flange of an end cap.
FIG. 5 is a partial isometric view of an end cap comprising planar surface housing
DESCRIPTION
U.S. Pat. No. 5,839,844 “Leaching Chamber Endplate” of Nichols et al. and U.S. Pat. No. 6,602,023 of Crescenzi et al., also entitled “Leaching Chamber Endplate” disclose details of how leaching chamber endplates are used in combination with chambers. U.S. patent application Ser. No. 09/949,768, “Storm Water Management System” of Krueger et al., filed May 4, 2001, and related application Ser. No. 10/402,408, filed Mar. 28, 2003, describe stormwater chamber and end plate use. See also patent application No. 10/677,938 “Corrugated Leaching Chamber” of the present applicants Brochu, Burnes and others, filed on even date herewith, which describes a new corrugated leaching chamber, with which the end cap of the present invention is particularly useful. The end cap of the present invention can be used with the chambers described in the foregoing patent applications and the other patents referenced therein. The drawings and descriptions in the foregoing patents, which are commonly assigned herewith, are hereby incorporated by reference.
FIG. 1 is a perspective view of an end plate 20 . FIG. 2 is a vertical centerplane cross section of the end cap. Endplate 20 has a flanged base 22 , for supporting the end cap against vertical load when it is attached to the end of a leaching or stormwater chamber. The end flange 24 is curved, and shaped for attachment to a continuous curve semi-elliptical cross section chamber like that described in the aforementioned Krueger et al. and Brochu et al. patent applications. Other shape of end flange may be used, to mate with other chamber end cross sections, such as those shown in the patents referenced above.
The shell 46 of the end cap has the essential shape of a dome, that is an inward curving structure, from which buttresses project. Transition section 28 leads from the curved dome surface 46 to the end flange. Corrugation 26 runs transversely to the longitudinal x axis of the end cap and to the chamber to which it mates, for strength. Five buttresses 38 L, 38 R, 38 C, and 40 L and 40 R rise from the dome surface 46 , to present planar surfaces, or facets, where pipes may be made to penetrate the end cap. Such pipes will be used to deliver or remove liquid from inside a chamber to which the dome is attached. Generally, large diameter pipes are associated with gravity flow systems. Sometimes, liquid is introduced by pump pressure, and smaller diameter pipes suffice. The suffixes L and R designate mating buttresses on opposing sides of the vertical lengthwise x-z centerplane. Suffix C designates the center buttress. The three buttresses 38 are similar, as are the two buttresses 40 . Buttresses 40 are smaller than buttresses 38 , to provide sufficient curved dome area between buttresses 38 , which gives the end cap adequate structural strength without the need for strengthening ribs.
FIG. 1 and 2 show that end flange 24 lies in the vertical y-z plane; and that bottom flange 22 lies in the horizontal x-y plane. The bottom flange runs from the bottom ends of the end flange, along the bottom of shell 46 , and extends outwardly from the y-z plane. Fig. 1 shows how buttresses 38 L, 38 C, 38 R, 40 L, 40 R and their outward-facing surface portions run upwardly from the bottom flange 22 .
The buttresses have several features in common, as follows. Referring to buttresses 38 , each has an essentially planar region 34 , shaped in dimension sufficiently to receive a selected diameter pipe running perpendicular thereto. Typically, the end cap is provided without any hole in buttress region 34 , and the installer in the field makes openings where pipe connection is desired. For instance, a hole saw or knife may be used to selectively remove a portion of region 34 and create a circular hole through which a pipe may enter. As shown in FIG. 3 , region 34 is preferably embossed or scored, to define different diameter circles C 1 , C 2 and C 3 . The plastic segments within one of the circles are removed by means of pull-out tabs 66 to create a suitable opening. An embossed or otherwise configured hole is often referred to as a seal or seal assembly. Obviously, a close fit with the pipe is desired, to prevent infiltration of soil. For examples of seals that may be used, see U.S. Pat. No. 5,882,014 to Gavin and the references thereof. Preferably, end cap 20 has a seal like those described in patent application No. 10/677,769 “Pipe Seal Made of Molded Thermoplastic” of Brochu et al, filed on even date herewith, the disclosure of which is hereby incorporated by reference. In the generality of the invention, the surface portions of buttresses 38 , 40 which receive pipes need not be planar, but may have other more complicated or contoured shapes
When a certain larger diameter pipe 60 , shown in phantom in FIG. 2 , is passed through an opening created in region 34 , inward penetration of the pipe is limited by contact of the top portion of the pipe with molded stop 42 . Buttresses 40 have similarly configured stops. Buttresses 38 L, 38 R have differently shaped, but analogously functioning, molded in stops 44 L, 44 R.
The exterior planar surfaces of all the buttresses are essentially vertical, having a slight slope inward, toward the vertical z axis, at about a six degree angle A, so that end caps will nest with each other for compact shipment. See FIG. 2 . Similarly, the sides of the buttresses slope inwardly at an about six degree angle B from the vertical. See FIG. 3 . When viewed head-on, the planar face of buttress 38 has the nominal shape of a truncated triangle with a curved apex. See FIG. 3 . The sides, face and top of buttresses may be shaped differently, for instance, with non-curved top, with differently sloped sides and face, in the context of the generality of the invention, where a buttress is structure attached to and projecting from the surface of an endplate, to provide a nominally vertical surface for a pipe connection.
The buttresses have molded in saddles 56 , 52 , for supporting pipes against vertical down loads. The saddles result from by slightly displaced planar segments of the essentially vertical faces of the buttresses. Buttresses 38 have three displaced planar portions, while buttresses 40 have two.
Saddles 56 on buttresses 38 are comprised of two spaced apart pads, bisected by sub-saddle 52 . Each buttress 38 has two sets of such saddles, so pipes may be received and supported near the base and near the top of the end cap.
As will be appreciated from FIG. 3 , saddle 56 will support any of the pipes having diameters of circles C 1 , C 2 or C 3 , or in-between. For example pipes of nominally 3 and 4 inch diameter will be supported on saddles 56 . Sub-saddle 52 of buttresses 38 provides support for a smaller diameter pipe, for instance a nominal 1 to 2 inch diameter pipe, which might be a pressure dosing pipe. Buttresses 40 have similar but continuous saddles 56 A. Different combinations or configurations of saddles may be used. In the generality of the invention buttresses may have a simple planar face and no steps and no saddles; and, the term “planar facet surfaces” is intended to encompass surfaces which are only essentially planar, and not perfectly planar. For instance, regions 34 can curve inwardly slightly as they rise upwardly; or they might be somewhat concave or convex.
The five buttress design of end cap 20 is preferred for maximum flexibility in the field. The faces of buttresses 40 run at 45 degrees to the lengthwise centerline or x axis of the end cap, when looking down into the x-y plane. The opposing faces of buttresses 38 R and 38 L lie along the y axis; thus are parallel to the x axis. The face of buttress 38 C lies along the x axis. The combination of corrugation 26 , buttresses, and saddles, provides good strength to the end cap, to support vertical loads, without interior ribbing of the type commonly known as necessary heretofore. Thus, the end caps nest well for shipment.
Other combinations of buttresses may be used. Compared to chamber 20 , in the generality of the invention, fewer buttresses, and buttresses having planar faces running at different angles than 0, 45 and 90 degrees to the x axis may be used. For example a faceted end cap may have only two buttresses, for instance, buttress 38 C and 38 R, running at 90 degree angles, or some other angle. Alternately, buttresses 38 may be present without buttresses 40 . Other variations in buttress arrangement and configuration will be apparent. In the generality of one mode of the invention, there is at least one buttress, 38 or 40 , having a stepped face to provide saddles. Buttresses may be mounted
A pipe which penetrates through an appropriate good fit hole in region 34 may be angled relative to the nominal plane of region 34 of a buttress, by as much as 10–20 degrees. This is achieved by making the buttresses interior dimension sufficiently wide at the point where the pipe is located, so the buttress sidewall allows the pipe stub inside the chamber to move sideways. The bendable character of the sheet material, which comprises region 34 , also enables the motion. Thus, with the preferred embodiment, pipes coming from virtually 180 degree arc direction can be accommodated.
Bottom flange 22 has a vertically extending fin 62 for strengthening. Apron areas 54 in front of the bases of buttresses 38 provide further “footprint” for bearing vertical loads. Two slots 48 , for receiving the tabs of a splash plate 50 , are present in the apron areas 54 of the base flange, at the bottom of the front face of each buttress 38 . Other slots, not shown, may be present with respect to buttresses 40 . Optional molded splash plate 50 , shown in FIG. 4 , has two tabs 64 , shaped to fit into the slots 48 . In the field, splash plate 50 is placed beneath the bottom flange of the end plate so it extends into the interior of the chamber, as illustrated in FIG. 2 . Splash plate 50 helps prevent erosion of underlying soil, when water drops from a pipe inserted into an upper elevation buttress opening.
In use, the end cap is attached to the end of a leaching or storm water chamber. One or more of the embossed regions is pulled out, suitable for the diameter of pipe being used the opening so it contacts the stop, where there is a stop associated with the opening. The chamber is then covered over with gravel, soil or other media and water is flowed from the pipe into the interior of the end cap and the chamber.
The stepped configuration of the buttress face, which provides the saddles for pipes, which have been described, may be applied to articles other than end caps, for instance, to chambers, distribution boxes, and any other molded articles where pipes are connected.
The stepped configuration of the buttress face, which provides the saddles for pipes, which have been described, may be applied to articles other than end caps, for instance, to chambers, distribution boxes, and any other molded articles where pipes are connected.
The preferred end cap is made of injection molded thermoplastic, such as polypropylene or high density polyethylene, materials well known in the art, with a wall thickness which will vary with location, but will typically be in the range 0.090 to 0.125 inch. Other thickness may be used; as may other materials of construction, for example, structural foam plastic.
The shell 46 is preferably a convex continuous curved dome surface, as has been shown. In the generality of the invention, other shape surfaces may be used to form shell of the end cap. For example, FIG. 5 shows a major portion of end cap 20 A, where shell 46 A comprises slanted planes, which converge at the top 27 of the end cap. Three planar sided buttresses, two of which are shown, 38 LA and 38 CA, extend upwardly from the base flange and outwardly from the surface of shell 46 A. As with the preferred embodiment end cap 20 , less or more buttresses may be present on end cap 20 A. When present, small buttresses, like buttresses 40 , will strengthen the planar parts of the shell which run between the larger buttresses.
Although this invention has been shown and described with respect to one or more preferred embodiments, and by examples, those should not be considered as limiting the claims, since it will be understood by those skilled in this art that various changes in form and detail thereof may be made without departing from the spirit and scope of the claimed invention.
|
A molded thermoplastic domed end cap, for attachment to the end of an arch shape cross section leaching chamber or stormwater chamber, has a multiplicity of buttresses, to provide facet surfaces where pipe connections may be made. The essentially planar surface portions have tear out or cut out regions, for pipe openings. The buttresses face in different directions, relative to the longitudinal axis of the end cap, to conveniently accommodate pipes running in different angular directions. Pipes, which pass through openings in the surfaces of the buttresses, are supported by molded in step-saddles of the buttresses. Molded in stops limit inward motion of pipes.
| 4
|
FIELD OF THE INVENTION
The invention relates to braided line splices including slipping and non-slipping braid splices and butt splices, as well as methods for making such splices in braided line.
BACKGROUND OF THE INVENTION
Braid line or rope splicing has been in common practice for many years. Braid splices are used in various occupational and utility contexts, one of the most common of which is in maritime occupations or recreational boating. For simplicity, but without limitation, the background and the description of the invention herein disclosed and claimed will be primarily in that context. Such applications include use with mooring lines, sail reefing lines, sail cover ties, fender lines, adjusting lines for boat tops such as bimini tops, anti-chafe sleeves, and stevedoring. However, some aspects of the invention are useful in personal, household and other workplace areas ranging from belts to shoe laces, eyeglass ties, chin straps, mask retainers, tool retainers, various tie-downs from trash cans to car-top carriers and equipment covers, and even medical applications as tourniquets.
Braided line splicing is typically used to join two pieces of braided line together. A closed loop or eye may be formed in the end of a braided line so that the eye can be used to either be placed over an object such as a bollard or cleat, or, after the eye is formed, to have the bitter end of the line reeved through the eye to form a loop which can then be placed about an object so that the line has the eye end loop secured to the object. The remainder of the line is then used to either secure the object, control its movements, or provide the opportunity for the line to then be secured to another object which is in that manner secured to the first object; and various modifications of these basic arrangements.
The basic commonly-used techniques of splicing braided line are well known by most sailors as well as longshoremen. There are numerous seamanship manuals used to teach the art of working with all types of lines, including braided lines. Information, including comprehensive instructions for braiding, is also commonly provided by various braided-line manufacturers. In addition, there are numerous patents showing various arrangements, tools and methods for such braiding to form splices. Some examples of such patents are noted and described below.
U.S. Pat. No. 4,099,750-McGrew discloses a method of forming an eye splice in a double braided line wherein the fid or other tool may open up the braid and allow the end of the line to be drawn through the braid to form the loop. After the loop is formed, the core and sheath of the line are alternately pulled to tighten the crossover of the core and sheath and bury them in the sheath to complete the splice. Once so completed, the eye is then fixed as to its size.
U.S. Pat. No. 4,974,488-Spralja discloses a splicing apparatus and method for braided line. A fid is used to pass through the braid and draw the end of the line through the braid to form the splice. This eye is also then fixed as to its size.
U.S. Pat. No. 5,062,344-Gerker shows an eye splice used with a looping bight in one end of a hollow braid type of cord. The bight in the free end of the cord is folded back to form the eye of the looping bight. The free cord end of the bight has an eye spliced therein with the cord end extending through the braided wall of the cord at an entry point, then through the center of the cord to a take-out point, and then outwardly through the wall to provide a cinch loop or eye through which the standing part of the cord is passed. Essentially, this disclosure is that of a small, tight, fixed eye spliced into the cord free end by use of a previously well-known splicing technique, with the standing part of the cord being routed through the fixed eye to form a "lasso" type of slipping loop.
U.S. Pat. No. 4,036,101-Burnett also shows a fixed eye splice in a double braided hollow rope assembly.
An extensive search made in the U.S. Patent and Trademark Office through various subclasses of the Patent Office classification Classes 24, 28, 57, 87, 119 and 403, did not turn up any better background art than those patents noted above.
SUMMARY OF THE INVENTION
The invention involves a family of slipping braid splices, and the process or method of forming such splices. The splices employ integral or separate braid sleeves, formed from and as a part of a braided line sheath by an inversion process which is a part of the invention, in conjunction with one or more suitable cores. The inverted braid sleeve is a portion of the braid sheath that encloses and grips the core of a double braid line. It also may be a portion of a hollow braid which has been inverted. The use of hollow braid in practicing the invention will be described later. Under longitudinal tension, the inverted braid sleeve contracts in diameter, producing a gripping force on the enclosed core. When the inverted braid sleeve is compressed longitudinally, it expands in diameter, releasing its grip on the core. By applying such longitudinal compression to the inverted sleeve, the gripping sleeve is loosened from the core and can be moved to a desired location on the core. By then applying such tension to the sleeve ends, the gripping sleeve is fixed at that desired location on the core. When, with a splice used to form a closed loop such as an eye or a round or oval loop, it is desired to change the closed-loop size, such compression is once again applied to the sleeve ends, the gripping action of the sleeve is released from the core, and the sleeve and core are then moved relative to each other to either enlarge the closed loop diameter or reduce it. Once it is positioned to the desired size, the splice is again subjected to such tension as noted above, and the gripping sleeve once again grips the core.
The inverted braid sleeve can be an integral part of the double braid; that is, with double braid, the sleeve is a portion of the sheath with the core removed in order to permit insertion of the end of the double braid as a core. In order to retain the full strength of double braid at the splice section, the core is removed from the length of the sheath that will be inverted. After the sleeve is formed, the core is reinserted in the sheath except for the sleeve section where it parallels the sleeve, thus retaining the full strength of the double braid.
With hollow braid, different sections of the sheath function as the inverted sleeve and as the core. When the sheath and the core of the double braid are separated, they can each function in the same fashion as hollow braid.
Specific physical properties are required for successful inversion of a braid sheath. For example, the expanded internal diameter of the braid sheath must be slightly more than the compressed diameter of the core material so that the compressed core can pass through the expanded sheath during the inversion process. A related requirement for successful operation of the slipping splice is that the tip of the core must be slightly smaller than the expanded sleeve internal diameter in order to permit easy insertion and removal. Likewise, the expanded diameter of the sheath must not be substantially greater than the diameter of the core, or it will have no effective gripping action as a sleeve. Other factors to be considered are the frictional properties of the core and the sheath, the length of the sleeve, and the number of wall openings. Staple fibers result in a fuzzy surface with higher frictional or gripping qualities, while fine multifilament fiber bundles lower friction. Tightly twisted, denser fiber bundles provide better gripping action. The relatively slick, coarser fibers of traditional polyolefin hollow braid are relatively slippery and their use is not advised where higher gripping action is needed.
The method or process aspect of the invention includes the formation of suitable readily accessible openings in the wall of the braid sheath or jacket in order to form the splice sleeve. This is referred to herein as an inversion process, in which a portion of the braid sheath is inverted or turned inside out to form the sleeve. A temporarily-existing eye splice is formed in a hollow braid sheath by inserting a compressed braid tip through the sheath wall, using a fid if desired. The braid tip is pushed through the center of the braid sheath to the desired sleeve length and then passed out through the braid sheath wall. The tightly twisted strands forming the braid sheath are sufficiently large and well formed that the braid tip passes between the strands instead of splitting them. The braid tip is pulled as it exits from the sheath so that the braid core is pulled through the sheath portion that forms the sleeve, gradually reducing the size of the temporarily-formed splice eye. With continued pulling, the splice eye disappears at the entrance point to the braid sleeve. Still further pulling causes the section of the braid sheath to invert or turn inside-out as it is also pulled through the exit point, forming the inverted sleeve.
This creates a pair of well-defined openings in the braid sheath at the entry and exit points of the sleeve. The openings of a pair face in opposite directions either on the same or on opposite lateral sides of the braid sheath. These inversion-created openings provide permanent and easily accessible entry and exit points to form the braid splice. In addition to this pair of entry and exit openings, there are additional secondary openings on the opposite side of the braid sheath from the respective entry and exit points. These secondary openings face in the opposite directions from the primary openings. These secondary openings are an essential feature for some splice applications.
The entry and exit points can be placed on the same or on opposite sides of the braid sheath depending upon the end use requirements. The length of the sleeve can be varied, and a plurality of sleeves can be created and used. If the inverted sleeve is located near the end of the braided length of line, it is desirable to have a tab or tail on the end of the sleeve to assist in tensioning or release of the splice. At times, the tab is all that remains of the standing part. See the closed-loop belt splice of FIG. 12, for example. The tab is particularly useful in such a splice.
In the limiting version of the braid splice, instead of inserting the braid tip through the sheath wall and passing it through a length of the sheath before exiting to form the sleeve by inversion, the tip is inserted directly through the sheath, exiting on the opposite side. The inversion process now produces a well-defined "hole" in the braid sheath. These "holes" can be used to insert braid cross-members to form a bridle which may be used, by way of example, as a set of ties for a mainsail or a cover for a trailer boat or a tarpaulin.
After the sleeve has been formed by the inversion process, the braid splice is formed. It may be a butt splice or a closed-loop splice such as a belt splice or an eye splice. The butt splice is used to join two lengths of braided line, which may be adjusted or even taken apart when desired. The belt splice is particularly useful as an slipping splice which retains its adjusted position upon being tensioned, but is easily released for adjustment. Its closed loop is oval or rounded. The belt splice may also be made as a non-slipping double belt splice which has a significantly higher gripping power than the slipping belt splice. The eye splice may be either a slipping version or a non-slipping version. Its closed loop is tear-drop shaped. A braid splice embodying the invention may be an integral splice which involves a braid sleeve that is an integral part of the braid sheath, with the main body of the braid functioning as the braid core. In a modified arrangement, the braid splice may be a separate splice having a joined pair of separate braid sleeves that utilize separate cores, or in the case of butt splices, one, two, or more pairs of separate braid sleeves using separate cores. When using a butt splice to join two braided lines, each line has one or more braid sleeves and also provides one of the cores. Similar splices may be used to join more than two lines together at the splice junction.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 through 7 are schematic representations showing the steps of making an inverted sleeve in a length of braided line, after which a closed loop splice or a butt splice may be made, all in accordance with the invention.
FIG. 1a shows a typical fid that may be used as desired.
FIG. 8 schematically shows a slipping belt splice forming a belt having a rounded or oval closed-loop and securing the belt ends together.
FIG. 9 is a somewhat schematic representation of an integral closed-loop adjustable braid eye splice of the slipping type embodying the invention.
FIG. 10 is a similar representation of another braid eye splice embodying the invention, the braid splice being an integral closed-loop eye splice of the non-slipping type.
FIG. 11 is a similar representation still another slipping braid closed-loop eye splice embodying the invention, the slipping braid splice being a joined-pair-of-separate-sleeves eye splice.
FIG. 12 schematically shows a closed-loop belt splice of the separate sleeve type.
FIG. 13 schematically illustrates a closed-loop belt splice using an integral inverted sleeve and embodying the invention.
FIG. 14 schematically illustrates a non-slipping but adjustable double belt splice.
FIG. 15 schematically shows an integral sleeve overlapping butt splice embodying the invention and joining two braided lines together.
DETAILED DESCRIPTION
In order to make the splices shown in FIGS. 8 THROUGH 15, one or more sleeves must be made in one or more lengths of braided line. These sleeves may be made in the manner illustrated in FIGS. 1 through 7. By first describing one of the splices to be made, there will be a better understanding of the need and manner of making the inverted sleeves which are requisite preliminaries to making a completed splice. Therefore, the splice in FIG. 9 will be first described to a sufficient extent that the disclosure of FIGS. 1 through 7 are better understood.
The integral eye splice 10 of FIG. 9 is made in a length of double braided line 12, which has a body 14 comprised of a core 16 and a jacket or sheath 18 surrounding the core. Splice 10 of FIG. 9 is a slipping eye splice. Line 12 has a standing part 20 extending beyond the splice 10 to form the tab, also identified as 20. Line 12 also has an end 22 commonly referred to as the bitter end of the line. The bitter end 22 has a tip 24 at its extremity.
The line standing end tip 24 is preferably smooth, somewhat rigid, and tapered. Its diameter is slightly smaller than the expanded diameter of the body of the braided sheath or jacket 18 where the splice is to be made. If the tip is not sufficiently rigid, a suitably sized fid can be used as a tip to perform the inversion which results in the formation of the splice sleeve. The formation of the splice inverted sleeve is shown in FIGS. 1 through 7 and will be described below.
The body of the length of line 12 has a bight 26 formed from a reversely bent or looped part of that body extending between the end 22 and the splice 10. Eye 28 is formed by the bight 26 of the line body 14 and the splice 10. In one typical use of a line having an eye splice in one end, the eye 28 is fitted over a bollard on a dock or pier and the standing part 20 is led aboard a boat through a chock and secured to a cleat on the boat. Before so securing it, the standing part is often gripped by the hands of a boat crewman or a shore hand, and the boat is pulled into position in relation to the dock before the standing part of the line is cleated. In this use, the line 12 is functioning as a mooring line or a dock line. It is therefore to be understood that the bitter end 22 is that portion of the line 12 which typically may connect the loop formed by the eye splice 10 to an object to which the line 12 is to be either secured or manipulated.
Before the slipping braid splice 10 of FIG. 9 is assembled, the inverted sleeve 40 is made. Referring now to FIG. 1, by first looping the line body 14 so that the braid tip 24 can be inserted, with the aid of a fid if desired, through the wall of the braided sheath 18 at a sleeve entry formed by opening 30. A fid 25 is shown in FIG. 1a. This can be done by the tip 24 if that tip is sufficiently rigid like a fid and is shaped like a fid, thus being fid-like. Any of several ways of making the braided line at the tip 24 more rigid may be used.
For example, when the braided line is made of a thermoplastic material such as Nylon or Dacron or similar synthetic fibers, the tip 24 may be heated to plasticize the thermoplastic braid strands and form the softened braid into the desired shape. A heated, shaped tip mold may be used for this purpose, or the plasticized tip may be manually rolled and shaped. The softened braid, when cooled, solidifies into a sufficiently hard tip to insert the tip 24 through the braided sheath wall, through the interior of the sheath, and then out of the sheath wall, all without the use of a fid.
Another way of making a sufficiently hard tip is by the use of a suitable adhesive or resin which will harden with the tip having been shaped to the desired tapered diameter. Some such adhesives are sold and used in marine supply stores as a liquid whipping for the end of a line. Thermoplastic or thermosetting resins can be molded to produce the desired tip.
In step A of the process of making the inverted sleeve 40, illustrated in FIG. 1, the tip 24 is inserted through the entry opening 30, which has been worked through the braided strands forming the braided sheath 18. In doing so, the closed loop 32 is formed by the part of the line body 14 between the opening 30 and the portion of the tip 24 entering that opening. In the process of inversion, the sheath also functions as the core in the forming of the sleeve.
In step B of the process of making the inverted sleeve 40, illustrated in FIG. 2, tip 24 is then pushed through the interior 34 of the braided jacket 18 in which the core 16 is located, as shown in FIG. 2, to the desired length of the sleeve 36 being created, either by pushing its hardened portion or by the use of a fid, or a combination of the two actions.
In step C of the process of making the inverted sleeve 40, illustrated in FIG. 3, tip 24 is then passed out through another opening 38 formed through the wall of the braided jacket 18 at sleeve exit 38. The braid strands of the braided jacket 18 are tightly twisted and sufficiently large and well formed so that the braid tip (and the fid if used) passes between the strands instead of splitting them as openings 30 and 38 are formed. Thus the braiding forming the sheath 18 is not weakened by this part of the method.
In step D of the process of making the inverted sleeve 40, illustrated in FIG. 4, the braid core 16 is then pulled through the sleeve 36, which is that portion of the braid sheath 18 between the sleeve entry opening 30 and the sleeve exit opening 38 as shown in FIG. 4.
In step E of forming the inverted sleeve 40, as the core 16 is pulled through the sleeve 36, the closed loop 32 is gradually reduced, as shown in FIGS. 4 and 5, until the loop disappears at the entry opening 30 of the braid sleeve 36, as shown in FIG. 6.
In step F of forming the inverted sleeve 40, continued pulling on the braid core 16 causes the section of the braided jacket forming the sleeve 36 to invert or turn inside out at the point of inversion 31 as it is then pulled through the exit opening 38, thus forming the inverted sleeve 40 as illustrated in FIG. 7.
This inversion process, when completed, results in step G of forming the inverted sleeve 40, which is the formation of a pair of well-defined entry and/or exit openings 48 and 44 at the sleeve entry and the exit points through which the core tip 24 has passed. These openings can be located on the same or the opposite diametrical sides of the braided line in lengthwise spaced relation along the length of braided line. This process also results in additional entry and/or exit openings 46 and 42 on the opposite inverted sleeve end from the openings 48 and 44. Openings 46 and 42 also face in the opposite directions. These openings are located on the opposite diametrical sides of the braided line so that openings 42 and 46 are respectively opposite openings 44 and 48. These two openings can be used for additional closures, an example of which is shown in FIG. 11.
As shown in FIG. 8, a closed-loop slipping belt splice may be made from a length of braided line 22 in which the inverted sleeve 40 has been made, as above described, near the end of the standing part 20 of the line. The tip 24 is inserted through the inverted sleeve entry opening 48 and exit opening 44 to form the slipping braid belt splice. In this arrangement, the standing part 20 and the bitter end 22 of line 12, on which tip 24 was formed, extend in opposite directions from opposite ends of the inverted sleeve 40 to form a round or oval closed loop 50, while, in the eye splice shown in FIG. 10, the standing part 20 and the bitter end 22 extend in the same direction from the sleeve 40 so that the closed loop 52 has an eye 28 which has a tear-drop shape. In FIG. 9, the standing part 20 and the bitter end 22 also extend in the same direction from the sleeve 40.
When used as a belt around a person's waist, for example, or around a package, it is readily adjustable to a smaller loop by pulling on the tip 24 while holding or pulling in the opposite direction on tab end 20. When the desired degree of tightness of the belt is attained, similar pulling on tab 20 and the part of the line body 14 forming the closed loop 50 near where the tip 24 is shown will cause the inverted sleeve 40 to grip the core 16 and any part of the line body located within the sleeve 40, preventing the closed loop from expanding. By pushing the opposite ends of the inverted sleeve toward each other, the gripping action is released, and the closed loop 50 may be expandably adjusted.
Returning now to the description of the eye splice of FIG. 9, the bight 26 is formed in the length of braided line between the inverted sleeve 40 and the bitter end 20. The tip 24 is then inserted in the entrance opening 42, pushed through the inverted sleeve 40, and exits the sleeve through exit opening 46. When tension is applied to the bitter end 22, the sleeve 40 slips on the core 16 because the sleeve 40 is not placed under tension by the bitter end 22. The eye 28 decreases in size until it tightly grips the bollard or other object enclosed by the eye. Additional tension on the standing part 20 causes the eye 28 to grip the enclosed object more tightly. The eye 28 can be enlarged by releasing the tension on the bitter end 22 and axially compressing the sleeve 40 to enlarge it by moving the ends 42 and 46 of the sleeve 40 toward each other.
The eye splice shown in FIG. 10 is similar to that of FIG. 9, but is a non-slipping eye splice. Similar parts have the same reference characters. In this configuration, the sleeve 40 is formed from part of the length of line 12 which is near the standing part 20, and the tip 24 is passed through the entry opening 48, through sleeve 40, and out through the exit opening 44. As can be seen by referring to FIG. 7, these two openings are on the same diametrical sides of the line 12. The non-slip action occurs because the sleeve 40 is tensioned by force exerted through the standing part 20, causing the gripping action of the sleeve to hold the part of line 12 adjacent the bitter end 22 in place within the sleeve.
The double-sleeve eye splice 10' of FIG. 11 is of the type that can be used on shoe laces or draw strings, by way of example. The two joined sleeves 40' and 40" are formed adjacently from the sheath body 18'. Line 12 is a separate core that can be similar to or quite different from the braid sheath which has been inverted to form sleeves 40' and 40" No inverted sleeves are made as a part of the line 12. The sheath body standing parts form tabs 20' and 20" and their corresponding adjacent openings 42' and 42" are at the exit ends of sleeves 40' and 40" formed from the sheath body 18'. The two sleeves 40' and 40" are joined together at the entrance openings 48' and 48".
The line 12 has both ends formed with tips 24' and 24" on the core 16. The core bitter ends 22' and 22" from which tips 24' and 24" are formed may be well beyond the exit openings 42' and 42", as indicated in FIG. 11. In this arrangement, the line 12 may be a shoe lace, so that the entire line body 14 forms the lacing section from the bight portion 26 and the tips are merely the shoe lace ends. The splice 10' is tightened so that the sleeves 40' and 40" grip the line parts extending therethrough by pulling the core bitter ends 22' and 22" in an outward direction as seen in FIG. 11. The splice is loosened by pulling at the juncture of the sleeve entrance openings at 48' and 48".
FIG. 12 illustrates a double-sleeve belt splice using separate sleeves 40' and 40" similar to the separate sleeves used in FIG. 11, but with the sleeves joined adjacent to their laterally opposed openings 46' and 48'. The sleeves have tabs 20' and 20" respectively adjacent their entrance openings 42' and 44". The length of line 12 forming the belt part of the assembly has tips 24' and 24" formed on its respective end bitter ends 22' and 22". Tip 24' is inserted into opening 44' through sleeve 40' and out through opening 46'. Tip 24" is inserted into opening 44" through sleeve 40" and out through opening 48". The belt closed loop 50' is defined by the continuous portion of the length of line 12 not within the sleeves 40' and 40" as well at the portions within the sleeves and the sleeves themselves. The belt is "buckled" by pulling on tabs 20' and 20" in opposite directions to tension the sleeves 40' and 40", and released by pushing these tabs toward each other to relax the sleeves 40' and 40".
FIG. 13 is similar to FIG. 12, but uses a self-contained or integral sleeve 40 formed near the standing part 20 of one line end. Sleeve 40 has an entrance opening 48 and an exit opening 44 through which the tip 24, formed on the other bitter end 22' of the other line end, extends so that the portion of the line within the sleeve 40 is gripped by that sleeve when tightened by longitudinal tension force applied to the tab 20 formed on the entry end of sleeve 40. The belt closed loop 50' is defined by the portion of the length of line 12 not within the sleeves 40 as well at the portion within the sleeve and the sleeve itself.
FIG. 14 schematically shows a non-slipping double belt splice embodying the invention. Instead of forming the tip and the gripping sleeve on the opposite ends of the braid, as shown in FIG. 8, the double belt splice uses tips 56 and 58 on the respective opposite ends of the braid, and suitably located inverted sleeves 60 and 62 adjacent the respective opposite ends of the braid. Tip 56 is inserted in the outer opening 64 of the inverted sleeve 62, and tip 58 is inserted in the outer opening 66 of the inverted sleeve 60, forming a belt with the two adjacent braid sleeves 60 and 62 being spaced apart. When the belt is tensioned, both sleeves 60 and 62 are placed in tension with resultant excellent gripping power. This splice is limited in decreasing-length adjustment since at a point in making such an adjustment the two sleeve ends 64 and 66 will meet and prevent further shortening of the belt. For most applications, the simpler belt splice of FIG. 8, even with its lesser gripping power, is quite adequate.
FIG. 15 shows a non-slipping double-sleeve butt splice 68 employing a similar technique to that shown in FIG. 14 to obtain significantly advantageous gripping power. An inverted sleeve 70, 72 is formed, by using a formed tip 74, 76 near each end of the two braid pieces that are to be joined. A fid may be used in forming the inverted sleeves 70 and 72 when desired, instead of using formed tips 74 and 76. The opposite tips 74 and 76 are respectively inserted into the corresponding inverted sleeve openings 78 and 80 in the two braid sections and out through the respective inverted sleeve openings 82 and 84. When tension is applied to the braid bodies 12 and 12' beyond the splice 68 connecting the now-joined braid sections, the splice has excellent gripping power. Whipping the exposed tips, or reinserting the tips into the braid sheath, provides a smoother splice. As an alternative, the tips can be inserted in the opposite ends of the splices, but this requires pulling the entire length of the braid sections through the corresponding sleeves. When tension is applied to the bitter ends of the braids, the sleeves are not placed in tension, but the two braid sleeves interlock, providing a secure butt splice.
When hollow braid is used, the sleeve is formed on one part adjacent one end, with that end becoming a formed end passing through another sleeve. In effect, in FIG. 9, the core 16 does not exist, so that the splice 10 comprises only the sleeve 40 through which another part of the hollow braid extends. This splice is then somewhat smaller in diameter than the splice shown in FIG. 9 because of the absence of the core 16, particularly in the area of the splice. It can be seen that other splices can be made of hollow braid which are comparable to the splices in the various FIGURES which are shown using double braid.
The invention may also be practiced with suitable braided line having the required compressed/expanded diameters. Such braids may be prepared for use in forming the splices shown and provided in a kit form. For example, a kit may include a suitable length of braided line (e.g., thirty feet of 5/8" braided line if a typical small craft dock line for which an eye on one end is to be constructed), a hardened tip such as is described above, or a fid, and instructions following the teachings of this disclosure on how to proceed to make either slipping or non-slipping tear-drop shaped eye splices or round or oval type eye, or belt, splices. The length of braided line may already have the inverted sleeve section or sections formed in it, or the instructions included may also include instructions for forming inverted sleeve sections.
Kits may also be provided with the line being small stuff in which the braided line is about the size of the typical shoe lace. The shoe lace may be laced onto the shoe and then the separate slipping braid splice such as that shown in FIG. 11 be used.
The disclosed and claimed splices have a broad range of applications. These include belts, laces, drawstrings, rigging, lashings, and numerous nautical functions. In many applications these splices are able to function in place of hook-and-loop fasteners, straps, buckles, knots and traditional splices.
|
Braided line splices and methods of making such splices using an inverted sleeve formed from a part of the braided line sheath, the steps forming the sleeve being at least a part of the method. The sleeve is formed by inverting it (turning it inside out), and then running a braided line part through the sleeve, tensioning the sleeve and having it grip the line part within the sleeve. Variations include making eye splices, both slipping and non-slipping; belt or loop splices, both slipping and non-slipping; and butt splices. Kits may be packaged which provide the necessary items and information to complete such splices.
| 3
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a magnetic resonance imaging apparatus of the type having a magnet with at least one patient receptacle and at least one support plate, as well as a predetermined number of transmit and/or receive coils, and which allows exposures with the subject in at least two predetermined exposure positions, with at least one exposure taking place using predetermined adjustment parameters.
2. Description of the Prior Art
In known magnetic resonance imaging apparatuses, for different exposure positions the associated exposure parameters must in general be modified at least partially. The exposure parameters that may have to be modified include e.g. the position of the support plate and the connection or disconnection of transmit and/or receive coils. As a rule, a modification of the exposure parameters requires a readjustment of the magnetic resonance imaging apparatus.
The adjustment essentially serves to optimize the RF chain (transmit and receive coils and associated amplifiers) and to optimize the homogeneity of the main magnetic field produced by the magnet (also called the basic magnetic field or B 0 field) in a volume under examination (imaging volume) located inside the patient receptacle. Due to the necessary homogeneity of the examination volume, this volume is also called the homogeneity volume.
The exposure parameters are also patient-dependent, since the patient represents an attenuation or damping for the transmit and/or receive coils. A precise adjustment thus also serves for patient safety with respect to the RF exposure.
In general, known magnetic resonance imaging apparatuses recognize automatically whether the. exposure parameters belonging. to particular exposure positions must be modified, and carry out a readjustment if warranted.
This adjustment normally requires 10 to 90 seconds per exposure position. Given certain examination procedures, this time is not available. This includes e.g. the tracking of doses of contrast agent over a larger body region that exceeds the available homogeneity volume of the nuclear spin resonance apparatus. In such cases, the patient must be guided by displacement of the support plate in a manner corresponding to the flow of contrast agent. If a smaller viewing field is not acceptable, the readjustment that is thereby required per imaging measurement (exposure) requires a multiple dosage of contrast agent, which is not desirable for the patient.
Alternatively to a smaller viewing field or to multiple injections of contrast agent, it is possible after the first adjustment to omit the further adjustments (readjustments) inherently required for high-contrast exposures. However, this leads to a considerable worsening of the image quality.
SUMMARY OF THE INVENTION
An object of the present invention is to provide magnetic resonance imaging apparatus of the type described above that provides high-contrast exposures in a short time, even given an examination of larger body segments.
This object is achieved in accordance with the principles of the present invention in a magnetic resonance imaging apparatus having a magnet and at least one patient receptacle and at least one support plate, as well as a predetermined number of transmit and/or receive coils. At least in two predetermined exposure positions, an exposure respectively takes place using predetermined adjustment parameters. The required adjustment parameters are inventively determined in a preceding adjustment process, and the exposures are executed in a subsequent exposure process.
For example, the exposure parameters can be modified by means of a spatial modification of position (longitudinal displacement, transverse displacement, rotation) of the support plate within the patient receptacle. Alternatively, or in addition, a modification of the adjustment parameters can take place by connection and/or disconnection of the transmit coils and/or the receive coils.
In the inventive magnetic resonance imaging apparatus, the required adjustment parameters are not determined immediately before each individual exposure, as is conventional. Rather, the required adjustment parameters are determined in an adjustment process that precedes the exposure process. Only after the determination of the required adjustment parameters are the exposures carried out, in a separate imaging exposure process.
The adjustment parameters are of course stored at least until the conclusion of the examination. The adjustment parameters thus can be used again, when identical or suitably similar exposure parameters (position of the support plate and configuration of the transmit and/or receive coils) are again reached in the context of the same examination.
In examinations with the inventive apparatus, high-contrast exposures are thus obtained, since it is not necessary to omit an adjustment. Due to the fact that the adjustment is carried out in a separate adjustment process, and the adjustment parameters are stored until the conclusion of the examination, the transmit and receive coils, or their coil elements, can be switched quickly during the examination, so that, in addition, reduced examination times result.
The inventive solution is suitable for a large number of different forms of magnetic resonance imaging apparatuses. Thus, for example, the magnet can be fashioned as a cylindrical magnet (solenoid) or as a horseshoe magnet (C-arm apparatus). Given cylindrically shaped magnets, the patient receptacle is fashioned as a patient tube.
DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic block diagram of a magnetic resonance imaging apparatus constructed and operating in accordance with principles of the present invention.
FIG. 2 schematically illustrates an embodiment of an apparatus in accordance with the invention, wherein the magnet which generates the basic magnetic field is a horseshoe magnet.
FIG. 3 schematically illustrates an embodiment of an apparatus in accordance with the invention, wherein the magnet which generates the basic magnetic field is a cylindrical magnet.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The apparatus in FIG. 1 has a support plate 1 that is arranged in longitudinally placeable fashion inside an examination volume of a magnet. Within the scope of invention, the magnet can for example a cylindrical magnet 18 as shown in FIG. 3 (solenoid) or a horseshoe magnet (C-arm) 19 as shown in FIG. 2 . Given cylindrically shaped magnets, the patient receptacle is fashioned as a patient tube as own in FIG. 3 .
The longitudinal displaceability of the support plate 1 is indicated with a double arrow 2 . Due to the longitudinal displaceability of the support plate 1 , larger body sections of a patient 3 lying on the support plate 1 can be examined.
The nuclear spin resonance apparatus shown in the drawing additionally has a predetermined number of transmit coils 4 and a predetermined number of receive coils 5 .
The transmit coils 4 can be connected, in a desired configuration, to a generator 7 by means of a transmit coil changeover switch 6 . The generator 7 supplies the transmit coils 4 with current via a-transmit amplifier 8 and via a matching element 9 .
The receive coils 5 can be connected, in a desired configuration, to a receiver 11 by means of a receive coil changeover switch 10 . The signals of the connected receive coils 5 are given to the receiver 11 via. a matching element 12 and via a receive amplifier 13 .
The configurations of the transmit coils 4 and the receive coils 5 , defined by the transmit coils changeover switch 6 and by the receive coils changeover switch 10 , are supplied to an adjustment unit 14 as inputs.
As a further input, the position of the support plate 1 , which is determined by a position sensor 15 , is supplied to the adjustment unit 14 .
The adjustment unit 14 processes the inputs that it has received from the transmit coils changeover switch 6 , from the receive coils changeover switch 10 , and from the position sensor 15 , and at its output supplies corresponding control signals to the generator 7 , to the transmit amplifier 8 , to the matching elements 9 and 12 , as well as to the receive amplifier 13 and to the receiver 11 .
In addition, the adjustment unit 14 supplies a control signal to a shim coil system 16 .
The inputs and the control signals (outputs) are stored, as adjustment parameters, in a memory 17 until the conclusion of the examination.
With the embodiment shown in the drawing of the inventive apparatus, larger bodily segments of the patient 3 can be examined. Such examinations are, for example, the tracking of doses of contrast agent over a larger body region, as carried out for example in subtraction angiography or in physiologically controlled imaging.
In the context of the preparation for measurement, which in the case of a peripheral angiography at the leg, includes slice positioning along the vascular tree, several measurements are already made without contrast agent. Due to the homogeneity volume of the magnet being too small, in these measurements the support plate 1 must be displaced, and so must be newly adjusted. The associated adjustment parameters for each position of the support plate 1 are stored in the memory 17 . As additional adjustment parameters, the connected configuration of the transmit coils 4 , as well as the connected configuration of the receive coils 5 , are stored in the memory 17 . In addition, the adjustment parameters include the corresponding control signals for the generator 7 , for the transmit amplifier 8 , for the matching elements 9 and 12 , as well as for the receive amplifier 13 , for the receiver 11 and for the shim coil system 16 .
After the conclusion of the measurement preparation, which includes the determination of the adjustment parameters, the support plate 1 is guided back into the initial position, and the contrast agent is administered. In the imaging measurement that now takes place, each of the positions of the support plate 1 used in the measurement preparation is newly set in succession, and the transmit coils 4 and the receive coils 5 are connected as in the measurement preparation. Subsequently, an imaging measurement (exposure). is immediately carried out with the known adjustment parameters stored in the memory 17 , i.e. without a new adjustment.
In the inventive apparatus, the required adjustment parameters are thus not determined immediately before each individual imaging measurement; rather, the required adjustment parameters are completely determined in a preceding adjustment process, in the context of the measurement preparation. According to the invention, the adjustment process thus precedes the exposure process. Only after the determination of the required adjustment parameters are the exposures (imaging measurement) carried out, in a separate exposure process. In examinations with the inventive apparatus, high-contrast exposures. are thereby obtained, since it is not necessary to omit an adjustment. In addition, due to the fact that the adjustment parameters are stored in a memory 17 until the conclusion of the examination, reduced examination times result. Due to the short examination times, in subtraction angiography the course of the contrast agent can thus be tracked without chronological gaps.
Although modifications and changes may be suggested by those skilled in the art, it is the intention of the inventors to embody within the patent warranted hereon all changes and modifications as reasonably and properly come within the scope of their contribution to the art.
|
A magnetic resonance imaging apparatus has a magnet with at least one patient receptacle and at least one support plate, as well as a predetermined number of transmit and/or receive coils. In at least two predetermined exposure positions, at least one exposure respectively takes place using predetermined adjustment parameters. High-contrast exposures can be obtained in a short time, by the required adjustment parameters being determined in a preceding adjustment process, and the exposures are carried out in a subsequent exposure process.
| 0
|
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority from U.S. Provisional Application Ser. No. 60/607,102, filed Sep. 3, 2004, the entire contents of which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The invention relates to low dielectric compositions, methods of use thereof in integrated circuits.
BACKGROUND OF THE INVENTION
[0003] The growth of Integrated Circuit (IC) technology is primarily based on the continued scaling of devices to ever-smaller dimensions. Smaller devices provide higher packing density and higher operating speed. In the ultra-large-scale integration (ULSI) era, millions, and soon to be billions, of transistors on a chip must be interconnected to give desired functions. As minimum device features shrink below 0.25 microns, the increase in propagation delay, cross-talk noise and power dissipation of the interconnect structure become limiting factors. It is therefore, essential to reduce the interconnect capacitance in order to maintain the trend of reduced delay time, reduced power consumption and reduced noise for future scaled devices. Capacitance is directly proportional to dielectric constant (k). Currently the most common semiconductor dielectric is silicon dioxide, which has a dielectric constant of about 4.0. Thus there is substantial interest in materials with low value of dielectric constant that can replace silicon dioxide based insulators as Interlayer Dielectrics (ILD).
[0004] One problem with essentially all candidates for low-k dielectrics is that copper has a relatively high diffusion coefficient in them, particularly when such dielectrics are rendered porous as a means of lowering the effective dielectric constant. When the copper layers are contacted with the dielectric layer, the copper will diffuse into the dielectric layer under an electrical bias at an elevated temperature, and will degrade the performance of the device. In order to prevent the copper diffusion problem, a barrier layer between the copper and the dielectric is generally required. The additional layer adds to the cost of processing, occupies valuable space, and requires an even lower dielectric constant for the dielectric material that is used in conjunction with such a barrier layer in order to meet the above requirements for the effective dielectric constant of the material between the copper interconnects.
[0005] Thus, a need exists for low dielectric compositions that overcome at least one of the aforementioned deficiencies.
SUMMARY OF THE INVENTION
[0006] An aspect of the present invention relates to a method for providing an interlayer dielectric comprising:
[0007] (a) applying a precursor mixture comprising:
(i) a polymeric or oligomeric carbosilane of the formula [cyclo-{R 1 Si(CH 2 ) 2 SiR 2 }—(CH 2 ) n ] wherein
R 1 is an alkyl, an aryl, or a substituted alkyl or aryl, R 2 is an alkyl, an aryl, or a substituted alkyl or aryl, n is 1-10, m is >10 and typically >100, and, optionally,
(ii) a solvent,
[0014] to an integrated circuit component; and
[0015] (b) heating said precursor to form an interlayer dielectric. The resulting dielectric contains mainly or entirely C—H, C—C, and Si—C bonds. When solvent is employed, an additional step of heating to volatize the solvent may be interposed.
[0016] A second aspect of the present invention is a method for capping an integrated circuit component comprising:
[0017] (a) applying a precursor mixture comprising:
(i) a polymeric or oligomeric carbosilane of the formula [cyclo-{R 1 Si(CH 2 ) 2 SiR 2 }—(CH 2 ) n ] m wherein
R 1 is an alkyl, an aryl, or a substituted alkyl or aryl, R 2 is an alkyl, an aryl, or a substituted alkyl or aryl, n is 1-10, m is >10 and typically >100, and, optionally,
(ii) a solvent,
[0024] to at least one surface of an integrated circuit component containing a non-carbosilane dielectric; and
[0025] (b) heating the precursor to form an interlayer dielectric. The resulting capping layer contains mainly or entirely, C—H, C—C, and Si—C bonds. When solvent is employed, an additional step of heating to volatize the solvent may be interposed.
[0026] A third aspect of the present invention is an integrated circuit comprising an integrated circuit component and an interlayer dielectric resultant from the above processes.
[0027] A fourth aspect of the present invention is an integrated circuit comprising an integrated circuit component having an interlayer dielectric on at least one surface of the integrated circuit component. The interlayer dielectric comprises a cross-linked carbosilane having mainly or entirely C—H, C—C, and Si—C bonds. The dielectric is derived by thermally-induced opening of a precursor polymer or oligomer containing sila- or disilacyclobutane rings. A preferred embodiment of this carbosilane is derived from heating of a cyclolinear carbosilane precursor and has the general formula:
wherein
R 1 is an alkyl, an aryl, or a substituted alkyl or aryl, preferably methyl; R 2 is an alkyl, an aryl, or a substituted alkyl or aryl, preferably methyl; n is 1-10; m is >10 and typically >100; and a and b are points of crosslinking.
BRIEF DESCRIPTION OF THE DRAWINGS
[0033] FIG. 1 depicts a plot of the capacitance as a function of Al electrode area for a dielectric measurement of the cured polymer, in accordance with the present invention;
[0034] FIG. 2 depicts a plot of current density vs applied field for the polymer film in accordance with the present invention; and
[0035] FIG. 3 depicts two plots of a copper/polycarbosilane (PCS) capacitor stressed at two different temperatures in accordance with the present invention; and
[0036] FIG. 4 depicts two stress plots of a capacitor having a PCS capping layer and a capacitor without the PCS capping layer in accordance with the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0000] Definitions
[0037] Throughout this specification the terms and substituents retain their definitions.
[0038] The term alkyl is intended to include a linear, a branched, or a cyclic hydrocarbon structure, and combinations thereof. A lower alkyl refers to alkyl groups having from about 1 to about 6 carbon atoms. Examples of lower alkyl groups include but are not limited to methyl, ethyl, n-propyl, isopropyl, and n-, s- and t-butyl, and the like. A cycloalkyl is a subset of alkyl and includes cyclic hydrocarbon groups having from about 3 to about 8 carbon atoms. Examples of cycloalkyl groups include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. Typical alkyl groups are those of C 20 or below in an embodiment of the present invention.
[0039] Aryl means a 6-membered aromatic ring or fused rings. Examples of aryl groups include but are not limited to phenyl, napthyl, and the like. Substituted refers to an alkyl or an aryl wherein one or more of the hydrogen atoms of the aforementioned groups are replaced with an alkyl, an aryl, a halogen, and the like. Examples of a substituted aryl include but are not limited to toluene, xylene, a halogenated tolyl such as C 6 H 4 CH 2 Br, and the like. Benzyl, for the purpose of the present invention, is included within the term substituted alkyl, in that it is an alkyl (methyl) substituted with an aryl (phenyl).
[0040] An integrated circuit (IC) component is an element of an IC. Examples of an IC component include, but are not limited to, an interconnected semiconductor device such as a transistor or a resistor; a copper interconnect; an aluminum interconnect; a porous or non-porous low k dielectric material; an insulating layer, a barrier layer, a wafer comprising a semiconducting material such as silicon, doped silicon, silicon on sapphire, gallium arsenide; and the like.
[0041] A method for providing an interlayer dielectric is presented in accordance with the present invention. The method comprises applying a carbosilane precursor mixture to an integrated circuit (IC) component and heating the precursor to form an interlayer dielectric. In an embodiment of the present invention, the precursor mixture comprises (i) a polymer or oligomeric carbosilane of the formula [cyclo-{R 1 Si(CH 2 ) 2 SiR 2 }-(CH 2 ) n ] m wherein R 1 is an alkyl, an aryl, or a substituted aryl, R 2 is an alkyl, an aryl, or a substituted aryl, n is 1-10, m is >10 and typically >100, and, optionally, (ii) a solvent. The substituents R 1 and R 2 may be chosen independent of each other. In an embodiment of the present invention, R 1 is the same as R 2 .
[0042] Examples of R 1 and R 2 substituents include but are not limited to a methyl group, a phenyl group, a tolyl group, a brominated tolyl group (—C 6 H 4 CH 2 Br), and the like. The aforementioned described examples of substitutents are not meant to limit the scope of the polymer subtitutents and the subsequent polymer that may be used in accordance with the present invention.
[0043] Examples of a solvent used in the polymer mixture include but are not limited to xylene, hexane, tetrahydrofuran, chloroform, toluene, ethylene glycol dimethylether, and the like.
[0044] In an embodiment of the present invention the polymer mixture is applied to an IC component via a spin coating or other casting technique. Examples of IC components that may have the precursor mixture applied thereon include but are not limited to a transistor or a resistor; a copper interconnect; an aluminum interconnect, an insulating layer, a barrier layer, a silicon wafer, a doped silicon wafer, a silicon on sapphire wafer, and a gallium arsenide wafer.
[0045] Subsequent to application of the polymer mixture, the polymer mixture is heated at a temperature range from about 200° C. to about 450° C. for about 6 hr to about 9 hr to form interlayer dielectric. The formed interlayer dielectric is the cured/cross-linked carbosilane derived from heating the carbosilane precursor. An intermediary heating step may be inserted or performed before the aforementioned heating to drive off solvent and/or induce cross-linking. The intermediary heat may be performed at a temperature range from about 120° C. to about 150° C. for a time period of about 20 min to about 45 min.
[0046] A method for capping an integrated circuit component is presented in accordance with the present invention. The method comprises applying a carbosilane precursor mixture to at least one surface of an integrated circuit (IC) component and heating the polymer mixture to form a capping layer. In an embodiment of the present invention, the polymer mixture comprises (i) a polymeric or oligomeric carbosilane of the formula [Cyclo-{R 1 Si(CH 2 ) 2 SiR 2 }—(CH 2 ) n ] m wherein R 1 is an alkyl, an aryl, or a substituted aryl, R 2 is an alkyl, an aryl, or a substituted aryl, n is 1-10, m is m is >10 and typically >100, and, optionally, (ii) a solvent. The substituents R 1 and R 2 may be chosen independent of each other. In an embodiment of the present invention, R 1 is the same as R 2 .
[0047] Examples of R 1 and R 2 substituents include but are not limited to a methyl group, a phenyl group, a tolyl group, a brominated tolyl group (—C 6 H 4 CH 2 Br), and the like. The aforementioned described examples of substituents are not meant to limit the scope of the carbosilane substituents and the subsequent cross-linked carbosilane that may be used in accordance with the present invention.
[0048] Examples of a solvent used in the precursor mixture include but are not limited to xylene, hexane, tetrahydrofuran, chloroform, toluene, ethylene glycol dimethyl ether, and the like.
[0049] Examples of R 1 and R 2 substituents include but are not limited to a methyl group, a phenyl group, a tolyl group, a brominated tolyl group (—C 6 H 4 CH 2 Br), and the like. The aforementioned described examples of substitutents are not meant to limit the scope of the polymer subtitutents and the subsequent polymer that may be used in accordance with the present invention.
[0050] Examples of solvents for use in the polymer mixture include but are not limited to xylene, hexane, tetrahydrofuran, chloroform, toluene, ethylene glycol dimethylether, and the like.
[0051] The precursor mixture may be applied to at least one surface of an IC component via a spin coating or other casting technique. In this case, a solvent will commonly be used to adjust the rheological properties of the liquid. The mixture may, however, be applied without the use of solvent, for example by spraying, chemical vapor deposition or any other method of direct application of a liquid to a solid surface. Examples of IC components that may have the polymer mixture applied to at least one surface thereon include but are not limited to a an a transistor or a resistor; a copper interconnect; an aluminum interconnect; a porous or non-porous low k dielectric material; an insulating layer, and a barrier layer.
[0052] Subsequent to application of the precursor mixture, the carbosilane is heated at a temperature range from about 200° C. to about 450° C. for about 3 hr to about 9 hr to form the capping layer. The formed capping layer is the cured/cross-linked carbosilane derived from heating the carbosilane precursor. When desirable for removing solvent, an intermediary heating step may be inserted or performed before the aforementioned heating. The intermediary heat may be performed at a temperature range from about 120° C. to about 150° C. for a time period of about 20 min to about 45 min. Vacuum could also be used to assist in removing solvent, and this would allow lower temperatures.
[0053] The cross-linked carbosilane derived from thermally-induced opening of a precursor polymer or oligomer containing sila- or disilacyclobutane rings has mainly (>90%) or entirely (>97%) C—H, C—C, and Si—C bonds. To the extent that other covalent bonds may be present in the crosslinked carbosilane, they are commonly O—H and Si—O bonds that arise from surface oxidation. A preferred embodiment of this carbosilane is derived from heating of a cyclolinear carbosilane precursor and has the general formula:
[0054] In one embodiment, the polymer of the invention can be used as a capping layer on Cu lines after the chemical mechanical planarization process. A thin layer of PCS can be spun on to the surface, which contains the Cu lines. After curing, a second layer of low K dielectric is applied. This PCS capping will serve as a diffusion barrier and adhesion promoter to enhance electromigration resistance. PCS can also be used as capping layer onto a non-carbosilane low k interlayer dielectric. The term “non-carbosilane, low k dielectric” refers to any material having a dielectric constant below 5 that is not a polymer having mainly or entirely C—H, C—C, and Si—C bonds. The capping layer of the invention can serve as a diffusion barrier and chemical mechanical planarization stop layer.
EXAMPLES
[0055] Examples of the preparation of the precursor mixture and subsequent materials, i.e. a interlayer dielectric or a capping layer (described supra), formed after cross-linking are not explained in depth below and not meant to be limiting to the polymer mixtures and subsequent materials that may be used in accordance with the present invention. Detailed examples of preparation and characterization of the carbosilane of the precursor mixture as well as the cross-linked material may be found in Zhizhong Wu, Jerry P. Papandrea, Tom Apple, and Leonard V. Interrante; Macromolecules 2004, 37, 5257-5264, which is hereby incorporated in its entirety by reference.
Example 1
[0056] Preparation of a Cyclolinear Unsaturated Polycarbosilane (PCS).
[0057] In a glove box under an inert N 2 atmosphere, 1.0 g of dry monomer (a) and 10 mg of the second generation Grubbs catalyst (1 wt %) were added to a round bottom flask. The mixture was stirred at room temperature in the glove box until a clear solution resulted, which indicated that the catalyst was completely dissolved in the monomer. The flask was then removed from the glove box, and the contents were stirred under vacuum on a Schlenk line and heated in an oil bath to 40° C.
[0058] After one day, the reaction mixture was again taken into the glove box, and an additional aliquot of catalyst was added. The mixture was then stirred at 65° C. until the evolution of ethylene was no longer visible and the stir bar did not stir. The reaction was terminated by exposure to air. The resultant polymer was dissolved in toluene or THF, treated with activated carbon, passed through silica gel column, twice precipitated by pouring into methanol, and then vacuum dried.
Example 2
[0059] Preparation of a Cyclolinear Saturated Polycarbosilane.
0.2 g (1 mmol) of the unsaturated polymer mixture with 20 ml of xylene was added to a two-necked round bottom flask with a reflux condenser. 0.29 g (2 mmol) of tripropylamine (TPA), and 0.37 g (2 mmol) of p-toluenesulfonhydrazine (TSH) was added to this flask and the mixture was heated at 100° C. in an oil bath for 4 h under nitrogen. The temperature was increased to 110° C. for another 4 h. After removing the solid precipitate, the entire liquid mixture was added to methanol, and the saturated form of the cyclolinear polycarbosilane (CLPCS) was recovered by decantation and dried in vacuum.
Example 3
[0060] Film Processing for Electrical Measurement.
[0061] N type, 4-inch silicon wafers with resistivity of ≦0.02 ohm-cm were used as substrates. After RCA cleaning of the wafers, HMDS was spin-coated at 3000 rpm for 40 sec onto the wafers prior to deposition. The cyclolinear carbosilane polymer was dissolved in xylene at a concentration of 15-20%. The solutions were filtered through a 0.2 mm filter and then spin-deposited onto the pretreated wafers at 3000 rpm for 100 sec, followed by drying in an oven at 140° C. for 30 min. The sample was then placed in a tube furnace and flushed with nitrogen gas for approximately half an hour. The furnace temperature was ramped at a rate of 1.0 C/min to 300° C. in a nitrogen atmosphere and held a temperature for 8 hours before cooling to room temperature. The resultant films were used for electrical property measurements. The measurements demonstrated the use of the polymer films as an interlayer dielectric material and a capping layer. From hereon in, the polymer film prepared by the aforementioned procedure will be referred to as the interlayer dielectric or capping layer interchangeably.
Example 4
[0062] Dielectric Constant Measurement
[0063] FIG. 1 depicts a plot of the capacitance as a function of Al electrode area for a dielectric measurement of the interlayer dielectric (ILD) in accordance with the present invention. The dielectric constant of the ILD was measured to be 2.3. The dielectric constant was measured from the capacitance data using the equation,
k=Cd /( e 0 A )
where ε 0 is the permittivity of vacuum (8.85×10 −12 C 2 /Nm 2 ), C is the capacitance, d is the thickness of the sample, and A is the area of the Al electrode. Here, Al electrodes with three different areas, with diameters 0.5, 1, and 1.5 mm, were used to validate the measurement (see FIG. 1 ). In an embodiment of the present invention, the ILD dielectric constant value is typically about 2.3 to about 2.4. The ILD dielectric constant of the present invention is lower than all of the currently available non-fluorine containing, non-porous dielectric materials available and presently used in IC technology.
Example 5
[0064] Leakage Current Measurement of the ILD.
[0065] FIG. 2 depicts a plot of current density vs applied field for the ILD in accordance with the present invention. Referring to FIG. 2 , leakage current curves for the ILD were determined as a function of the applied field. Five measurements of I-V were taken and show the strong firm base of the extreme value statistics. The intrinsic leakage current curves show that the leakage current densities of the ILD are less than 2×10 −9 A/cm 2 at the applied field of 1 MV/cm and the average breakdown field for the capping layer was greater than 5 MV/cm.
Example 6
[0066] Copper Diffusion Test on the Capping Layer.
[0067] FIG. 3 depicts two plots of a copper/polycarbosilane (PCS) capacitor stressed at two different temperatures in accordance with the present invention. The capacitor sample tested comprised of a Cu/PCS/SiO 2 /Si. The Cu represents the metal line, the PCS is the capping layer, and the SiO 2 is the dielectric material deposited on a silicon wafer (Si). Referring to FIG. 3 , the Cu/PCS/SiO 2 /Si samples showed no capacitance-voltage (C-V) shifts after stressing at a temperature of 150° C. for 90 min, while only a small C-V shift was seen after stressing 200° C., with no further change even for 90 min. The results indicated the capping layer has excellent resistance to copper diffusion under standard Bias Thermal Stress (BTS) test conditions.
Example 7
[0068] A Second Copper Diffusion Test on the Capping Layer.
[0069] FIG. 4 depicts two stress plots of a capacitor having a polycarbosilane (PCS) capping layer and a capacitor without the PCS capping layer in accordance with the present invention. The capacitor samples tested comprised of a Cu/PCS/MSQ/SiO 2 /Si and Cu/MSQ/SiO 2 /Si structure. The Cu represents the metal line, the PCS is the capping layer, the MSQ (methylsilsequioxane) is a porous dielectric material, and the SiO 2 is the surface oxide on a silicon wafer (Si).
[0070] Referring to FIG. 4 , the Cu/MSQ/SiO 2 /Si structure showed C-V shifts after stressing at 160° C. for 5 min, while no C-V shift was seen for the Cu/PCS/MSQ/SiO 2 /Si sample after 90 min. Examples 6 and 7 demonstrate the use of the PCS capping layer on Cu lines to prevent Cu diffusion at the interface between the capping layer and the Cu line.
[0071] An integrated circuit (IC) is presented in accordance with the present invention. The IC comprises: one or more integrated circuit components, and an interlayer dielectric resultant from applying a carbosilane precursor mixture. The precursor mixture comprises:
(i) a polymeric or oligomeric carbosilane of the formula [cyclo-{R 1 Si(CH 2 ) 2 SiR 2 }—(CH 2 ) n ] m wherein
R 1 is an alkyl, an aryl, or a substituted alkyl or aryl, R 2 is an alkyl, an aryl, or a substituted alkyl or aryl, n is 1-10, m is >10 and typically >100, and optionally,
(ii) a solvent,
to at least one surface of the integrated circuit component and heating the polymer mixture to form the interlayer dielectric.
[0079] A second integrated circuit (IC) is presented in accordance with the present invention. The IC comprises: an integrated circuit component, and an interlayer dielectric on at least one surface of the integrated circuit component. The interlayer dielectric comprises repeating units of the formula:
wherein
R 1 is an alkyl, an aryl, or a substituted alkyl or aryl, R 2 is an alkyl, an aryl, or a substituted alkyl or aryl, n is 1-10, m is >10 and typically >100, and a and b are points of crosslinking.
|
Low dielectric compositions and methods of use thereof in integrated circuits are disclosed. The low dielectric compositions are derived from carbosilane polymers and oligomers containing imbedded sila- or disilacyclobutane rings and, after heating to induce cross-linking, may be used as an interlayer dielectric as well as a capping layer within an integrated circuit.
| 7
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a pontoon boat of the type including a substantially horizontal deck and a plurality of horizontally spaced apart above deck components projecting upwardly from the deck to define passageways between the horizontally spaced apart components. Such passageways usually open immediately outward of marginal portions of the deck and, for safety reasons, are provided with gates in order to prevent accidental movement of any passengers through the passageways and into the water while the pontoon boat is underway. In addition each of the gates includes a control switch operatively associated therewith and serially connected within the ignition circuit of the associated marine engine and each of the switches is "open" when the associated gate is moved even slightly from the closed position thereof toward the open position thereof. In this manner, operation of the marine propulsion engine of the pontoon boat may not occur unless all of the gates are in the fully closed positions, an emergency bypass switch under the control of the helm being provided to override the control of the gate switches in an emergency or otherwise necessary condition.
2. DESCRIPTION OF RELATED ART
Various different forms of gates heretofore have been provided including electric circuit controlling switches operatively associated therewith. In addition, it is also known to provide gates, in one form or another, for above deck passageways between horizontally spaced apart boat components projecting upward from a deck surface. However, I am unaware of any boat passageway gate having a control switch operatively associated therewith in a manner such that an associated marine propulsion system may be rendered operative only when the gate is in the fully closed position and is automatically rendered inoperative when the associated gate is shifted a predetermined amount from the fully closed position thereof toward the open position.
SUMMARY OF THE INVENTION
This invention relates to a gate for an above deck passageway and which is shiftable between open and closed positions enabling and preventing, respectively, passage through the associated passageway. In addition, the gate is operatively associated with a control switch serially connected within a marine propulsion system control circuit in a manner such that the associated marine propulsion system may not be rendered operable (with one exception) unless the gate is in the fully closed position thereof.
The exception resides in the provision of a bypass circuit having an override switch operatively associated therewith whereby the gate associated switch may be overridden and the associated marine propulsion system may be rendered operative by actuation of the override switch, which switch is disposed immediately adjacent the helm of the associated boat.
The main object of this invention is to provide a pontoon boat equipped with openable and closable gates at above deck passageways opening outwardly toward outer margins of the deck of an pontoon boat and with each of the gates including a control switch operatively associated therewith serially connected within a control circuit for the associated marine propulsion system, whereby the marine propulsion system may not be rendered operative unless all gates are in the fully closed positions thereof.
Another object of this invention, in accordance with the immediately preceding object is to provide a marine passageway gate of simple construction and which may be readily shifted between the open and closed positions thereof as well as locked in the closed position.
Still another object of this invention is to provide a marine passageway gate incorporating slidable bars arranged in a framed system with a guide wheel on the outer end of the gate to thereby render the gate reciprocating rather than swingable so as to maximize space utilization.
Another important object of this invention is to provide a marine passageway gate incorporating a lock construction which may be readily used to releasably lock the gate in a closed position.
Yet another object of this invention is to provide a marine passageway gate including mounting components therefore which may be readily installed on two horizontally opposed upstanding surfaces defining the side boundaries of a passageway extending therebetween.
A final object of this invention to be specifically enumerated herein is to provide a marine passageway gate which will conform to conventional forms of manufacture, be of simple construction and easy to use so as to provide a device that will be economically feasible, long-lasting and relatively trouble free in operation.
These together with other objects and advantages which will become subsequently apparent reside in the details of construction and operation as more fully hereinafter described and claimed, reference being had to the accompanying drawings forming a part hereof, wherein like numerals refer to like parts throughout.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a pontoon boat incorporating three passageways between pairs of horizontally spaced apart components projecting upwardly from the deck of the pontoon boat and with one of the gates in an open position and the other two gates in closed positions;
FIG. 2 is an enlarged fragmentary vertical sectional view illustrating the external and internal components of the gate and with the gate in a closed position;
FIG. 3 is a vertical sectional view taken substantially upon the plane indicated by the section line 3--3 of FIG. 2;
FIG. 4 is a diagrammatic view illustrating the manner in which all three of the passageway gates have control switches operatively associated therewith serially connected within the ignition circuit of the outboard engine of the pontoon boat and with the ignition circuit including a bypass circuit for bypassing the gate actuated switches; an
FIG. 5 is an enlarged fragmentary vertical sectional view similar to FIG. 2 and illustrating a slightly modified form of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now more specifically to the drawings, the numeral 10 generally designates a typical form of pontoon boat including a pair of opposite side pontoons 12 and 14 and a generally rectangular deck 16 supported therefrom. The deck 16 includes a plurality of hollow, upwardly projecting above deck components 18, 20, 22, 24 and 26. The components 18 and 20 are horizontally spaced apart and define a passageway 30 therebetween, the components 22 and 24 are horizontally spaced apart and define a passageway 32 therebetween and the components 24 and 26 are horizontally spaced apart and define a passageway 34 therebetween, the passageways 30, 32 and 34 having horizontally shiftable gates 36, 38 and 40, respectively, operatively associated therewith.
The pontoon boat 10 includes a helm position 40 and a marine propulsion system comprising an outboard engine 42 controlled from the helm position 40. The outboard engine 42, shown only schematically in FIG. 4, but in practice mounted at the transom of the pontoon boat 10, includes a control (ignition) circuit 44 including the usual key operated ignition switch 46 and safety kill switch 48 serially connected therein. The ignition circuit 44 is electrically connected to a suitable source 50 of electrical potential and further has three switches 52, 54 and 56 serially connected therein. A bypass circuit 58 is provided and is connected in parallel to the circuit 44 bypassing the switches 52, 54 and 56, the bypass circuit 58 including a manual override switch 60 which may be readily actuated from the helm position 40. Of course, the ignition 46 and kill switch 48 also are disposed at the helm position 40.
Considering now the gates 36, 38 and 40, only the gate 38 will be specifically described, inasmuch as all the gates are similar.
The gate 38 is disposed between the components 22 and 24, each of which components are hollow.
In the embodiment shown components 22 and 24 are constructed of fiberglass and the component 22 includes an upstanding wall 64 opposing an upstanding wall 66 of the component 24. The wall 64 has an opening 68 formed therein and the wall 66 has three vertically spaced openings 70, 72 and 74 formed therethrough. In addition, the interior of the component 24 includes a fiberglass partition 76 spaced inward from the wall 66 and through which guide sleeves 80, 82 and 84 are secured in axial registry with the openings 70, 72 and 74.
The outer surface of the wall 66 includes an open sided housing 86 secured thereover in a vertically extending zone in which the openings 70, 72 and 74 are formed and the housing 86 includes guide sleeves 90, 92, and 94 secured therethrough in registry with the openings 70, 72, and 74.
The gate 38 includes an elongated vertical member 96 having a support wheel 98 journaled from its lower end and three vertically spaced, horizontal elongated members 100, 102, and 104 including one set of corresponding ends secured through openings provided therefore in the vertical member 96. The vertical member 96 includes an upper end portion 106 extending above the uppermost horizontal member 100 and the members 100, 102, and 104 are guidingly received through the guide sleeves 90, 92, and 94; the openings 70, 72 and 74 and the guide sleeves 80, 82 and 84. Furthermore, the support wheel 98 is rollingly engaged with the deck 16 and thereby supports the extendable and retractable end of the gate 38.
The vertical side wall 64 includes an open sided housing 108 secured thereto corresponding to the housing 86 and including guide sleeves 110, 112 and 114 corresponding to the sleeves 90, 92 and 94 secured thereto, the guide sleeve 110 being registered with the opening 68 formed in the vertical side wall 64.
The one set of corresponding ends of the horizontal members 100, 102 and 104 which extend through the vertical member 106 are substantially fully received within the guide sleeves 110, 112 and 114 when the gate 38 is in the fully closed position and the upper end of the housing 108 includes a bail-type latch 116 pivotally supported therefrom as at 118 and swingable between an upstanding inoperative position and a horizontal operative position such as that illustrated in FIG. 2 engaged over the upper end portion 106 to thereby prevent retraction of the vertical member 106 away from the housing 108.
The housing 108 additionally includes a pair of mounting brackets 119 and 120 supported therefrom which project through the opening 68 and support the switch 54 therefrom, the switch 54 including a plunger-type actuator 122 for closing the switch 54 when inwardly depressed by the horizontal member 100 as the gate 38 is shifted to the closed position thereof illustrated in FIG. 2. The switches 52, 54 and 56 are normally open and each includes a plunger-type actuator such as the actuator 122 for inward displacement by engagement of the corresponding horizontal member 100 when the associated gate is in the fully closed position.
The gates 36, 38 and 40 control the passageways, 30, 32 and 34 (as for example to prevent small children from moving through the passageways toward the outer periphery of the boat 10) and if either one of the gates 36, 38 and 40 is not fully closed, the corresponding switch will be opened to thereby open the ignition circuit 44 (assuming that the override switch 60 is open). When the ignition circuit 44 is open, the outboard engine 42 may not be operated.
In an emergency situation, the override switch 60 at the control of the operator of the helm position 40 may be closed to actuate the ignition circuit 44 even if one or all of the gates 36, 38 and 40 are open.
With attention now invited more specifically to FIG. 5 of the drawings, there may be seen a modified form of gate 38' between components 22' and 24'. The gate 38' is substantially similar to the gate 38, but the component 24' does not include the equivalent of the partition 76 and guide sleeves 80, 82 and 84 and the component 22' does not include an opening corresponding to the opening 68 or a switch corresponding to the switch 54. Rather, the gate 38' has its upper horizontal member 100' disposed in operative association with a switch 54' including a pivoted actuator 122' mounted within the interior of the component 24'. Otherwise, the gate 38' is structurally and operationally identical to the gate 38 and the various components thereof are referred to by prime reference numerals corresponding to the reference numerals appearing in FIG. 2.
The foregoing is considered as illustrative only of the principles of the invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention.
|
A boat including a deck equipped with peripherally upwardly projecting components surrounding a passenger area is provided including passageways from the passenger area between adjacent components leading to the deck periphery. Openable and closable gates are provided to control passenger movement through the passageways and the boat includes a marine propulsion system including an electrical control circuit therefore equipped with normally opened control switches operatively associated with the gates in a manner closing the switches when the gates are closed, to thereby enable operation of the marine propulsion system only when all gates are closed.
| 1
|
BACKGROUND OF THE INVENTION
The present invention relates to vinyl-phenyl monomers and polymers prepared therefrom. More particularly, the present invention is to provide the vinyl-phenyl monomers expressed by formula (1) which are capable of various polymerization such as radical polymerization, cationic polymerization, anion polymerization and metallocene catalyzed polymerization due to the resonance effect of phenyl group and changing characteristics variously and thus, suitable in the synthesis of polymers which can be used in photo-functional materials by forming a polymer complex with a metal component having an optical characteristic.
Continuous polymerization can be divided to ionic polymerization and radical polymerization depending on an initiator. It is difficult to do a controlled polymerization due to side reaction with the radical chain ends in radical polymerization, and reaction termination for the repulsion between the functional groups chain ends in ionic polymerization. Reactivity of radical polymerization varies with resonance stability of vinyl group and that of ionic polymerization varies with the polarity.
Monomers used in continuous polymerization can be polymerized by means of radical, cationic or anionic polymerization depending on Q-e value shown in the following table. Especially, either cationic or anionic polymerization can be expected with e value representing the degree of polarity.
Cationic
Anionic
Monomer
◯
e
Polymerization
Polymerization
0.02
−1.8
⊚
X
0.98
−1.27
⊚
◯
1.00
−0.80
◯
◯
0.42
0.62
X
◯
0.60
1.20
X
⊚
The polarity of a monomer is important in anionic polymerization because reactivity is highly dependent on the polarity of the monomer. That is, a selection of monomers plays an essential role in the synthesis of block copolymers. A monomer having an electron-withdrawing character in vinyl group is preferable for anionic polymerization. Representative anionic monomers are styrene, α-methylstyrene, butadiene and isoprene which undergo the polymerization with a carbanion having strong reactivity because they have −e values. The order of polymerization is α-methylstyrene, isoprene and styrene.
Polymers having functional groups can be widely used for photo-functional materials. In order to polymerize styrene, butadiene and methacrylate having a variety of functional groups through anionic polymerization, it is required to protect the functional groups during the polymerization to prevent from the termination reaction between carbanion and the functional groups. S. Nakahama et. al have reported that styrene monomer having amine, hydroxy, carbonyl, carboxyl, or mercapto group can be protected with an appropriate protecting group such as trimethyl silyl, t-butyldimethyl silyl, oxazoline and ester groups during the polymerization and the protected functionality is then deprotected to regenerate the original functional group after the polymerization [S. Nakahama, Prog. Polym. Sci., 15, 299 (1990); Makromol, Chem., 186, 1157 (1985); Polymer, 28, 303(1987); Macromolecules, 19, 2307 (1986); ibid. 26, 4995 (1993); ibid. 26, 35 (1993); Macromolecules, 20, 2968 (1987); ibid. 24, 1449 (1991); ibid. 26, 6976 (1993); Macromolecules, 19, 2307 (1986); ibid. 21, 561 (1988); ibid. 22, 2602 (1989)]. And further, the research and development of photo conductive and organic light emitting devices using phenylpyridines have been actively studied and some examples have been reported [Alistair J. Lee, Chem. Rev. 1987, 87, 711˜743; M. A. Baldo, S. Lamansky, P. E. Burrows, M. E. Thompson, S. R. Forrest, Appl. Phys. Lett., 75, 4, (1999); Raymond C. Kwong, Sergey Lamansky, and Mark E. Thompson, Adv. Mater., 2000, 12, No. 15, 1134; Catherine E. Housecroft, Coordination Chemistry Reviews, 152, (1996), 141˜156; K. Dedeian, P. I. Djurovich, F. O. Garces, G. Carlson, R. J. Watts, Inorg. Chem., 1991, 30, 1687˜1688; King, K. A, Spellane, P. J., Watts, R. J., J. Am. Chem. Soc., 1985, 107, 1431].
However, the study of phenylpyridines is limited to only organic molecule and there is no report in the synthesis of the corresponding polymers using phenylpyridine monomers.
The present invention is to provide 2-(4-vinyl-phenyl)pyridine monomers and polymers with controllable molecular weight and molecular structure which can be widely useful for photo-functional materials since said polymers of such monomers is reliable to form a complex of a metal component (iridium, ruthenium and the like).
SUMMARY OF THE INVENTION
Vinyl-phenyl monomers of formula (1) of the present invention are capable of various polymerization such as radical polymerization, cation polymerization, anion polymerization and metallocene catalyzed polymerization due to the resonance effect of the phenyl group.
The molecular weight and molecular structure of polymers can be controlled during the polymerization and the prepared polymers can further form a complex with various metal components such as iridium, ruthenium and the like to be useful for photo-functional materials.
Therefore, an object of the present invention is to provide vinyl-phenyl pyridine monomers and the preparation method thereof which can be easily introduced to synthesize polymers with the controlled functional groups and thus, such polymers can be applied in the preparation of thin film or fiber depending on the purpose.
Another object of the present invention is to provide the polymers prepared by using the monomers of formula (1).
Further objection of the present invention is to provide a complex of the polymers and iridium, ruthenium or platinum having optical character.
BRIEF DESCRIPTION OF THE INVENTION
FIG. 1 represents 1 H-NMR spectrum of 2-(4-vinyl-phenyl)pyridine.
FIG. 2 represents 13 C-NMR spectrum of 2-(4-vinyl-phenyl)pyridine.
FIG. 3 represents FT-IR spectrum of 2-(4-vinyl-phenyl)pyridine.
FIG. 4 represents GC spectrum of 2-(4-vinyl-phenyl)pyridine.
FIG. 5 represents Mass spectrum of 2-(4-vinyl-phenyl)pyridine.
FIG. 6 represents 1 H-NMR spectrum of poly[2-(4-vinyl-phenyl)pyridine].
FIG. 7 represents FT-IR spectrum of poly[2-(4-vinyl-phenyl)pyridine].
FIG. 8 represents DSC spectrum of poly[2-(4-vinyl-phenyl)pyridine].
FIG. 9 represents TGA spectrum of poly[2-(4-vinyl-phenyl)pyridine].
FIG. 10 represents GPC spectrum of poly[2-(4-vinyl-phenyl)pyridine].
FIG. 11 represents 1 H-NMR spectrum of poly[2-(4-vinyl-phenyl)pyridine-co-9-vinylcarbazole].
FIG. 12 represents FT-IR spectrum of poly[2-(4-vinyl-phenyl)pyridine-co-9-vinylcarbazole].
FIG. 13 represents GPC spectrum of poly[2-(4-vinyl-phenyl)pyridine-co-9-vinylcarbazole].
FIG. 14 represents 1 H-NMR spectrum of poly({[2-(4-vinyl-phenyl)pyridine](phenylpyridine) 2 iridium}-co-9-vinylcarbazole).
FIG. 15 represents FT-IR spectrum of poly({[2-(4-vinyl-phenyl)pyridine](phenylpyridine) 2 iridium}-co-9 -vinylcarbazole).
FIG. 16 represents UV and PL spectrum of poly({[2-(4-vinyl-phenyl)pyridine](phenylpyridine) 2 iridium}-co-9-vinylcarbazole).
DETAILED DESCRIPTION OF THE INVENTION
The present invention is characterized by vinyl-phenyl pyridine monomers expressed by the following formula (1).
The present invention is described in detail as set forth hereunder.
Examples of vinyl-phenyl pyridine monomers of the present invention are 2-(2-vinyl-phenyl)pyridine, 2-(3-vinyl-phenyl)pyridine, and 2-(4-vinyl-phenyl)pyridine.
The vinyl-phenyl pyridine monomers of formula (1) are prepared by the following methods.
The first is Suzuki coupling reaction as shown in Scheme 1.
In Scheme 1, the vinyl-phenyl pyridine of formula (1) is prepared by Suzuki coupling reaction of vinyl-phenylboronic acid of formula (2) and 2-bromopyridine of formula (3) in the presence of alkali metallic base and palladium catalyst. Examples of alkali metallic base used are sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide. Examples of palladium catalyst are tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ) and palladium acetate. Examples of reaction solvent are tetrahydrofuran (THF), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and toluene. The Suzuki coupling reaction is performed it a temperature of from 80 to 120° C.
The second is Suzuki coupling reaction and Wittig reaction as shown in Scheme 2.
In Scheme 2, formylphenyl pyridine of formula (5) is prepared by Suzuki coupling reaction of formylphenylboronic acid of formula (4) and 2-bromopyridine of formula (3) in the presence of alkali metallic base and palladium catalyst and further, Wittig reaction of the prepared formylphenyl pyridine of formula (5) is performed in the presence of methyltriphenylphosphonium bromide (PPh 3 CH 3 Br) and sodium hydride to to yield vinyl-phenyl pyridine of formula (1).
Examples of alkali metallic base used in Suzuki coupling reaction are sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide and examples of palladium catalyst are tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ) and palladium acetate. Examples of reaction solvent are tetrahydrofuran (THF), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and toluene. The Suzuki coupling reaction is performed at a temperature of from 80 to 120° C. and Wittig reaction is from 90 to 130° C.
Besides Suzuki coupling and Wittig reactions, there are other reactions such as Stille coupling reaction using trimethyltin chloride or tributyltin chloride, Grignard reaction using magnesium and nickel catalyst and coupling reaction using zinc, bipyridine, triphenylphosphine and nickel chloride to prepare vinyl-phenyl pyridine monomers.
The present invention is also characterized by polymers prepared with the vinyl-phenyl pyridine monomers of formula (1) which can be homopolymers or copolymers. Particular monomers used in the polymerization are 4-(9-carbazoylcarbozoyl)methyl styrene, 2-(N-carbazoyl)ethyl methacrylate, and 3-(vinyl-9-ethyl)carbazole.
Conventional polymerizations of such monomers are performed. Polymerization methods are not limited and can be any one of bulk polymerization, solution polymerization, and suspension polymerization. Polymerization system can be radical polymerization, cationic polymerization or anionic polymerization. A polymerization initiator can be any conventional initiator which is generally used in the polymerization of styrene-based monomers. Particular examples of polymerization initiator include azobisisobutyronitrile (AIBN), benzoyl peroxide, hydrogen peroxide, cumyl peroxide, tert-butyl peroxide, tert-butyl hydroperoxide, lauroyl peroxide and the like. The content of 2-(4-vinyl-phenyl)pyridine can be controlled depending on the purpose in the range of from 0.01 to 99.9%.
Number average molecular weight, weight average molecular weight, and molecular weight distribution (M w /M n ) of the prepared polymers are analyzed by GPC and the content of the vinyl-phenyl pyridine is analyzed by FT-NMR and FT-IR.
Examples of polymers of the present invention are the following formulas 6-8,
wherein n+m=100 and n is an integer of 0.01 to 99.99.
The present invention is further characterized by a complex of the prepared polymers and a metal such as iridium, ruthenium and platinum which is useful for photo-functional materials. Representative example of the complex is the following formula 9,
wherein M represents iridium, ruthenium or platinum; and n+m=100 and n is an integer of 0.01 to 99.99.
Example of preparation method of the polymer complex is shown in the following Scheme 3.
In Scheme 3, iridium (III) acetylacetonate (Iracac) and 2 equivalents of 2-phenylpyridine are reacted in glycerol and then 1 equivalent of the polymer having 2-(4-vinyl-phenyl)pyridine is added and heated at reflux. After the reaction is completed, the reaction mixture is poured into aqueous hydrogen chloride solution and then extracted with chloroform. The residue is precipitated out from chloroform/methanol solution. The crude product is purified by column chromatography and dried to obtain the desired polymer complex. Such polymer complex is very useful for photo-functional materials.
The following examples are intended to be illustrative of the present invention and should not be construed as limiting the scope of this invention defined by the appended claims.
EXAMPLE 1
Preparation of 2-(4-vinyl-phenyl)pyridine
4-Vinyl-phenylboronic acid (10 g, 0.0676 mol), 2-bromopyridine (12.64 g, 0.08 mol), tetrahydrofuran (100 ml), 2M potassium carbonate aqueous solution (26 ml), and tetrakis(triphenylphosphine) palladium (Pd(Ph 3 ) 4 , 0.06 g, 1 mol %) were placed into 250 ml of 2-necked round-bottomed flask under N 2 . The reaction mixture was refluxed at 80° C. for 24 hr and then poured in 200 ml of water in beaker. The reaction mixture was extracted with ether (3×150 ml) and the ether layer was then dried over magnesium sulfate (10 g) by stirring for 30 min. The dried ether layer was evaporated in vacuo to dryness and purified further by column chromatography on silica gel with eluting hexane/ethylacetate (1/9) to yield 2-(4-vinyl-phenyl)pyridine (90%).
mp: 19.3° C.; bp: 115° C./1 mmHg; 1 H-NMR, 13 C-NMR, FT-IR, GC and Mass spectra were shown in FIGS. 1-5.
EXAMPLE 2
Preparation of 2-(3-vinyl-phenyl)pyridine
The reaction was performed with 3-vinyl-phenylboronic acid (10 g, 0.0676 mol), 2-bromopyridine (12.64 g, 0.08 mol), tetrahydrofuran (100 ml), 2M potassium carbonate aqueous solution (26 ml), and tetrakis(triphenylphosphine) palladium (Pd(Ph 3 ) 4 , 0.06 g, 1 mol %) according to Example 1. The yield was 80%.
EXAMPLE 3
Preparation of 2-(2-vinyl-phenyl)pyridine
The reaction was performed with 2-vinyl-phenylboronic acid (10 g, 0.0676 mol), 2-bromopyridine (12.64 g, 0.08 mol), tetrahydrofuran (100 ml), 2M potassium carbonate aqueous solution (26 ml), and tetrakis(triphenylphosphine) palladium (Pd(Ph 3 ) 4 , 0.06 g, 1 mol %) according to Example 1. The yield was 75%.
EXAMPLE 4
Preparation of 2-(4-vinyl-phenyl)pyridine
4-Formylphenylboronic acid (10.14 g, 0.0676 mol), 2-bromopyridine (12.64 g, 0.08 mol), tetrahydrofuran (100 ml), 2M potassium carbonate aqueous solution (26 ml), and palladium acetate (Pd(OAc) 2 , 0.04 g, 1 mol %) were placed into 250 ml of 2-necked round-bottomed flask under N 2 . The reaction mixture was refluxed at 90° C. for 24 hr and then poured in 200 ml of water in beaker. The reaction mixture was extracted with ether (3×150 ml) and the ether layer was then dried over magnesium sulfate (10 g) by stirring for 30 min. The dried ether layer was evaporated in vacuo to dryness and purified further by column chromatography on silica gel with eluting hexane/ethylacetate (1/5) to yield 2-(4-vinyl-phenyl)pyridine (80%).
EXAMPLE 5
Preparation of 2-(4-vinyl-phenyl)pyridine
Methyltriphenylphophonium bromide (25 g, 0.07 mol), sodium hydride (NaH, 3.36 g, 0.14 mol), and toluene (100 ml) were placed into 250 ml of 2-necked round-bottomed flask under N 2 . The reaction mixture was refluxed at 110° C. for 3 hr while changing the reaction solution to orange color. After cooling the reaction mixture, 2-(4-formyl-phenyl)pyridine (10 g, 0.0545 mol) was added and further refluxed at 110° C. for 12 hr. The reaction mixture was poured in 300 ml of water in beaker and extracted then with ether (3×150 ml). The ether layer was then dried over magnesium sulfate (10 g) by stirring for 30 min. The dried ether layer was evaporated in vacuo to dryness and purified further by column chromatography on silica gel with eluting hexane/ethylacetate (1/10) to yield 2-(4-vinyl-phenyl)pyridine (85%).
EXAMPLE 6
Preparation of poly[2-(4-vinyl-phenyl)pyridine] homopolymer
2-(4-Vinyl-phenyl)pyridine (0.5 g, 2.761 mmol) and azobisisobutyronitrile (AIBN, 0.0045 g, 2.761 mmol) were placed into 10 ml of round-bottomed flask under N 2 . The reaction mixture was bulk polymerized at 75° C. for 30 min, dissolved in chloroform (15 ml), and filtered through 0.2 μm Teflon filter. The filtrate was dropped into 200 ml of methanol to precipitate out while stirring. The precipitate was filtered through glass filter to collect the polymer product which was further dried in vacuum oven at 60° C. for 24 hr. The yield was 95%. The polymer was analyzed to have 54,000 g/mole of number average molecular weight, 230,000 g/mole of weight average molecular weight and 4.32 of molecular weight distribution (M w /M n ). 1 H-NMR, 13 C-NMR, FT-IR, GC and Mass spectra were shown in FIGS. 6-10.
EXAMPLE 7
Preparation of poly[2-(4-vinyl-phenyl)pyridine-co-9-vinylcarbozole] copolymer
2-(4-Vinyl-phenyl)pyridine (0.5 g, 2.76 mmol), 9-vinylcarbazole (2.22 g, 10.9 mmol) and azobisisobutyronitrile (0.015 g, 1 mol %) were bulk-polymerized at 75° C. for 30 min, dissolved in chloroform (20 ml), and filtered through 0.2 μm Teflon filter. The filtrate was dropped into 250 ml of methanol to precipitate out while stirring. The precipitate was filtered through glass filter to collect the polymer product which was further dried on vacuum oven at 60° C. for 24 hr. The yield was 87%. The prepared poly[2-(4-vinyl-phenyl)pyridine-co-9-vinylcarbozole] copolymer having 20% content of 2-(4-vinyl-phenyl)pyridine was analyzed to have 43,000 g/mole of number average molecular weight, 71,000 g/mole of weight average molecular weight and 1.65 of molecular weight distribution (M w /M n ). 1 H-NMR, 13 C-NMR, FT-IR, GC and Mass spectra were shown in FIGS. 11-16.
EXAMPLE 8
Preparation of poly[2-(4-vinyl-phenyl)pyridine-co-4-(9-carbozoyl)methyl styrene] copolymer
By the same procedure as described in Example 7, poly[2-(4-vinyl-phenyl)pyridine-co-4-(9-carbozoyl)methyl styrene] copolymer having 20% content of 2-(4-vinyl-phenyl)pyridine was prepared except using 4-(9-carbazolyl)methyl styrene instead of 9-vinylcarbazole in 80%.
EXAMPLE 9
Preparation of poly[2-(4-vinyl-phenyl)pyridine-co-2-(vinyl-9-ethyl)carbozole] copolymer
By the same procedure as described in Example 7, poly[2-(4-vinyl-phenyl)pyridine-co-3-(vinyl-9 -ethyl)carbozole] copolymer having 20% content of 2-(4-vinyl-phenyl)pyridine was prepared except using 2-(N-carbazoyl)ethyl methacrylate instead of 9-vinylcarbazole in 87%.
EXAMPLE 10
Preparation of poly[2-(4-vinyl-phenyl)pyridine-co-3-(vinyl-9-ethyl)carbozole] copolymer
By the same procedure as described in Example 7, poly[2-(4-vinyl-phenyl)pyridine-co-2-(vinyl-9 -ethyl)carbozole] copolymer having 20% content of 2-(4-vinyl-phenyl)pyridine was prepared except using 3-(vinyl-9-ethyl)carbazole instead of 9-vinylcarbazole in 90%.
EXAMPLE 11
Preparation of poly[2-(4-vinyl-phenyl)pyridine-co-9-vinylcarbozole] copolymer
By the same procedure as described in Example 6, poly[2-(4-vinyl-phenyl)pyridine-co-9-vinylcarbozole] copolymer having 12% content of 2-(4-vinyl-phenyl)pyridine was prepared using 2-(4-vinyl-phenyl)pyridine (0.4 g, 2.2 mmol), 9-carbazole (2 g, 10.3 mmol) and azobisisobutyronitrile (0.021 g, 1 mol %). The copolymer has 22,000 g/mole of number average molecular weight, 57,000 g/mole of weight average molecular weight and 2.56 of molecular weight distribution (M w /M n ).
EXAMPLE 12
Preparation of poly{[(2-(4-vinyl-phenyl)pyridine)(phenylpyridine) 2 iridium]-co-9-vinyl carbazole}
Iridium(III) acetylacetonate (0.5 g, 1.02 mmol), 2-phenylpyridine (0.32 g, 2.04 mmol), and glycerol (50 ml) were placed into 250 ml of 2-necked round-bottomed next flak. The reaction mixture was refluxed at 170° C. for 3 hr. Poly[2-(4-vinyl-phenyl)pyridine-co-9-vinylcarbozole] copolymer (0.32 g, 2.04 mmol) prepared in Example 11 and chloroform (50 ml) were added and further refluxed for 24 hr. The reaction mixture was poured into 200 ml of 1N hydrogen chloride aqueous solution and extracted with chloroform. The chloroform layer was evaporated to dryness. The residue was dissolved in chloroform (10 ml) and precipitated out from 200 ml of 99.9% methanol. The precipitate was filtered through glass filter to collect the polymer complex which was further dried on vacuum oven at 60° C. for 24 hr. The yield was 95%. The polymer was analyzed to have 43,000 g/mole of number average molecular weight, 71,000 g/mole of weight average molecular weight and 1.65 of molecular weight distribution (M w /M n ). 1 H-NMR, FT-IR, UV and PL spectra were shown in FIGS. 14-16.
Vinyl-phenyl monomers of the present invention are capable of various polymerization such as radical polymerization, cation polymerization, anion polymerization and metallocene catalyzed polymerization due to resonance effect of phenyl group unlike other monomers. Such vinyl-phenyl monomers can be polymerized to homopolymers or copolymers. Molecular weight and molecular structure of polymers can be controlled during the polymerization and the polymers with the controlled weight and structure can further incorporate with a metal such as iridium, ruthenium and platinum to form a polymer-metal complex which is useful in a variety of fields using photo-functional materials.
|
The present invention relates to vinyl-phenyl monomers and polymers prepared therefrom. More particularly, the present invention is to provide the vinyl-phenyl monomers expressed by formula (1) which are capable of various polymerization such as radical polymerization, cation polymerization, anion polymerization and metallocene catalyzed polymerization due to resonance effect of phenyl group and changing characteristics variously and thus, suitable in the synthesis of general-purpose polymers which can be used in photo-functional materials by forming a complex with a metal component having an optical characteristic:
| 2
|
FIELD OF THE INVENTION
The present invention relates generally to deflashing apparatus and systems, and more particularly to a cryogenic deflashing apparatus adapted to rapidly remove residual flash from molded articles. Although not by way of limitation, the present invention is specifically directed toward the removal of residual flash from relatively small-sized molded articles, such as medical apparatus parts, microelectronic parts, and precision elastomeric parts such as O-rings and the like.
BACKGROUND OF THE INVENTION
As is well known, numerous articles of manufacture are molded from various elastomeric rubber and plastic materials. In such molding processes, there oftentimes exists residual material or flash formed on the articles at their part lines, i.e. the area adjacent the interfacing mold surfaces. Such residual flash is not only aesthetically objectionable, but additionally functionally objectionable, and therefore must be removed, i.e. deflashed, from the article prior to use of the same.
Heretofore, it has been customary practice to deflash such articles by hand, requiring the severing of the flash from the article by way of a knife or razor. Such hand deflashing process is costly due to the substantial labor time required to be expended to properly trim the particular article. Furthermore, in some instances it is difficult if not impossible to accomplish a satisfactory deflashing operation as where a particular molded article configuration prohibits manual access to the flash. As a articles is oftentimes substantially increased above actual molding production costs due to the high costs involved with deflashing procedures.
As a consequence of such high deflashing costs, in recent years, cryogenic deflashing apparatus have been introduced into the marketplace which in many instances have eliminated the requirement of costly hand trimming of residual flash from molded rubber and/or plastic manufactured articles. Basically such prior art cryogenic deflashing apparatus comprise a chamber maintained at an extremely low temperature by use of a cryogen gas such as nitrogen into which is introduced a high velocity stream of blasting media typically comprising plastic pellitized shot. The molded articles to be deflashed, such as O-rings, grommets, bushings, and the like, are emplaced within the deflashing chamber wherein, due to the relatively greater thickness of the molded article compared to the residual flash thereon, only the residual flash becomes embrittled in the low temperature environment. In its embrittled state, the residual flash is rapidly separated from or broken off of the molded article by the impact of the high velocity blasting media stream. By controlling the exposure duration of the molded articles within the cryogenic environment, as well as the velocity and dispersion of the deflashing media thereagainst, it has been found that satisfactory article deflashing may be accomplished, typically at a substantial reduction over hand deflashing operations.
Although such prior art cryogenic deflashing apparatus have generally proven to be superior over hand deflashing operations, they have possessed inherent deficiencies which have detracted from their widespread use in the trade. Foremost of these deficiencies has been the relatively large size and cost heretofore associated with such apparatus. In this regard, to insure continuous transport of media to the throwing wheel and thereby insure proper deflashing operations, it has been customary for prior art cryogenic deflashing apparatus to include complicated feed hopper/transport auger mechanisms to convey the blasting media to the throwing wheel. The use of such feed hopper/auger transport mechanisms has necessarily increased the overall size and cost of the apparatus and has mandated that large amounts of deflashing media be maintained within the apparatus, i.e. sufficient amounts to fill the hopper and auger conduit. Further, since the media accumulates spent flash removed in the deflashing process, the requirement of large amounts of media in such deflashing apparatus has additionally required the use of expensive media/flash separation units to be incorporated into the apparatus or alternatively the replacement of large amounts of blasting media during prolonged operation. Additionally, the use of such feed hopper/auger/separating systems in the prior art have proven to be prone to mechanical failure, thereby increasing maintenance costs for the apparatus.
In addition, conventional cryogenic deflashing apparatus have typically proven defective in preventing spillover, i.e. loss, of molded articles within the deflashing chamber during the deflashing operation. Such spillover problems arise primarily upon impact of the molded articles with the blasting media, whereby the molded articles are thrown out of the article basket and enter into the blasting media transport mechanism. As such it has not been uncommon for a relatively large percentage of molded articles to be lost during the cryogenic deflashing process, thereby reducing overall cost effectiveness of the same.
Further, due to the cost and size limitations of the prior art, most cryogenic deflashing apparatus have required dedicated production space to be provided for the apparatus as well as have required permanent hardwire electrical service to the same. As such, the prior art cryogenic deflashing apparatus have proven to be immobile and non-transportable to a particular job location to increase overall production efficiency.
SUMMARY OF THE PRESENT INVENTION
These as well as other deficiencies of the prior art are specifically addressed and alleviated by the present invention. More particularly, the present invention comprises a cryogenic deflashing apparatus specifically adapted to rapidly remove residual flash from molded articles and particularly relatively small-sized molded articles.
In the preferred embodiment, the cryogenic deflashing apparatus of the present invention comprises a readily transportable apparatus which is preferably formed having a double wall, insulated stainless steel housing. The cryogenic deflashing apparatus of the present invention incorporates a novel throw wheel assembly formed as a pump to create a vacuum which is utilized to continuously recirculate blasting media from the sump of the deflashing chamber back to the intake of the throw wheel assembly. The throw wheel assembly is powered by a pneumatic motor, the exhaust of which is supplied to the intake port of the throw wheel to perform a tuborcharging effect to pre-accelerate the blasting media onto the throw wheel and subsequently into the deflashing chamber. This particular turbo-assist feature of the present invention additionally serves to supplement the vacuum assist utilized to transport the blasting media to the intake of the throw wheel to insure consistent input of blasting media to the throw wheel even during low speed throw wheel operation. Although particularly suited for transporting deflashing media in a cryogen environment, the throw wheel assembly is applicable to other media transport and acceleration systems unrelated to cryogenic environments and deflashing applications.
Additionally, the cryogenic deflashing apparatus of the present invention incorporates a novel article basket drive and basket seal arrangement which positively prevents overspill of molded articles from the article basket during the deflashing operation and isolates the drive motor from cryogenic environment exposure. As such, repair and maintenance costs over conventional cryogenic deflashing apparatus are substantially reduced.
To aid in insertion and removal of the article basket from the deflashing chamber, the basket drive mechanism additionally incorporates a spring biased extractor mechanism which further serves to provide a continuous biasing force to maintain the dynamic seal formed upon the open end of the article basket within the deflashing chamber. To accommodate varying marketplace demands, the article basket may be provided having differing perforation sizes suitable for differing molded article deflashing applications.
In the preferred embodiment, the cryogenic deflashing apparatus of the present invention is formed as a compact, table top unit and operates with only two moving part systems, i.e. the throw wheel assembly and the basket drive mechanism. Further, in the preferred embodiment the cryogenic deflashing apparatus of the present invention incorporates standard 120-volt, 15 amp electrical service and operates utilizing a source of compressed shop air and a small low-pressure liquid nitrogen dewar so as to be transportable as well as insure low nitrogen consumption and low power usage.
DESCRIPTION OF THE DRAWINGS
These as well as other features of the present invention will become more apparent upon reference to the drawings wherein:
FIG. 1 is a front perspective view of the cryogenic deflashing apparatus of the present invention with the deflashing chamber access door being disposed in an opened orientation;
FIG. 2 is a rear perspective view of the cryogenic deflashing apparatus, of the present invention with the deflashing chamber access door being disposed in a closed orientation;
FIG. 3 is a partial perspective view depicting the upper interior surfaces of the deflashing chamber illustrating the throw wheel exit port, nitrogen port, and article basket registering and seal means formed thereon;
FIG. 4 is a perspective view of the article basket extractor mechanism and article basket drive mechanism disposed within the interior of the deflashing chamber;
FIG. 5 is a perspective view of the interior of the deflashing chamber with the article basket disposed within the deflashing chamber and engaged with the basket drive mechanism;
FIG. 6 is a partial cross-sectional view taken about line 6--6 of FIG. 5 illustrating the dynamic seal formed between the open end of the article basket and the deflashing chamber;
FIG. 7 is a perspective view depicting the throw wheel impeller and input tube of the throw wheel mechanism of the present invention;
FIG. 8 is a cross-sectional view taken about line 8--8 of FIG. 7 and illustrating the input throat of the input tube and the turbo-assist for the same; and
FIG. 9 is a perspective view of the input tube and impeller assembly disposed adjacent the deflashing chamber with the arrows depicting blasting media thrown from the throw wheel into the deflashing chamber.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIGS. 1 and 2, the cryogenic deflashing apparatus 10 of the present invention is depicted composed generally of a housing 12, throw wheel mechanism or assembly 14, article basket drive mechanism 16, cryogen gas storage system 18, and control panel 20. The housing 12 is preferably formed having a spaced double walled, stainless steel construction including a polyurethane foam thermal insulating core disposed therebetween. The housing 12 defines an interior cavity or deflashing chamber 22 therewithin, and includes a pivotally mounted access panel or door 24 to provide ingress and egress to the deflashing chamber 22. Although by way of example and not limitation, in the preferred embodiment, the housing 12 has an approximate dimension of 19 inches wide, 21 inches deep, and 26 inches high, and as such comprises a table top unit which can be utilized in restricted physical space applications.
The throw wheel mechanism 14 is preferably mounted to the exterior of the housing 12 upon an angularly inclined surface 26 thereof. In the preferred embodiment, the throw wheel mechanism 14 is composed of a fluidic, i.e. pneumatic, motor 28, the output shaft of which 29 drives an impeller or throw wheel 30 (shown in FIGS. 6, 7, and 9). The pneumatic motor 28 receives a supply of compressed fluid, i.e. dry, shop air (not shown) through input conduit 34 which additionally includes a conventional water trap 36 thereon. The rotational speed of the pneumatic motor 28 is controlled by a manually adjustable pressure valve 38 connected to the conduit 34 and disposed upon the control panel 20. In the preferred embodiment, when utilizing shop compressed air at 100 psig at 15 cfm, the rotational speed of the output shaft 29 of the pneumatic motor may be varied between 100 to 10,000 revolutions per minute by selected adjustment of the valve 38.
Referring more particularly to FIGS. 6, 7, and 9, it may be seen that the throw wheel or impeller 30 comprises a star-shaped member having plural vanes 42 extending radially outward from its central axis. Although the impeller may be formed from any low temperature compatible material, in the preferred embodiment, the impeller 30 is formed of an extruded aluminum material thereby being conducive to mass production techniques and is rigidly mounted to the output shaft 29 of the pneumatic motor 28. The central distal edges 44 of the vanes 42 are formed having an angular inclination complementary to an angular frusto-conical shaped surface 46 formed on the end of a input tube 48 of the throw wheel mechanism. As best shown in FIG. 8, the input tube 48 comprises a generally cylindrical member preferably formed of aluminum having a central flow cavity extending therethrough defined by an axially extending flow channel 50 and an angularly extending flow channel 52 which terminates at the beveled surface 46 of the input tube 48.
As best shown in FIG. 6, the impeller 30 and input tube 48 are assembled in a coaxial orientation whereby the distal edges 44 of the vanes 42 are proximate to the frusto-conical shaped beveled surface 46 of the input tube 48 and the impeller 30 and input tube 48 are encased within a throw wheel housing defining a pumping chamber 54 which extends about the impeller 30 and frusto-conical shaped beveled surface 46 of the input tube 48. A discharge opening or outlet 56 is provided through the throw wheel housing which is aligned with a rectangular slot 58 formed through the angular inclined panel 26 of the housing 12 and extending into the deflashing chamber 20.
As will be recognized, upon rotation of the impeller 30 relative the stationary input tube 48 and pumping chamber 54, the distal edges 44 of the impeller 30 wipe against the frusto-conical shaped beveled surface 46 of the input tube and thereby form a mechanical pump whereby a vacuum is drawn through the angular flow channel 52 and axial flow channel 50 in a direction indicated by the arrows in FIG. 8. As will be explained in more detail infra, this vacuum serves to draw blasting media from the interior of the deflashing chamber 20 for subsequent acceleration upon impact by the impeller 30 and final introduction into the deflashing chamber 20.
As best shown in FIG. 1, the distal end of the input tube 48 is rigidly connected to a media transfer tube or conduit 60 positioned on the exterior surface of the housing 12. The opposite end of the conduit 60 extends through the housing 12 so as to be disposed within the interior of the deflashing chamber 20 adjacent its lower region, i.e. sump. As such, blasting media or shot disposed within the lower region or sump of the deflashing chamber 20 may be transported by the vacuum created by the rotation of the impeller 30 through the media transfer conduit 60 and into the axial flow channel 50 and angular flow channel 52 of the input tube 48.
The cryogen gas storage system 18 generally comprises a cryogen gas dewar (not shown) containing a cryogen gas, such as liquid nitrogen, which is positioned adjacent the exterior of the housing 12. The dewar is connected via suitable tubing or conduits to a conventional cryogen valve 72, the operation of which is controlled by a temperature controller 74 disposed upon the control panel 20. A conduit 76 extends from the valve 72 on the exterior of the housing 12 and through the angular panel 26 of the housing terminating within the interior of the deflashing chamber 20 (as shown in FIG. 3). In the preferred embodiment, the temperature controller 74 comprises a conventional digital temperature controller with a set point and actual temperature display, with the temperature existing within the deflashing chamber 20 being sensed by a thermocouple (not shown) disposed within the interior of the deflashing chamber 20. As such, it will be recognized, that via the temperature controller 74, a supply of cryogen gas is periodically transported from the dewar through the valve 72 and conduit 76, and into the interior the deflashing chamber 20.
It is an important feature of the present invention that the exhaust from the pneumatic motor 28 is utilized to pre-accelerate blasting media onto the impeller 30 as well as supplement the vacuum created through the media transfer conduit 60. This beneficial result is achieved by supplying the exhaust from the pneumatic motor 28 through a motor exhaust conduit 80 and introducing the same within the flow channels 50 and 52 formed within the input tube 48. As shown in FIG. 8, the conduit 80 is rigidly connected to an input port 82 formed within the input tube 48. Preferably, the port 82 is coaxial with the angular flow channel 52 formed within the input tube 48 such that exhaust gas from the pneumatic motor 28 extends through the port 82 and angular flow channel 52 in a direction indicated by the arrows in FIG. 8. As the exhaust gas flows through the port 82, media particles traveling through the axial flow channel 50 are accelerated by the gas flow through the angular flow channel 52 in a turbocharging effect. This particular turbocharging effect has been found to substantially increase the speed of blasting media exiting the throw wheel assembly 16. Further, it will be recognized that the introduction of the exhaust gas through port 82 and angular flow channel 52 forms a venturi effect which serves to increase the amount of vacuum developed within the axial flow channel 50 of the input tube 48, which increase in vacuum serves to supplement the vacuum lift existing within the media transfer conduit 60 even during low rotational speed of the impeller 30.
Referring more particularly to FIGS. 2, 4, 5, and 6, the detailed construction of the article basket drive mechanism 16 may be described. By way of overview, the article basket drive mechanism 16 includes an article basket 100, a basket extraction mechanism designated generally by the numeral 101, and a basket rotating mechanism designated generally by the numeral 103 (in FIG. 2). The article basket 100 is preferably formed as a cylindrical stainless steel container having perforated walls, which is sized to receive molded articles to be deflashed therewithin. The basket extraction mechanism 103 allows rapid insertion and removal of the article basket 100 from the deflashing chamber 20. The basket rotating mechanism 103 rotates the article basket 100 about it's central axis to cause the molded articles to be tumbled within the basket 100, thereby insuring that all of the molded articles to be deflashed are exposed to the blasting media being thrown by the throw wheel mechanism 14 within the deflashing chamber 20.
The basket rotating mechanism 103 comprises an electric motor 110 which is rigidly mounted on the exterior of the housing 12. The output shaft of the motor 110 cooperates with a gear reduction unit or transmission 112 having an output shaft 114 which extends through the housing 12 into the interior of the deflashing chamber 20. The output shaft 114 includes a spline and is engaged with a basket drive shaft 116 disposed within the interior of the deflashing chamber 20. The spline connection between the output shaft 114 and basket drive shaft 16 allows moderate axial reciprocation of the basket drive shaft 116 along the length of the output shaft 114 while causing simultaneous rotation of the shafts 114 and 116. The distal end of the basket drive shaft 116 is connected to a cylindrical drive hub 120 which is journaled for rotational movement upon a yoke member 122. The yoke member 122 is mounted by a pair of axles 124 to a pair of support arms 126 which extend laterally from the rear wall 21 of the deflashing chamber 20. As best shown in FIG. 4, both support arms 126 are pivotally attached to a mounting block 128 depending from the rear wall 21 of the deflashing chamber 20. An elongate handle 130 is rigidly attached to the yoke 122 and extends laterally outward therefrom and a coil spring 132 is disposed between the yoke 122 and the interior wall 23 of the deflashing chamber 20. A retainer arm 134 extends outwardly from the interior wall 23 of the deflashing chamber 20 and includes a slot or recess 136 along its upper surface sized to receive the handle 130 therewithin.
The drive hub 120 includes plural lugs or pins 140 extending outwardly from its upper surface which mate with complementary-shaped recesses 144 (shown in phantom lines in FIG. 6) extending axially outward from a flange 146 mounted on the lower closed end 148 of the article basket 100. The opposite end of the article basket 100 is provided with a generally L-shaped circumferential flange 150 which extends a short distance over the open end of the article basket 100 as well as downwardly along its axial length. In the preferred embodiment, the flange 150 is formed of a high molecular weight polyethylene material which the applicants have found is highly conducive to withstand cryogenic environments. The flange 150 is received within an annular recess 152 formed on a bearing block or plate 154 rigidly mounted within the interior of the deflashing chamber 20 upon the inside surface of the angular housing wall 26. In the preferred embodiment, the bearing plate 154 is additionally formed of a high molecular weight polyethylene material and the diameter of the recess 152 is sized to be slightly greater than the maximum diameter of the flange 150. As such, when the flange 150 is disposed within the recess 152, the article basket 100 is axially registered with the recess 152 and with the article basket drive shaft 116. Further, a dynamic, i.e. rotational, seal is formed between the flange 150 and bearing plate 152 which serves to prevent any molded article spillover from the interior of the article basket 100 during the deflashing operation.
The motor 110 is controlled by a potentiometer 160 disposed upon the control panel 20. As will be recognized, during activation of the motor 110 by the potentiometer 160, output shaft 114 is rotated causing a corresponding rotational movement of the article basket drive shaft 116 and hub 120. Due to the engagement of the lugs 140 of the hub 120 within the plural recesses 144 of the flange 146, rotational movement of the hub 120 additionally causes rotational movement of the article basket 100 within the deflashing chamber 20. As such, molded articles contained within the interior of the article basket 100 are tumbled therein at a rotational speed determined for the particular deflashing application and controlled by the potentiometer 160.
The control panel 20 additionally includes a conventional on/off power switch 170 and power on light 172 as well as a conventional cycle timer 174 operative to provide automatic operation of the throw wheel assembly 14, article basket drive wheel mechanism 16, and cryogen gas storage system 18 on timed production cycles.
With the structure defined the operation of the cryogenic deflashing apparatus 10 of the present invention may be described. Initially, the apparatus 10 is placed upon a support surface and the electrical power cord (not shown) of the apparatus 10 may be plugged into a standard 120-volt, 15-amp grounded electrical line. A source of compressed dry shop air (not shown) may then be attached to the coupling 35 disposed upon the exterior of the housing 12 and upstream of the water trap 36. A filled dewar of cryogen gas, preferably nitrogen, may then be connected to the valve 72 of the cryogen gas storage system 18. Subsequently, the access door 24 may be disposed into its open configuration, as depicted in FIG. 1, and a quantity of conventional blasting media may be inserted within the interior of the deflashing chamber 20. In contradistinction to conventional systems, the apparatus 10 requires an extremely small quantity of blasting media, i.e. approximately 1 liter, as opposed to conventional systems which require approximately 50 pounds of media. This substantial reduction in media requirements is due primarily to the elimination of the prior art storage hopper and auger media transport systems which necessarily required substantial media volume to deliver continuous amounts of media to the throw wheel assembly.
The article basket 100 may be removed from the interior of the deflashing chamber 20 by manually grasping the handle 130 formed on the basket extraction mechanism 101 and urging the same in a direction from left to right, as viewed in FIG. 6. As will be recognized, due to the spline connection between the basket drive shaft 116 and output shaft 114, as well as the pivotal connection of the support arms 126 with the mounting block 128, this left to right movement of the handle 130 allows the yoke 122, support arms 126, and handle 130 to pivot about the mounting block 128 from its full line position to its phantom line position, shown in FIG. 6, whereby the coil spring 132 is compressed from its initial axial length. To maintain the retracted position of the yoke 122 relative the article basket 100, the handle 130 may be inserted within the recess 136 formed on the retainer arm 134. With the yoke 121 spaced from the lower end 148 of the article basket 100, the article basket 100 may then be axially reciprocated such that its flange 150 is disengaged from the recess 152 whereby the basket 100 can be removed from the interior of the deflashing chamber 20.
Depending upon the particular desired deflashing operation, the perforation size of the article basket 100 is selected to insure that the molded articles disposed therein cannot extend through the perforations, yet the blasting media may readily extend therethrough. In this regard, it is specifically contemplated that multiple article baskets 100 will be inventoried for the apparatus 10 to allow diversity in the deflashing operations carried out on the apparatus 10. When the appropriate article basket 100 is selected, the molded articles (not shown) desired to be deflashed are inserted within the interior of the article basket 100 and the basket 100 is then positioned within the deflashing chamber 20. The flange 150 formed on the open end of the article basket 100 may then be inserted within the recess 152 formed on the bearing block 154 whereby the article basket 100 is axially registered with the basket rotating mechanism 103. Subsequently, the handle 130 may be released from engagement with the recess 136 formed on the retainer arm 134 whereby the coil spring 160 urges the yoke 122 and handle 130 from its phantom line position to its full line position, shown in FIG. 6. In its full line position, the plural drive lugs 140 formed on the drive hub 120 may be inserted within the complementary formed apertures 144 formed on the lower flange mount 146 of the basket 100 to mechanically couple the article basket 100 to the basket rotating mechanism 103. Additionally, due to the coil spring 132, a continuous axial biasing force is applied to the article basket 100 thereby insuring that a dynamic seal is maintained between the flange 150 and recess 152 formed on the bearing block 154.
With the molded articles disposed within the deflashing chamber 120, the access door or panel 24 may be returned to its closed orientation, as depicted in FIG. 2, and the main power switch 170 may be turned to it's on position whereby the power-on light 172 is illuminated. Subsequently, the temperature controller 160 may be manually set to the desired cryogenic temperature to be maintained within the deflashing chamber 20 whereby, in response thereto, a suitable supply of cryogen gas is released from the dewar through the valve 72 through conduit 76 and within the interior of the deflashing chamber 20. As best shown in FIG. 3, the location of the distal end of conduit 76 causes the supply of cryogen gas to be released in a generally axial direction directly within the interior of the article basket 100 thereby insuring that the molded articles maintained within the interior of the basket 100 are exposed to the low temperature gas flow. Further, this axial flow of gas serves to conserve cryogen gas consumption by primarily cooling the molded articles maintained within the article basket 100 as opposed to the entire volume of the deflashing chamber.
The article basket drive mechanism 16 may then be activated by manually turning the potentiometer 160 upon the control panel 20, thereby causing the motor 110 to reach a desired rotational speed. As explained supra, rotation of the drive shaft 114 of the mechanism 16 causes a corresponding rotation of the article basket drive shaft 116 whereby the article basket 100 is rotated at the desired speed within the deflashing chamber 20. During this rotation, the peripheral flange 150 formed on the open end of the article basket 100 rides upon the recess 152 formed on the bearing block 154 which, due to the biasing force of the spring 116, forms a dynamic seal preventing any inadvertent overspilling of the molded articles out of the article basket 100.
The throw wheel control knob or valve 38 may then be manually turned, causing the valve 38 to allow a metered flow of compressed air into the pneumatic motor 28, thereby causing rotation of the impeller 30 relative the input tube 48. Due to the throw wheel assembly 14 being formed as a pump, during rotation of the impeller 30, a vacuum is created within the axial flow channel 50 and angular flow channel 52 of the input tube 48, which vacuum is communicated through the media transfer conduit 60 into the lower region, i.e. sump, of the deflashing chamber 20. The magnitude of this vacuum has been found to be sufficient to continuously draw blasting media contained within the sump of the deflashing chamber 20 upwardly through the media transfer tube 60 and into the input tube 48 of the throw wheel assembly 14. As the blasting media is drawn through the axial flow channel 50, it encounters the exhaust air flow from the pneumatic motor 28, which is supplied to the port 82 formed in the input tube 48 via conduit 80. Upon encountering the exhaust air flow, the particles are rapidly accelerated through the angular flow channel 52 in a generally radial or tangential direction to the rotational axis of the impeller 30 and subsequently contact the rotating impeller 30. As the blasting media contacts the vanes 42 of the impeller 30, they are further accelerated by mechanical contact with the impeller vanes 42 and discharged through the rectangular opening 58 to contact the molded articles maintained within the article basket 100. As will be recognized, due to the impeller 30 discharging the blasting media axially within the interior of the article basket 100, the molded articles contained therein are continuously bombarded by the blasting media which, in combination with their tumbling provided by the article basket drive mechanism 16, insures thorough and rapid article deflashing.
As the blasting media is propelled by the throw wheel mechanism 14 within the interior of the article basket 100, the blasting media proceeds through the multiple perforations formed within the article basket 100 and fall back to the lower sump portion of the deflashing chamber 20 so as to be continuously recycled back to the throw wheel assembly 16 via the transfer media conduit 60. Additionally, it will be recognized that due to the exhaust from the pneumatic motor 28 being supplied to the input tube 48, the blasting media particles are pre-accelerated into the impeller 30 which the applicants have found increases the velocity of the discharged blasting media from the throwing wheel assembly by a magnitude of approximately two-fold. Finally, it will be recognized that the amount of vacuum developed through the axial and angular flow channels 50 and 52, respectively, of the input tube 48 and through the media transport conduit 60, is dependent upon the rotational speed of the impeller 30 across the angular flow channel 52. As such, in relatively low rotational speed applications of the impeller 30, the use of the exhaust flow from the pneumatic motor 28 into the input tube 48 serves to supplement the amount of vacuum developed within the axial flow channel 50 and media transport conduit 60 to insure a continuous supply of media to the impeller 30. As such, the throw wheel mechanism 14 of the present invention provides a turbo-charging affect wherein blasting media is pre-accelerated into contact with the rotating impeller 30 as well as provides a supplemental transport force which augments the continuous transport of blasting media to the impeller even during low rotational speed of the impeller.
When the molded articles have had a sufficient residence time within the deflashing chamber 20 so as to be thoroughly deflashed by the deflashing media, operation of the throw wheel mechanism 14, article basket drive mechanism 16, and cryogen gas storage system 18 may be discontinued, whereby the access panel 24 may be opened and the article basket 100 may be removed by articulation of the basket extraction mechanism in a manner previously described. Subsequently, additional deflashing operation may be effectuated in the manner previously described.
For continuous production run batches, the automatic cycle timer 174 may be preset as desired to enable time sequentual batch operation of molded articles within the deflashing apparatus 16. Further, after continuous operation, the apparatus 10 of the present invention is specifically adapted to allow rapid removal of the blast media from the interior of the deflashing chamber 20, as by way of a vacuum, and subsequent refilling with new media which is not contaminated by flash removed in the deflashing process.
Although for purposes of illustration certain part configurations, materials, and sizes have been disclosed herein, those skilled in the art will recognize that various modifications to the same can be made without departing from the spirit of the present invention and such modifications are clearly contemplated herein. Additionally, although the throw wheel mechanism 14 has been described with specific use in relation to cryogenic deflashing apparatus, those skilled in the art will recognize that the throw wheel mechanism 16 additionally has utility in transporting and projecting blasting media in non-cryogenic environments and such additional uses of the throw wheel assembly 14 are clearly contemplated herein.
|
A cryogenic deflashing apparatus is disclosed specifically adapted to rapidly remove residual flash from molded articles. The cryogenic deflashing apparatus incorporates a novel throw wheel assembly formed as a pump to create a vacuum utilized to continuously recirculate blasting media within the deflashing chamber. The throw wheel is powered by a pneumatic motor the exhaust of which is supplied to the intake port of the throw wheel to pre-accelerate the blasting media onto the throw wheel as well as supplement the magnitude of vacuum lift of the blasting media into the throw wheel. An article basket and basket drive mechanism is disposed within the deflashing chamber and includes biasing seal means for eliminating article spillover during the deflashing operation as well as facilitating ease in removal and insertion of the article basket within the deflashing chamber.
| 1
|
CROSS REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. provisional application No. 61/530,540, filed Sep. 2, 2011, entitled “Coiled Tubing Injector Head with Chain Guides,” which is incorporated herein in its entirety by reference for all purposes.
BACKGROUND
The invention relates generally to tubing injectors for insertion of tubing into and retrieval from a well bore.
Coiled tubing well intervention has been known in the oil production industry for many years. A great length, often exceeding 15,000 feet, of small diameter, typically 1.5 inch, steel tubing is handled by coiling on a large reel, which explains the name of coiled tubing. The tubing reel cannot be used as a winch drum, since the stresses involved in using it, as a winch would destroy the tubing. The accepted solution in the oil industry is to pull tubing from the reel as it is required and pass it around a curved guide arch, or ‘gooseneck,’ so that it lies on a common vertical axis with the well bore. To control passage of tubing into and out of the well bore, a device called a coiled tubing injector head is temporarily mounted on the wellhead, beneath the guide arch. By use of the injector head, the tubing weight and payload is taken from the approximately straight tubing at the wellhead, leaving only a small tension necessary for tidy coiling to the tubing reel. Examples of coiled tubing injectors include those shown and described in U.S. Pat. Nos. 5,309,990, 6,059,029, and 6,173,769, all of which are incorporated herein by reference. Coiled tubing injector heads can also be used to run straight, jointed pipe in and out of well bores. General references to “tubing” herein should be interpreted to include both coiled tubing and jointed pipe, unless the context clearly indicates otherwise.
Coiled tubing is externally flush and is thus well adapted for insertion through a pressure retaining seal, or stuffing box, into a live well, meaning one with wellhead pressure that would eject fluids if not sealed. In a conventional coiled tubing application, an injector head needs to be able to lift, or pull, 40,000 pounds or more as tubing weight and payload when deep in the well. It also has to be able to push, or snub, 20,000 pounds or more to overcome stuffing box friction and wellhead pressure at the beginning and end of a trip into a well bore. Coiling tension is controlled by a tubing reel drive system and remains approximately constant no matter if the injector head is running tubing into or out of the well, or if it is pulling or snubbing. The coiling tension is insignificant by comparison to tubing weight and payload carried by the tubing in the well bore and is no danger to the integrity of the tubing. The tubing is typically run to a great depth in the well and then cycled repetitively over a shorter distance to place chemical treatments or to operate tools to rectify or enhance the well bore. It is by careful control of the injector head that the coiled tubing operator manipulates the tubing depth and speed to perform the programmed tasks.
In order that the injector head may manipulate tubing, it has to grip the tubing and then, concurrently, move the means of gripping so as to move the tubing within the well bore. Although other methods of achieving this aim are known, injector heads used for well intervention and drilling utilize a plurality of chain loops for gripping the tubing. There are many examples of such injector heads. Most rely on roller chains and matching sprocket forms as the means of transmitting drive from the driving shafts to the chain loop assemblies. Roller chain is inexpensive, very strong, and flexible. Yet, when the roller chain is assembled with grippers, which sometimes are comprised of a removable gripping element or block mounted to a carrier, the result is a massive subassembly, which is required to move at surface speeds of up to 300 feet per minute in some applications, changing direction rapidly around the drive and tensioner sprockets.
FIG. 1 schematically illustrates the basic components of an injector head that is a representative example of injector heads used for running tubing in and out of oil and gas wells. The injector head comprises, in this example, two closed or endless chains loops 12 , though more than two can be employed. Each chain loop 12 , which is closed or endless, is moved by drive shafts 14 via mounted sprockets 16 engaging with roller chain links, which form part of the total chain loop assembly. Each chain loop 12 has disposed on it a plurality of gripping blocks. As each chain loop is moved through a predetermined path, the portion of each chain loop that is adjacent to the other chain loop(s) over an essentially straight and parallel length, which is also the portion of its path along tubing 18 , is forced by some means, for example the hydraulically motivated roller and link assembly 20 , toward the tubing 18 , so that the grippers along this portion of the path of the chain loop, which may be referred to as the gripping portion, length or zone, engage and are forced against the tubing 18 , thereby generating a frictional force between the grippers and the coiled tubing that results in a firm grip. The non-gripping length(s) 22 of each loop 12 , which extends between the drive sprockets 16 and idler sprocket 24 , contrast to the chain along the gripping portion of the path of the chain loop, is largely unsupported and is only controlled, in the illustrated example, by centrally mounted tensioner 26 . However, many modern injectors dispense with the central tensioners on the non-gripping length and control the chain loop tension instead by means of adjustment at the bottom idler sprocket 24 .
SUMMARY
Oscillations can develop in portions of the path along which a chain loop moves that is not being biased for gripping, particularly during deployment of small diameter coiled tubing, sometimes known as capillary tubing. These portions of the path of the chain loop, as well as the portions of the chain loop present at any given time in these portions of the path, will be referred to as the free, non-gripping or non-biased portions. In such deployments operational speeds are higher than those with larger tubing. Chain oscillations cause rough running of the injector head, with attendant noise, reduced tubing control and reduced service life. Increasing tension of the chain has been found to increase the frequency of oscillation without sufficient dampening of the oscillations, and thus does not solve this problem. Increased chain tension can also be deleterious to the injector head by increasing bearing loads, resulting in reduced efficiencies, increased wear rates and reduced service life.
In the representative examples of injector heads described below, which are comprised of a plurality of chain loops mounted on sprockets, at least one of the chains loops is supported along a free or unbiased portion of a path of the chain loop by a chain guide. The support of the chain guide dampens or substantially prevents chain oscillations that otherwise could or would develop when the injector head is operated under certain conditions, without the need of having to increase chain tension.
In one example of an injector head, a straight portion of the path of each of a plurality of chain loops that extends between the sprockets, adjacent to the other chain loop(s), is biased for causing frictional engagement of grippers on the chains against tubing between the chain loops, so as to grip the tubing and allow its transit into and out of a well. An unbiased portion of the path of each chain loop on the other side of the sprockets from the biased portion of the chain, that is otherwise susceptible to oscillations when running in at least certain conditions, is constrained by a chain guide. The chain guide extends, in one embodiment, substantially over the full length of the unbiased section of the chain loop between the sprockets. The chain guide allows the chain to move freely as it is driven by the sprockets in loop, but dampens or prevents development of oscillations in the chain loop along one or more portions of its path in which it is not otherwise being pressed against tubing or constrained by sprockets or tensioners.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates basic components of a typical coiled tubing injector head of a general type, as found in the prior art.
FIG. 2 illustrates an embodiment of a frame for a coiled tubing injector, in an isometric view, with a continuously curved chain guide surface incorporated into a machine frame.
FIG. 3 illustrates an isometric view of a representative coiled tubing injector comprising the frame of FIG. 2 .
FIG. 4 is an isometric, sectional view of the representative coiled tubing injector of FIG. 3 .
FIG. 5 shows a section of a representative chain loop assembly for use in connection with a coiled tubing injector of FIGS. 2, 3 and 4 , illustrating roller chains, with gripping elements to the front and rolling elements to the back.
FIGS. 6A and 6B are schematic diagrams illustrating that a continuously curved guide surface for a free portion of a chain provides a distributed radial force.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
In the following description, like numbers refer to the same or similar features or elements throughout. The drawings are not to scale and some aspects of various embodiments may be shown exaggerated or in a schematic form.
With reference to FIGS. 2, 3, 4, and 5 coiled tubing injector head 30 has many of the same basic elements as injector head 10 of FIG. 1 , and therefore the same reference numbers are used for similar elements. However, use of the same numbers does not imply identity. The injector head 30 comprises a plurality of endless or closed chain loops 12 mounted to move along an elongated closed loop or path. A section of each chain loop path adjacent to the other chain loop paths is, in this example, practically straight, enabling engagement of an extended length of tubing when between the chain loops. The chain along this portion of the path is so that the gripping elements, disposed on the chains are biased toward each other, so that they are pressed against tubing inserted between the chain loops by a normal force. This portion of the path, and the length of chain along this portion of the path, may be referred to as the gripping or biased portion, length, zone, or segment. The mechanism or system used for biasing could include, for example, a biasing means similar to biasing means 20 of the exemplary injector head 10 of FIG. 1 . The biasing system illustrated by FIGS. 3 and 4 includes hydraulic rams 32 acting on pressure bars 32 , also referred to as skates. No particular form or construction or pressure bar or skate is intended to be implied. It could be a single element or comprised of multiple elements. In this particular example, the rams pull together opposing pressure bars. Any other mechanism or structure for causing gripping elements on a chain to be urged or pressed against the tubing would be substantially equivalent to this example and other examples given above for purposes of the invention described herein.
Referring now only to FIG. 5 , the chain loops 12 are, in this example, of the type comprising roller chain, which is comprised of roller links 36 , with gripping elements 38 mounted on pins 40 . One or more of the gripping elements can be of a type, for example, that comprise a carrier portion connected to one of the pins 40 in the chain, and a gripper attached or joined to the carrier in a removable fashion. The gripper 38 has a portion 40 that is shaped for engaging the tubing. On the back of each gripping element is mounted a rolling element in the form of a roller 42 . The rolling elements are positioned to facilitate free motion of the chain assembly along the pressure bar 34 . Rollers 42 on the backside of the gripping elements 38 connected to the chains roll along the pressure bars, causing the gripping elements 38 to be pressed against tubing captured between the chains, and thus create a normal force that increases the friction between the gripping elements and the tubing, allowing the chain loops to grip the tubing between them and transit the tubing into and out of a well by motion of the chains. Alternately, rollers could be carried by the biasing means.
Referring now back to FIGS. 2-5 , in the illustrated embodiment, the roller 42 is also positioned to roll along a chain guide. The chain guide is in the form of elongated member 44 that constrains non-gripping or non-biased portions 22 of the path of each of the chain loops 12 . The illustrated embodiment of the chain guide is continuously curved and positioned such that it contacts the portion of the chain loop over a length of its path in which it will not be pressed against or gripping tubing or otherwise constrained by sprockets or tensioners, ending close to both the drive sprocket 16 at the top and the idler/tensioner sprocket 24 at the bottom. The elongated curved member can be made from, for example, one or more steel plates. The roller 42 on the back of each gripper rolls along the curved member 44 . Furthermore, this particular guide is an example of a structural element that has been incorporated into the machine frame 46 . The elongated curved member forming the illustrated guide has been welded to the frame. The machine frame transmits from the load-bearing drive shafts 14 at the top of the frame, which are drive by hydraulic motors 48 , to pivot and load cell points, 48 and 50 , respectively, at the bottom. By combining load carrying with chain guide, the frame 46 reduces or minimizes the space and mass requirements of both functions.
Referring to FIGS. 6A and 6B , each chain loop 12 of an injector head, such as the ones shown in FIGS. 1-5 , comprises a flexible tensile member with distributed mass. It maintains a constant tensile force at any point throughout its entire length. If the member is of constant section and material, it will have its mass evenly distributed along its length. The chain will have a resistance to bending, but this may be very low. The combination of such a member's mass, flexibility, length, and tension together provide the mechanism for oscillation. Higher mass and greater length reduce the frequency of oscillation; higher tension increases it. Once induced, an oscillation in such a system will persist until its energy is exhausted by friction.
Any deflection of a continuous, flexible, tensile member from a straight path causes a compressive load approximately perpendicular to the tensile force. Conversely, if there is no deflection there will be no force. FIG. 6A shows a representation of chain 12 constrained by slight deflections 54 at the top and at the bottom. A length of chain 56 between the constraints causing the deflections is significant and may sustain an oscillation. FIG. 6B illustrates an embodiment showing frequent small deflections 58 , caused by a plurality of constraints placed along the path of the chain, distributed from top to bottom, approximating a continuously curved path for the flexible tensile member. When a sufficient number of constraints are provided along the length, the system will no longer have a frequency that can be excited by the environment. Provision of frequent small deflections along its length sufficiently constrains or controls the chains so that oscillations caused by the environment of the chain are effectively blocked without necessarily having to increase substantially the tension on the chain.
Chain guide 13 in FIGS. 2-5 provides a continuous, curved path for the chain loop and has the advantage of being incorporated into a frame. Furthermore, such a guide is well adapted for a roller chain with rolling elements mounted to its backside. However, multiple structures that provide a sufficient number of constrains along the length of the free portion of the chain could be substituted for it. One example includes two or more curved segments, which can be separated by gaps that together approximate a continuously curved path. Another example comprises multiple, discretely positioned constraints in the form of, for example, a bearing surface or, for chains without rolling elements, a roller which are appropriately spaced apart or distributed to prevent the environment from inducing oscillations in the unsupported portions of the chain that extend between the constraints.
The invention, as defined by the appended claims, is not limited to the described embodiments, which are intended only as examples. Alterations and modifications to the disclosed embodiments may be made without departing from the invention. The meaning of the terms used in this specification are, unless expressly stated otherwise, intended to have ordinary and customary meaning and are not intended to be limited to the details of the illustrated or described structures or embodiments.
|
In an injector head ( 30 ) for handling tubing for insertion into and retrieval from a wellbore, a non-gripping portion of the path ( 22 ) of each chain loop ( 12 ), which is otherwise susceptible to oscillations when running in at least certain conditions, is constrained by a chain guide ( 44 ). The chain guide allows the chain to move freely as it is driven by the sprockets ( 16 ) in a loop, but dampens or prevents development of oscillations in the chain loop ( 12 ) when moving along one or more sections of its path in which it is not otherwise be pressed against tubing or constrained by sprockets or tensioners.
| 4
|
TECHNICAL FIELD
The present invention relates to a solar heat boiler for collecting heat from the sun and generating steam using the heat, and a solar heat electric power generation plant using the solar heat boiler. Particularly, it relates to a solar heat boiler which is inexpensive and capable of preventing thermal damage to a heat transfer tube, and a solar heat electric power generating plant using the solar heat boiler.
BACKGROUND ART
In some sites, the amount of collected heat in a solar heat boiler inevitably repeats sudden increase and decrease in accordance with the amount of solar radiation varying suddenly in a short time due to the sunlight blocked by cloud or the like.
On the other hand, solar heat boilers are often introduced into a region called the Sunbelt, that is, a region where annual Direct Normal Irradiance (DNI) is beyond 2,000 kWh/m 2 , in order to obtain as large the annular total amount of collected heat as possible.
It is usually sunny in the Sunbelt throughout the year, and the amount of solar radiation hardly changes suddenly due to the change in weather. Thus, the stable amount of collected heat over time prevents the aforementioned problem from coming to the surface.
In regions other than the Sunbelt, for example, in Japan, however, the amount of solar radiation frequently changes suddenly in a day due to the change in weather or the movement of clouds so that sudden increase or decrease in the amount of collected heat may appear repeatedly. It is therefore important to take measures against such a problem.
Concentrating solar power generation plants are roughly classified into stand-alone type electric power generation plants and integrated type electric power generation plants. In the stand-alone type electric power generation plants, heat may be secured mostly by solar heat and partially backed up with fossil fuel etc. On the other hand, in the integrated type electric power generation plants, heat is secured mostly by fossil fuel or nuclear fuel and partially backed up with solar heat.
In each type of the stand-alone type electric power generation plants and the integrated type electric power generation plants, heat from the sunlight is collected and used as a heating source, and both the types may use substantially common solar collectors.
Solar collectors used typically include trough type ones, Fresnel type ones, tower type ones, etc. Ina trough type solar collector, a heat transfer tube is disposed above an inner circumferential curved surface of a reflecting mirror extending like a trough so that the sunlight can be collected in the heat transfer tube by the mirror. Thus, water circulating in the heat transfer tube is heated to generate steam. In a Fresnel type solar collector, a several number of reflecting mirrors having flat surfaces or slightly curved surfaces are arranged side by side at angles differing bit by bit from one to another, and a several number of heat transfer tubes are disposed above the group of the reflecting so that the sunlight can be collected in the heat transfer tube by the group of the reflecting to generate steam. In a tower type solar collector, a heat transfer tube panel is disposed on a tower having a predetermined height and a large number of reflecting mirrors (heliostats) are disposed on the ground surface so that the sunlight can be collected in the heat transfer tube panel by the group of the reflecting mirrors (heliostats) to generate steam.
Among them, in the trough type and the Fresnel type, the focal length is so short that the concentration ratio of the sunlight (the heat density in a heat collecting portion) is low. On the other hand, the tower type has an advantage that the focal length is so long that the concentration ratio of the sunlight (the heat density in a heat collecting portion) is high.
High heat density in a heat collecting portion leads to increase in the amount of collected heat per unit heat transfer area, so that higher-temperature steam can be obtained. However, when the heat density is simply increased to make a phase change from a water state to superheated steam, there arises a problem that a high-temperature area is formed locally to thereby cause damage to transfer tubes or the like.
In a thermal power generation boiler or the like, the amount of fuel is managed properly to avoid such damage to any heat transfer tube. In the case of solar heat, however, the heat input amount fluctuates so largely that it is difficult to avoid thermal damage to the heat transfer tubes.
To solve such a problem in the tower type with high heat density, a solar heat boiler configured as shown in FIG. 17 and FIG. 18 has been proposed, for example, in Patent Literature 1, Patent Literature 2, etc.
FIG. 17 is a schematic configuration diagram of a solar heat boiler. FIG. 18 is an enlarged schematic configuration diagram of a heat collecting device for use in the solar heat boiler.
In FIGS. 17 and 18 , the reference numeral 1 represents a heat collecting device; 2 , an evaporator; 3 , a superheater; 4 , a steam-water separation device; 5 , a tower; 6 , a heliostat; 7 , the sun; 8 , a steam turbine; 9 , an electric power generator; and 11 , a water supply pump.
As shown in FIG. 18 , the heat collecting device 1 is functionally divided into the evaporator 2 and the superheater 3 , and the steam-water separation device 4 is placed between the evaporator 2 and the superheater 3 . The heat collecting device 1 is placed on the tower 5 which is about 30 to 100 meters high. Light from the sun 7 is reflected by the heliostats 6 placed on the ground, and condensed on the heat collecting device 1 so as to heat the evaporator 2 and the superheater 3 . Superheated steam generated in the heat collecting device 1 is sent to the steam turbine 8 so as to rotate the electric power generator 9 . Electric power is generated in such a mechanism.
Further, FIG. 19 is a schematic configuration diagram of a solar heat electric power generation system described in U.S. Pat. No. 7,296,410 (Patent Literature 3). In FIG. 19 , the reference numeral 200 represents a solar heat electric power generation system; 201 , a fluid channel; 202 , a valve; 203 , a pump; 204 , a trough device; 205 , a heat collection tube; 206 , a solar heat collector; 207 , a tower; 208 , a low-temperature heat storage tank; 209 , an intermediate heat storage tank; 210 , a high-temperature heat storage tank; 211 , a high-output generation device; 212 , a turbine; and 213 , an electric power generator.
In the solar heat electric power generation system, a thermal fluid stored in the low-temperature heat storage tank 208 is supplied to the trough devices 204 by the pump 203 , and heated by heat derived from the condensed light of the sun 106 . The thermal fluid further heated in the tower 207 is then sent to the high-temperature heat storage tank 210 . The thermal fluid sent to the high-temperature heat storage tank 210 is sent to the high-output generation device 211 by the pump 203 . The thermal fluid whose temperature has decreased due to heat exchange is returned to the low-temperature heat storage tank 208 .
On the other hand, configuration is made in such a manner that steam generated by the high-output generation device 211 is sent to the turbine 212 so that electric power is generated by the electric power generator 213 .
Further, FIG. 20 is a schematic configuration diagram of a solar heat/light collection plant described in U.S. Pat. No. 8,087,245 (Patent Literature 4). In FIG. 20 , the reference numeral 301 represents a trough type collector; 302 , a tower with heliostats; 303 , a low-temperature heat storage; 304 . a high-temperature heat storage; 305 , an auxiliary device using fossil fuel; 306 , a turbine; 307 , an electric power generator; 308 , a condenser; and 309 , a pump.
In the solar heat/light collection plant, water is sent to the trough type collector 301 by the pump 309 and heated by the heat of the sun so as to generate saturated steam. The generated saturated steam is sent to the tower with heliostats 302 . The turbine 306 is driven by the superheated steam generated thus, so as to generate electric power in the electric power generator 307 .
The steam is returned to water in the condenser 308 , and the water is supplied again by the pump 309 . Further, the configuration includes a line in which the saturated steam from the trough type collector 301 is not circulated in the tower with heliostats 302 but is passed through the auxiliary device 305 using fossil fuel so as to generate superheated steam.
CITATION LIST
Patent Literature
Patent Literature 1: WO 2009/129166A2
Patent Literature 2: WO 2010/048578A1
Patent Literature 3: U.S. Pat. No. 7,296,410
Patent Literature 4: U.S. Pat. No. 8,087,245
SUMMARY OF INVENTION
Technical Problem
In the aforementioned background-art technique shown in FIGS. 17 and 18 , it is, however, necessary to place not only the evaporator 2 and the superheater 3 but also the steam-water separation device 4 in an upper portion of the tower 5 which is 30 to 100 meters high. It is therefore necessary to build the tower 5 strong enough to withstand earthquakes etc. and to support not only the loads of the evaporator 2 and the superheater 3 which are assemblies of a large number of heat transfer tubes but also the load of the steam-water separation device 4 which holds saturated water internally. Therefore, there is a problem that the facility cost and the construction cost increase.
In addition, water must be pumped up to the steam-water separation device 4 at a high site by the water supply pump 11 . Therefore, the water supply pump 11 must be high in pumping-up capacity and expensive. Therefore, the facility cost and the running cost increase.
Further, the amount of collected heat in the heat collecting device 1 must be suppressed in order to avoid thermal damage to the heat transfer tubes constituting the evaporator 2 and the superheater 3 . Thus, there is another problem that the volume and temperature of steam supplied to the steam turbine 8 fluctuate, with the result that the amount of power generation is not constant.
In the background-art technique shown in FIG. 19 , the high-output generation device 211 is required for heat exchange between the thermal fluid and the water-steam. Further, the low-temperature heat storage tank 208 , the intermediate heat storage tank 209 and the high-temperature heat storage tank 210 , etc. are required for suppressing the temperature change caused by the fluctuation of the solar radiation to thereby stabilize the output of the electric power generator 307 . Thus, there is a problem that the facility cost increases and the installation space increases.
On the other hand, in the background-art technique shown in FIG. 20 , horizontal heat collecting tubes are placed in the trough type collector 301 . Therefore, the fluctuation of the solar radiation leads to a change in the fluid state of a two-phase flow of steam and water in the horizontal heat collecting tubes. Thus, the bottom portion of each tube is filled with water and the top portion of the tube is filled with steam. In the trough type collector 301 which is heated on one side, the temperature on the side (upper portion) where steam exists increases extraordinarily. It is therefore likely that the heat collecting tubes may be damaged.
Further, the auxiliary device 305 using fossil fuel must be placed for supporting the fluctuation of the solar radiation. There is a problem that the facility cost and the running cost increase thus.
To solve such disadvantages belonging to the background-art techniques, an object of the present invention is to provide a solar heat boiler capable of avoiding thermal damage to a heat transfer tube without increasing facility cost and construction cost, and capable of suppressing fluctuation in the amount of power generation in a steam turbine to thereby supply high-quality electricity, and an independent type or composite type solar heat electric power generation plant using the solar heat boiler.
Solution to Problem
In order to attain the foregoing object, according to a first configuration of the present invention, there is provided a solar heat boiler, including:
a low-temperature heating device including a heat transfer tube which is disposed horizontally so that water supplied from a water supply pump can circulate through the heat transfer tube, and a reflecting mirror which collects sunlight in the heat transfer tube, so that the low-temperature heating device can heat the water by heat of the sunlight;
a steam-water separation device by which two-phase fluid of water and steam generated in the low-temperature heating device is separated into water and steam;
a high-temperature heating device by which the steam separated by the steam-water separation device is superheated by heat of sunlight; and
a circulating pump by which the water separated by the steam-water separation device is supplied to the low-temperature heating device.
According to a second configuration of the invention, there is provided a solar heat boiler according to the first configuration, wherein:
the low-temperature heating device, the steam-water separation device and the circulating pump are placed on or near a ground surface, and the high-temperature heating device is placed in a higher site than the low-temperature heating device and the steam-water separation device; and
a water level gauge which measures a water level in the steam-water separation device, a water supply valve which adjusts a flow rate of water supplied to the low-temperature heating device, and a circulation flow rate control valve which adjusts the amount of water circulating between the low-temperature heating device and the steam-water separation device are provided so that the flow rate of the supplied water or the amount of the circulating water can be adjusted by the water supply valve or the circulation flow rate control valve with the water level in the steam-water separation device being set at a predetermined value.
According to a third configuration of the invention, there is provided a solar heat boiler according to the first or second configuration, wherein:
the low-temperature heating device includes a trough type 1 solar collector in which a heat transfer tube is disposed above an inner circumferential curved surface of a reflecting mirror extending like a trough so that the sunlight can be collected in the heat transfer tube by the reflecting mirror to heat water circulating through the heat transfer tube and generate steam, or a Fresnel type solar collector in which a several number of reflecting mirrors having substantially flat surfaces are arranged side by side and a heat transfer tube is disposed above the group of the reflecting mirrors so that the sunlight can be collected in the heat transfer tube by the group of the reflecting mirrors to heat water circulating through the heat transfer tube and generate steam; and
the high-temperature heating device includes a tower type solar collector in which a heat transfer tube panel is placed on a tower having a predetermined height and a large number of reflecting mirrors are disposed so that the sunlight can be collected in the heat transfer tube panel by the group of the reflecting mirrors to superheat steam circulating through the heat transfer tube panel.
According to a fourth configuration of the invention, there is provided a solar heat boiler according to any one of the first to third configurations, wherein:
a glass tube with a predetermined length is disposed on the periphery of the heat transfer tube with a predetermined length so as to form a double structure, and an airtight state or a vacuum state is kept between the heat transfer tube and the glass tube;
the heat transfer tube with the predetermined length is formed by a plurality of heat transfer tubes joined to each other by welding, and the glass tube with the predetermined length is formed by a plurality of glass tubes joined to each other through metal joint tubes which are disposed in joint portions between the glass tubes and which are welded with the glass tubes respectively; and
outlet fluid temperature in the low-temperature heating device is regulated to 300° C. or less.
According to a fifth configuration of the invention, there is provided a solar heat boiler according to the fourth configuration, wherein:
a thermometer and a flowmeter are placed in an outlet of the low-temperature heating device and a flow rate of water supplied to the low-temperature heating device is adjusted so that a temperature measured by the thermometer and a flow rate measured by the flowmeter can be set at predetermined values.
According to a sixth configuration of the invention, there is provided a solar heat boiler according to the fourth configuration, wherein:
a thermometer and a flowmeter are placed in an outlet of the low-temperature heating device and the amount of collected heat in the low-temperature heating device is adjusted so that a temperature measured by the thermometer and a flow rate measured by the flowmeter can be set at predetermined values.
According to a seventh configuration of the invention, there is a provided a solar heat boiler according to any one of the first to third configurations, wherein:
a thermometer and a flowmeter are placed in an outlet of the low-temperature heating device and the amount of collected heat in the high-temperature heating device is adjusted in accordance with a value of a temperature measured by the thermometer and a value of a flow rate measured by the flowmeter.
According to an eighth configuration of the invention, there is provided a solar heat boiler, including:
a solar collector including a thermal channel in which a thermal such as diphenyl, biphenyl, 1,1-diphenylethane, etc. circulates, a thermal fluid circulating pump which is provided in the middle of the thermal fluid channel, a heat transfer tube which is provided in the middle of the thermal fluid channel and which is disposed horizontally so that the thermal fluid can circulate through the heat transfer tube, and a reflecting mirror which collects sunlight in the heat transfer tube, so that heat generated by collection of the sunlight can be transferred to the thermal fluid circulating through the heat transfer tube;
a heat exchanger-including low-temperature heating device in which a part of the thermal fluid channel of the solar collector is placed internally as a heat exchanger;
a water supply pump which supplies water to the heat exchanger-including low-temperature heating device;
a steam-water separation device by which two-phase fluid of water and steam generated by transferring the heat collected by the solar collector through the thermal fluid to water in the heat exchanger-including low-temperature heating device is separated into water and steam;
a high-temperature heating device by which the steam separated by the steam-water separation device is superheated by heat of sunlight; and
a circulating pump by which the water separated in the steam-water separation device is supplied to the heat exchanger-including low-temperature heating device.
According to a ninth configuration of the invention, there is provided a solar heat boiler according to any one of the first to eighth configurations, wherein:
the circulating pump is placed on a channel extending from the steam-water separation device to the low-temperature heating device.
According to a tenth configuration of the invention, there is provided a solar heat electric power generation plant, including:
a solar heat boiler according to any one of the first to ninth configurations;
a steam turbine which is driven by steam generated by the solar heat boiler; and
an electric power generator which is driven by the steam turbine.
According to an eleventh configuration of the invention, there is provided a solar heat electric power generation plant, including:
a boiler which generates steam by burning fuel or generating heat therefrom;
a water supply pump which supplies water to the boiler;
a steam turbine which is driven by steam generated by the boiler;
an electric power generator which is driven by the steam turbine;
a water supply heater which heats the water supplied from the water supply pump using steam extracted from the steam turbine;
a low-temperature heating device including a heat transfer tube which is disposed horizontally so that water supplied from the water supply pump can circulate through the heat transfer tube, and a reflecting mirror which collects sunlight in the heat transfer tube, so that the low-temperature heating device can heat a part of the water by heat of the sunlight;
a steam-water separation device by which two-phase fluid of water and steam generated in the low-temperature heating device is separated into water and steam;
a high-temperature heating device by which the steam separated by the steam-water separation device is heated by heat of sunlight; and
a circulating pump by which the water separated by the steam-water separation device is supplied to the low-temperature heating device.
According to a twelfth configuration of the invention, there is provided a solar heat electric power generation plant according to the eleventh configuration, wherein:
the low-temperature heating device, the steam-water separation device and the circulating pump are placed on or near a ground surface, and the high-temperature heating device is placed in a higher site than the low-temperature heating device and the steam-water separation device; and
a water level gauge which measures a water level in the steam-water separation device, a water supply valve which adjusts a flow rate of water supplied to the low-temperature heating device, and a circulation flow rate control valve which adjusts the amount of water circulating between the low-temperature heating device and the steam-water separation device are provided so that the flow rate of the supplied water or the amount of the circulating water can be adjusted by the water supply valve or the circulation flow rate control valve with the water level in the steam-water separation device being set at a predetermined value.
According to a thirteenth configuration of the invention, there is provided a solar heat electric power generation plant according to the eleventh or twelfth configuration, wherein:
the low-temperature heating device includes a trough type solar collector in which a heat transfer tube is disposed above an inner circumferential curved surface of a reflecting mirror extending like a trough so that the sunlight can be collected in the heat transfer tube by the reflecting mirror to heat water circulating through the heat transfer tube and generate steam, or a Fresnel type solar collector in which a several number of reflecting mirrors having substantially flat surfaces are arranged side by side and a heat transfer tube is disposed above the group of the reflecting mirrors so that the sunlight can be collected in the heat transfer tube by the group of the reflecting mirrors to heat water circulating through the heat transfer tube and generate steam; and
the high-temperature heating device includes a tower type solar collector in which a heat transfer tube panel is placed on a tower having a predetermined height and a large number of reflecting mirrors are disposed so that the sunlight can be collected in the heat transfer tube panel by the group of the reflecting mirrors to heat water circulating through the heat transfer tube panel and generate steam.
According to a fourteenth configuration of the invention, there is provided a solar heat electric power generation plant according to any one of the eleventh to thirteenth configurations, wherein:
a glass tube with a predetermined length is disposed on the periphery of the heat transfer tube with a predetermined length so as to form a double structure, and an airtight state or a vacuum state is kept between the heat transfer tube and the glass tube;
the heat transfer tube with the predetermined length is formed by a plurality of heat transfer tubes joined to each other by welding, and the glass tube with the predetermined length is formed by a plurality of glass tubes joined to each other through metal joint tubes which are disposed in joint portions between the glass tubes and which are welded with the glass tubes respectively; and
outlet fluid temperature in the low-temperature heating device is regulated to 300° C. or less.
According to a fifteenth configuration of the invention, there is provided a solar heat electric power generation plant according to the fourteenth configuration, wherein:
a thermometer and a flowmeter are placed in an outlet of the low-temperature heating device and a flow rate of water supplied to the low-temperature heating device is adjusted so that a temperature measured by the thermometer and a flow rate measured by the flowmeter can be set at predetermined values.
According to a sixteenth configuration of the invention, there is provided a solar heat electric power generation plant according to the fourteenth configuration, wherein:
a thermometer and a flowmeter are placed in an outlet of the low-temperature heating device and the amount of collected heat in the low-temperature heating device is adjusted so that a temperature measured by the thermometer and a flow rate measured by the flowmeter can be set at predetermined values.
According to a seventeenth configuration of the invention, there is provided a solar heat electric power generation plant according to any one of the eleventh to thirteenth configurations, wherein:
a thermometer and a flowmeter are placed in an outlet of the low-temperature heating device and the amount of collected heat in the high-temperature heating device is adjusted in accordance with a value of a temperature measured by the thermometer and a value of a flow rate measured by the flowmeter.
According to an eighteenth configuration of the invention, there is provided a solar heat electric power generation plant according to any one of the eleventh to thirteenth configurations, wherein:
a water level gauge which measures a water level in the steam-water separation device, a water supply valve which adjusts a flow rate of water supplied to the low-temperature heating device, and a circulation flow rate control valve which adjusts the amount of water circulating between the low-temperature heating device and the steam-water separation device are provided so that the flow rate of the supplied water or the amount of the circulating water can be adjusted by the water supply valve or the circulation flow rate control valve with the water level in the steam-water separation device being set at a predetermined value.
According to a nineteenth configuration of the invention, there is provided a solar heat electric power generation plant according to any one of the eleventh to thirteenth configurations, wherein:
a steam extraction valve is provided on the outlet side of the steam turbine; and
the steam extraction valve is operated in accordance with the amount of steam supplied from the high-temperature heating device, so that a steam extraction_flow in the steam turbine can be adjusted.
Advantageous Effects of Invention
According to the invention configured as described above, it is possible to provide a solar heat boiler capable of avoiding thermal damage to a heat transfer tube without increasing facility cost and construction cost, and capable of suppressing fluctuation in the amount of power generation in a steam turbine to thereby supply high-quality electricity, and an independent type or composite_type solar heat electric power generation plant using the solar heat boiler.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 A schematic configuration diagram of a stand-alone type solar electric power generation plant according to a first embodiment of the invention.
FIG. 2 A view showing principles for explaining the configuration and so on of a tower type solar collector where a high-temperature heating device is placed.
FIG. 3 An enlarged schematic configuration diagram of a heat transfer tube panel for use in the high-temperature heating device.
FIG. 4 A schematic configuration diagram of a stand-alone type solar electric power generation plant according to a second embodiment of the invention.
FIG. 5 A view showing principles for explaining the configuration and so on of a trough type solar collector.
FIG. 6 A view showing principles for explaining the configuration and so on of a Fresnel type solar collector.
FIG. 7 A schematic configuration diagram of a stand-alone type solar electric power generation plant according to a third embodiment of the invention.
FIG. 8 A partially enlarged sectional view showing the vicinities of a heat transfer tube for use in a trough type (or Fresnel type) solar collector.
FIG. 9 A schematic configuration diagram of a solar heat integrated type electric power generation plant according to a fourth embodiment of the invention.
FIG. 10 A diagram showing an example in which the opening degree of a steam extraction valve provided on the outlet side of a steam turbine is adjusted in accordance with a change in the amount of steam passing through a steam valve provided on the outlet side of a high-temperature heating device according to the fourth embodiment.
FIG. 11 A schematic configuration diagram of a solar heat integrated type electric power generation plant according to a fifth embodiment of the invention.
FIG. 12 A schematic configuration diagram of a solar heat integrated type electric power generation plant according to a sixth embodiment of the invention.
FIG. 13 A schematic configuration diagram of a stand-alone type solar electric power generation plant according to a seventh embodiment of the invention.
FIG. 14 A characteristic graph showing the relationship between a water level L in a steam-water separation device and an outlet steam quality X in a low-temperature heating device.
FIG. 15 (a) is a view showing classification of fluid states in a two-phase flow of water and steam in a horizontal heat transfer tube of a low-temperature heating device, and (b) is a schematic view showing each fluid state of the two-phase flow of water and steam in the horizontal heat transfer tube.
FIG. 16 A schematic configuration diagram of a solar heat integrated type electric power generation plant according to an eighth embodiment of the invention.
FIG. 17 A schematic configuration diagram of a solar heat boiler according to the background art.
FIG. 18 An enlarged schematic configuration diagram of a heat collecting device for use in the solar heat boiler.
FIG. 19 A schematic configuration diagram of a solar heat electric power generation system proposed in Patent Literature 3.
FIG. 20 A schematic configuration diagram of a solar heat/light collecting plant proposed in Patent Literature 4.
DESCRIPTION OF EMBODIMENTS
(First Embodiment)
Next, embodiments of the invention will be described with reference to the drawings. FIG. 1 is a schematic configuration diagram of a stand-alone type solar electric power generation plant according to a first embodiment of the invention.
In this solar heat electric power generation plant, as shown in FIG. 1 , water supplied from a water supply pump 11 is sent to a water supply heater 12 through a water supply valve 19 . The water heated thus by the water supply heater 12 is introduced into a low-temperature heating device 13 through a steam-water separation device 4 . In the low-temperature heating device 13 , the supplied water is heated by light 32 from the sun 7 . The water is circulated between the steam-water separation device 4 and the low-temperature heating device 13 by a circulating pump 15 .
Two-phase fluid of water and steam generated in the low-temperature heating device 13 is separated into saturated water and saturated steam by the steam-water separation device 4 . The separated steam is sent to a high-temperature heating device 14 placed on a tower 16 . The steam introduced into the high-temperature heating device 14 is further superheated by solar heat reflected by heliostats 6 and introduced into the high-temperature heating device 14 .
The superheated steam generated in the high-temperature heating device 14 is designed to rotate a steam turbine 8 so that electric power can be generated by an electric power generator 9 due to the rotation of the steam turbine 8 . In order to adjust the amount of steam supplied to the steam turbine 8 , the water supply valve 19 is placed between the water supply pump 11 and the water supply heater 12 , and a steam valve 18 is placed between the high-temperature heating device 14 and the steam turbine 8 .
FIG. 2 is a view showing principles for explaining the configuration and so on of a tower type solar collector where the high-temperature heating device 14 is placed.
In the tower type solar collector, as shown in FIG. 2 , the high-temperature heating device 14 (heat transfer tube panel 27 ) is placed on the tower 16 having a predetermined height (about 30 to 100 meters). On the other hand, a large number of heliostats 6 are disposed on the ground surface so as to face in various directions. The heliostats 6 are designed to follow the movement of the sun 7 so that light can be collected in the high-temperature heating device 14 (heat transfer tube panel 27 ) by the group of the heliostats 6 so as to generate superheated steam.
The tower type solar collector can generate steam at a higher temperature than a trough type solar collector. Thus, the tower type solar collector has a merit that the turbine efficiency can be increased to obtain higher electric power.
FIG. 3 is an enlarged schematic configuration diagram of the heat transfer tube panel 27 for use in the high-temperature heating device 14 . The heat transfer tube panel 27 is constituted by a superheater lower header 22 , a large number of superheater heat transfer tubes 21 , and a superheater upper header 23 . The superheater lower header 22 distributes steam from the steam-water separation device 4 evenly. The superheater heat transfer tubes 21 are disposed in parallel so that the steam distributed by the superheater lower header 22 can be circulated through the superheater heat transfer tubes 21 . The superheater upper header 23 collects superheated steam flowing out from the superheater heat transfer tubes 21 . The superheated steam outputted from the superheater upper header 23 is supplied to the steam turbine 8 .
The low-temperature heating device 13 and the steam-water separation device 4 hold a large amount of water internally and therefore each device is heavy as a whole. Thus, the low-temperature heating device 13 and the steam-water separation device 4 are placed on the ground surface or near the ground surface by use of a low foundation which is, for example, about 1 to 2 meters high. Since the low-temperature heating device 13 and the steam-water separation device 4 are thus placed on or near the ground surface, it is not necessary to pump up water to a site which is, for example, 30 to 100 meters high as in the background art. Therefore, the water supply pump 11 which is low in pumping-up capacity and low in price can be used.
On the other hand, light 32 from the heliostats 6 is collected with high optical density in the high-temperature heating device 14 . Therefore, the high-temperature heating device 14 is placed in a site which is 10 or more meters (for example, 30 to 100 meters) high from the ground surface. Since fluid flowing inside the high-temperature heating device 14 is only steam, the high-temperature heating device 14 is much lighter in weight and much smaller in size than the background-art heat collecting device 1 (see FIG. 18 ) which is constituted by the evaporator 2 , the superheater 3 and the steam-water separation device 4 . Incidentally, the ratio in the amount of collected heat between the low-temperature heating device 13 and the high-temperature heating device 14 is generally 9:1 to 7:3. The amount of collected heat in the high-temperature heating device 14 is much smaller than that of the low-temperature heating device 13 .
In the embodiment shown in FIG. 1 , the circulating pump 15 is placed on a channel from the steam-water separation device 4 to the low-temperature heating device 13 . The use temperature of the circulating pump 15 can be decreased as compared with that in the case where the circulating pump 15 is placed on a channel from the low-temperature heating device 13 to the steam-water separation device 4 . Thus, it is not necessary to use a pump which is high in heat resistance and high in price, but it is possible to reduce the cost and improve the reliability. This effect can be also obtained in each embodiment on and after a second embodiment in the same manner.
(Second Embodiment)
FIG. 4 is a schematic configuration diagram of a stand-alone type solar electric power generation plant according to a second embodiment of the invention.
In the embodiment, a low-temperature heating device 24 consisting of a trough type solar collector is used. The other configuration, the mechanism of electric power generation, etc. are similar to those in the aforementioned first embodiment, and redundant description thereof will be omitted.
FIG. 5 is a view showing principles for explaining the configuration and so on of a trough type solar collector.
The trough type solar collector has the following mechanism, as shown in FIG. 5 . That is, a heat transfer tube 31 is disposed horizontally in a focal position above the inner circumferential curved surface of each reflecting mirror 30 extending like a trough, so that sunlight 32 can be collected in the heat transfer tube 31 by the reflecting mirror 30 . Water 33 circulates through each heat transfer tube 31 . The water 33 is heated by heat collected in the heat transfer tube 31 so that two-phase fluid 34 of water and steam can be obtained from the heat transfer tube 31 .
The trough type solar collector has a merit that it does not require any advanced light condensing technique but the structure is comparatively simple.
Although the low-temperature heating device 24 consisting of a trough type solar collector is used in the embodiment, a low-temperature heating device consisting of a Fresnel type solar collector may be used.
FIG. 6 is a view showing principles for explaining the configuration and so on of a Fresnel type solar collector.
The Fresnel type solar collector has the following mechanism, as shown in FIG. 6 . That is, a several number of reflecting mirrors 35 having flat surfaces or slightly curved surfaces are arranged side and side at angles differing bit by bit from one to another, and a group of heat transfer tubes 31 formed like a panel are disposed horizontally several meters above the group of the reflecting mirrors 35 .
The mechanism works as follows. Sunlight 32 is collected in the group of the heat transfer tubes 31 by the group of the reflecting mirrors 35 so that water 33 circulating through each heat transfer tube 31 can be heated. Thus, two-phase fluid 34 of water and steam can be obtained from the heat transfer tube 31 .
The Fresnel type solar collector can be manufactured more easily and more inexpensively than the aforementioned trough type curved reflecting mirrors 30 . The Fresnel type solar collector has another merit that the reflecting mirrors 35 are rarely affected by wind pressure.
(Third Embodiment)
FIG. 7 is a schematic configuration diagram of a stand-alone type solar electric power generation plant according to a third embodiment of the invention.
In the embodiment, as shown in FIG. 7 , a thermometer 25 and a flowmeter 28 for measuring the temperature and flow rate of fluid are provided on the outlet side of a low-temperature heating device 24 . Measurement signals of the thermometer 25 and the flowmeter 28 are supplied to an arithmetic unit 26 . In the arithmetic unit 26 , a control signal for controlling the opening degree of a water supply valve 19 , that is, the flow rate of water supply is outputted to the water supply valve 19 so as to make the outlet fluid temperature of the low-temperature heating device 24 always not higher than 300° C.
When the outlet fluid temperature of the low-temperature heating device 24 is limited to 300° C. or less in this manner, there is a merit that the structure of the low-temperature heating device 24 consisting of a trough type (or Fresnel type) solar collector can be simplified while the lowering of the heat transfer efficiency can be suppressed. Specifically, it is impossible to suppress cracking in a peripheral glass tube caused by a difference in thermal expansion between the heat transfer tube and the peripheral glass tube and radiative cooling caused by increase in surface temperature of the heat transfer tube, which are problems to be solved when a trough type (or Fresnel type) solar collector is used under high temperature.
FIG. 8 is a partially enlarged sectional view showing the vicinities of a heat transfer tube for use in a trough type (or Fresnel type) solar collector. As shown in FIG. 8 , a peripheral glass tube 42 is disposed on the periphery of a horizontal heat transfer tube 38 so as to form a double structure. The peripheral glass tube 42 is provided to make an airtight state or a vacuum state between the horizontal heat transfer tube 38 and the peripheral glass tube 42 so that heat radiation from the horizontal heat transfer tube 38 to the outside air can be suppressed.
A plurality of heat transfer tubes 38 are joined together as one long heat transfer tube 38 . The heat transfer tubes 38 are made of metal such as carbon stainless steel. Therefore, the heat transfer tubes 38 may be formed into a predetermined length by welding 43 with each other as shown in FIG. 8 .
On the other hand, peripheral glass tubes 42 cannot be welded with each other directly. As shown in FIG. 8 , joint tubes 44 made of metal are disposed on the inner and outer sides of a joint portion between peripheral glass tubes 42 , and the peripheral glass tubes 42 are welded with the joint tubes 44 so as to form a structure in which the peripheral glass tubes 42 are joined to each other through the joint tubes 44 to have a predetermined length.
The heat transfer tube 38 jointed into a predetermined length is inserted inside the peripheral glass tube 42 joined into a predetermined length in this manner, and attached into the solar collector. Thus, when the difference in thermal expansion between the heat transfer tube 38 and the peripheral glass tube 42 increases, cracking may occur near the joint portion between the peripheral glass tube 42 and the joint tube 44 .
In addition, there is another problem that heat radiation to the outside air may increase due to a radiative cooling phenomenon (movement of heat in the fourth power of a temperature difference) when the difference in temperature between the surface temperature of the heat transfer tube 38 and the outside air increases due to increase in the surface temperature of the heat transfer tube 38 .
In the embodiment, therefore, the outlet fluid temperature of the low-temperature heating device 24 is limited to 300° C. or less, specifically within a range of from 250° C. to 300° C., so as to suppress cracking in the peripheral glass tube 42 caused by the difference in thermal expansion between the heat transfer tube 38 and the peripheral glass tube 42 and the radiative cooling caused by increase in surface temperature of the heat transfer tube 38 .
The amount of collected heat in the high-temperature heating device 14 can be adjusted based on the measurement signals of the thermometer 25 and the flowmeter 28 so as to make the outlet fluid temperature of the high-temperature heating device 14 not lower than 300° C. The opening degree of the water supply valve 19 is adjusted to change the flow rate of water supply to thereby adjust the amount of the collected heat.
The other configuration, the mechanism of electric power generation, etc. are similar to those in the aforementioned second embodiment, and redundant description thereof will be omitted.
Although the thermometer 25 and the flowmeter 28 are placed on the outlet side of the low-temperature heating device 24 and the flow rate of water supply to the low-temperature heating device 24 is adjusted to set the measured temperature and flow rate at predetermined values in the embodiment, the amount of collected heat in the low-temperature heating device 24 may be adjusted so that the temperature and flow rate measured by the thermometer 25 and the flowmeter 28 placed on the outlet side of the low-temperature heating device 24 can be set at predetermined values.
(Fourth Embodiment)
FIG. 9 is a schematic configuration diagram of a solar heat integrated type electric power generation plant according to a fourth embodiment of the invention, in which a boiler plant and a solar heat electric power generation plant are combined so that steam can be generated by burning of fuel, heat generated therefrom (for example, in the case of nuclear fuel), or heat recovered from exhaust gas.
The solar heat integrated type electric power generation plant includes a boiler plant 10 , a water supply pump 11 , a steam turbine 8 , a water supply heater 12 , etc. in addition to the solar heat electric power generation plant shown in FIG. 1 . In the boiler plant 10 , steam is generated by burning of fuel, heat generated therefrom, or heat recovered from exhaust gas. The water supply pump 11 supplies water to the boiler plant 10 . The steam turbine 8 is driven by superheated steam generated by the boiler plant 10 . In the water supply heater 12 , the water supplied from the water supply pump 11 is heated using steam extracted from the steam turbine 8 .
In the solar heat integrated type electric power generation plant, a major part of the water supplied from the water supply pump 11 is supplied to the boiler plant 10 , and the water is finally converted into superheated steam by burning of not-shown fuel or heat generated therefrom. The superheated steam is sent to the steam turbine 8 to operate an electric power generator 9 , which generates electric power.
On the other hand, a part of the steam is extracted from the steam turbine 8 and sent to the water supply heater 12 through an steam extraction valve 17 so as to heat the supplied water.
Of the water supplied from the water supply pump 11 , the water excluding the water supplied to the boiler plant 10 is supplied to a low-temperature heating device 13 through a water supply valve 20 . The water is heated by light 32 of the sun 7 and made into two-phase fluid of water and steam, in which a part of the water has been converted into steam. The two-phased fluid of water and steam flows into a steam-water separation device 4 . The two-phased fluid of water and steam is separated into saturated steam and saturated water by the steam-water separation device 4 . The saturated water is supplied again to the low-temperature heating device 13 by a circulating pump 15 . The saturated steam separated by the steam-water separation device 4 is heated by a high-temperature heating device 14 and formed into high-temperature steam. The high-temperature steam is sent to the water supply heater 12 (from A to A in FIG. 9 ).
In addition, as shown in FIG. 9 , the high-temperature steam heated by the high-temperature heating device 14 may be supplied to the boiler plant 10 (from A to A′ in FIG. 9 ) or may be supplied to the steam turbine 8 together with the superheated steam outputted from the boiler plant 10 (from A to A″ in FIG. 9 ).
FIG. 10 is a diagram showing an example in which the opening degree of the steam extraction valve 17 provided on the outlet side of the steam turbine 8 is adjusted (see FIG. 10( b ) ) in accordance with a change in the amount of steam passing through a steam valve 18 provided on the outlet side of the high-temperature heating device 14 (see FIG. 10( a ) ) as shown in FIG. 9 .
As shown in FIG. 10 , the opening degree of the steam extraction valve 17 is reduced with the increase in the amount of steam passing through the steam valve 18 , and on the contrary, the opening degree of the steam extraction valve 17 is increased with the decrease in the amount of steam passing through the steam valve 18 . In this manner, the steam extraction valve 17 is operated in accordance with the amount of steam supplied from the high-temperature heating device 14 , so as to increase/decrease (adjust) the amount of extracted steam in the steam turbine 8 . Thus, large fluctuation in the output of electric power generation can be avoided.
The adjustment of the amount of extracted steam in the steam turbine 8 in accordance with the amount of steam supplied from the high-temperature heating device 14 may be also applied to the following embodiments.
(Fifth Embodiment)
FIG. 11 is a schematic configuration diagram of a solar heat integrated type electric power generation plant according to a fifth embodiment of the invention.
The embodiment is different from the aforementioned fourth embodiment in that a low-temperature heating device 24 consisting of a trough type or Fresnel type solar collector is used.
The other configuration, the mechanism of electric power generation, etc. are similar to those in the aforementioned fourth embodiment, and redundant description thereof will be omitted.
(Sixth Embodiment)
FIG. 12 is a schematic configuration diagram of a solar heat integrated type electric power generation plant according to a sixth embodiment of the invention.
In the embodiment, as shown in FIG. 12 , a thermometer 25 for measuring the temperature of fluid and a flowmeter 28 are provided on the outlet side of a low-temperature heating device 24 . Measurement signals of the thermometer 25 and the flowmeter 28 are supplied to an arithmetic unit 26 . In the arithmetic unit 26 , a control signal for controlling the opening degree of a water supply valve 20 , that is, the flow rate of water supply is outputted to the water supply valve 20 so as to make the outlet fluid temperature of the low-temperature heating device 24 always not higher than 300° C.
The reason why the outlet fluid temperature of the low-temperature heating device 24 is limited thus to 300° or less is similar to that in the aforementioned third embodiment, and redundant description thereof will be omitted.
(Seventh Embodiment)
In any of the aforementioned embodiments, the low-temperature heating device 13 ( 24 ) and the high-temperature heating device 14 serve as Solar collectors by which fluid consisting of steam (water) for finally driving the steam turbine 8 is used as a thermal fluid which is heated directly by the light 32 of the sun 7 .
Accordingly, the solar heat boiler will use no other heat exchanger but the low-temperature heating device 13 ( 24 ) and the high-temperature heating device 14 . Thus, there is an advantage that the configuration of the boiler as a whole is simple enough to thereby achieve reduction in the size and cost or the like.
On the other hand, when the fluid consisting of water and steam is heated directly by the light 32 of the sun 7 , a change of phase from water to steam may occur within a heat transfer tube in a Fresnel type or trough type solar collector particularly for use in the low-temperature heating device 13 ( 24 ). When a two-phase flow is generated, there is a possibility that the heat transfer tube may be thermally damaged locally.
That is, particularly in the Fresnel type or trough type solar collector, of the peripheral surface of the heat transfer tube disposed horizontally, a region where light is collected receives heat. Therefore, the Fresnel type or trough type solar collector has a structure in which an uneven distribution of heat flux may be generated easily over the periphery of the heat transfer tube.
For this reason, when the internal fluid forms a two-phase flow, there is a possibility that abnormality in heat transfer may occur due to an instant change in the amount of collected light and heat, so as to cause thermal damage to that portion of the heat transfer tube.
In the Fresnel type or trough type solar collector, a long heat transfer tube is disposed substantially horizontally and placed in a wide area. The amount of collected heat derived from the sunlight fluctuates largely in a day, or changes suddenly depending on the weather. It is therefore difficult to beforehand specify the region where two-phase fluid may flow.
As a result, there is a problem that the heat transfer tube must be entirely made of a high-performance material, that is, an expensive material that hardly suffers thermal damage, thereby causing the increase in cost.
The seventh embodiment of the invention is a solution to such a problem. FIG. 13 is a schematic configuration diagram of a solar heat independent type electric power generation plant according to the seventh embodiment.
In the embodiment, as shown in FIG. 13 , a water supply circulating flow rate control valve 37 and a flowmeter 28 for adjusting the circulating flow rate are provided on the inlet side of a low-temperature heating device 13 , and a water level gauge 29 for detecting the water level of a steam-water separation device 4 is provided.
A flow rate measurement signal of the flowmeter 28 and a water level measurement signal of the water level gauge 29 are supplied to an arithmetic unit 26 , which outputs a control signal to a water supply valve 19 for adjusting the flow rate of water supply and (or) the water supply circulating flow rate control valve 37 for adjusting the circulating flow rate, so that the water level of the steam-water separation device 4 can be set at an intended value.
When the water level of the steam-water separation device 4 is controlled as in this embodiment, operation can be made to prevent phase separation from occurring in the heat transfer tube of the low-temperature heating device 13 . This principle will be described with reference to FIG. 14 and FIG. 15 .
FIG. 14 is a characteristic graph showing the relationship between a water level L (abscissa) in the steam-water separation device 4 and an outlet steam quality (ratio of steam mass flow rate to total mass flow rate) X (ordinate) in the low-temperature heating device 13 . A total mass flow rate G of the steam-water separation device 4 is used as a parameter for showing the relationship between the water level L and the outlet steam quality X.
The outlet steam quality X of the low-temperature heating device 13 corresponds to the ratio of the mass flow rate of steam to the total mass flow rate G. In addition, the total mass flow rate G of the steam-water separation device 4 corresponds to the flow rate of fluid circulating in the low-temperature heating device 13 through the steam-water separation device 4 .
FIG. 15( a ) is a view showing respective regions of classified fluid states in a two-phase flow of water and steam in the horizontal heat transfer tube 38 of the low-temperature heating device 13 , with the outlet steam quality X of the low-temperature heating device 13 in the abscissa and the total mass flow rate G of the steam-water separation device 4 in the ordinate. The classified fluid states include a spray flow, an annular flow, a bubble flow, a slug flow and a stratified flow.
FIG. 15( b ) is a schematic view showing each fluid state of the two-phase flow of water and steam in the horizontal heat transfer tube 38 . In FIG. 15( b ) , the states of a spray flow, an annular flow, a bubble flow, a slug flow and a stratified flow are depicted.
In the FIG. 15( b ) , in the state where the two-phase flow of water and steam is a spray flow, a major part of the two-phase flow in the tube is steam, and very small water drops accompanied by the steam flow in the steam. In the state of the annular flow, a very thin water film is formed on the tube wall, and a spray flow chiefly consisting of steam is located inside the water film. In the state of the bubble flow, a major part of the tube is filled with water, and small bubbles are present in the water. In the state of the slug flow, bubbles are much larger in size than in the aforementioned bubble flow, showing an intermediate state between the bubble flow and the stratified flow. In the state of the stratified flow, a vapor phase and a liquid phase are vertically separated by the effect of gravity.
Therefore, a preferred flow state for the two-phase flow of water and steam in the horizontal heat transfer tube 38 is the spray flow or the annular flow.
As apparent from the aforementioned result of FIG. 14 , it is known that there is a correlation between the water level L of the steam-water separation device 4 and the outlet steam quality (the ratio of the steam flow rate to the total mass flow rate) X of the low-temperature heating device 13 . Accordingly, for example, an outlet steam quality X 1 of the low-temperature heating device 13 can be obtained by measurement of a water level L 1 of the steam-water separation device 4 in a mass flow rate G 1 of the steam-water separation device 4 .
Next, as shown in FIG. 15( a ) , the flow state of the two-phase flow of water and steam in the low-temperature heating device 13 can be grasped if the outlet steam quality X of the low-temperature heating device 13 and the total mass flow rate G of the steam-water separation device 4 are known. When description is made along the example shown in FIG. 14 , it is understood that the outlet steam quality is X 1 when the water level of the steam-water separation device 4 is L 1 in the condition that the mass flow rate is G 1 .
From FIG. 15( a ) , it is understood that the flow state of the two-phase flow of water and steam in the horizontal heat transfer tube 38 of the low-temperature heating device 13 is a spray flow because the outlet steam quality is X 1 when the mass flow rate is G 1 .
In order to prevent phase separation from being generated in the horizontal heat transfer tube of the low-temperature heating device 13 , the flow state of the bubble flow, the annular flow or the spray flow is preferred in any operation conditions. When a thermal load on the low-temperature heating device 13 is high, it is particularly desired to set the flow state in the annular flow or the spray flow.
In the tube of the low-temperature heating device 13 which is heated on one side as shown in FIG. 13 , the horizontal heat transfer tube 38 is superheated locally when the flow is separated into two phases of water and steam as in the slug flow or the stratified flow shown in FIG. 15( b ) . As a result, there occurs an undesired event, such as high-temperature creep or tube deformation, for stable operation of the electric power generation plant. It is therefore extremely important on stable operation of the electric power generation plant to properly manage the flow state of the two-phase flow of water and steam in the low-temperature heating device 13 .
Accordingly, in the embodiment, an intended value of the water level in the steam-water separation device 4 corresponding to each value of the outlet steam quality X to make a desired flow state as described above is stored in the arithmetic unit 26 in advance. Measurement signals of the flow rate of the flowmeter 28 and the water level of the water level gauge 29 are supplied to the arithmetic unit 26 . The arithmetic unit 26 is designed to output a control signal to the water supply valve 19 for adjusting the flow rate of water supply and (or) the water supply circulating flow rate control valve 37 for adjusting the circulating flow rate, so that the water level of the steam-water separation device 4 can be set at the intended value. Thus, the electric power generation plant can be operated stably.
Although the embodiment has been described in the case of a stand-alone type solar electric power generation plant, the invention can be also applied to the case of a solar heat composite type electric power generation plant.
(Eighth Embodiment)
An eighth embodiment of the invention is to solve the same problem as the problem the aforementioned seventh embodiment is to solve. FIG. 16 is a schematic configuration diagram of a solar heat integrated type electric power generation plant according to the eighth embodiment.
As shown in FIG. 16 , a low-temperature heating device 51 and a solar collector 52 are formed separately, and a thermal fluid channel 53 is added to the solar collector 52 . A thermal fluid circulating pump 55 is provided in the middle of the thermal fluid channel 53 . A part of the thermal fluid channel 53 is disposed as a heat exchanger in the low-temperature heating device 51 , which serves thus as a heat exchanger-including low-temperature heating device. A thermal fluid 54 is designed to circulate from the solar collector 52 into the thermal fluid channel 53 .
Heat collected in the solar collector 52 is transferred to the low-temperature heating device 51 through the thermal fluid 54 circulating through the thermal fluid channel 53 , so as to heat fluid consisting of water and steam in the low-temperature heating device 51 .
The heat exchanger in the low-temperature heating device 51 (in this embodiment, a part of the thermal fluid channel 53 ) does not have to be limited especially as long as it is a noncontact type in which the thermal fluid 54 is not in direct touch with the fluid consisting of water and steam in the low-temperature heating device 51 .
In the embodiment, a solar collector such as a Fresnel type or trough type solar collector in which a light collecting unit and a heat collecting unit can be placed in a low position close to the ground surface is preferable as the solar collector 52 .
A thermal fluid whose phase does not change within an operating temperature range is used as the thermal fluid 54 . The thermal fluid 54 circulates from the solar collector 52 into the thermal fluid channel 53 by the thermal fluid circulating pump 55 . A chemical synthesis oil of diphenyl oxide, biphenyl, 1,1-diphenylethane, etc. alone or blended may be used as the thermal fluid 54 .
The maximum operating temperature of the thermal fluid 54 represented above is about 400° C. Beyond the maximum operating temperature, remarkable deterioration or loss in performance may occur. It is therefore necessary to manage the temperature strictly. However, a thermal fluid thermometer 56 may be added to the thermal fluid channel 53 as shown in FIG. 16 , in order to monitor the outlet thermal fluid temperature of the solar collector 52 . When the temperature of the thermal fluid 54 is limited to be lower than the maximum operating temperature, for example, to be not higher than 300° C., it is not necessary to take special measures within the operation range.
In this manner, there is no fear that the phase of the thermal fluid 54 changes into a two-phase flow in the solar collector 52 . Therefore, there is no fear that abnormality in heat transfer may occur due to an instant change in the amount of collected light or collected heat. Accordingly, there is no fear that thermal damage to the heat transfer tube may occur even under the condition of an uneven distribution of heat flux, but it is possible to improve the reliability and reduce the material cost.
The following configuration may be further provided.
As shown in FIG. 16 , a thermal fluid thermometer 56 and a thermal fluid flowmeter 57 for measuring the temperature and flow rate of the thermal fluid 54 are provided on the outlet side of the solar collector 52 , and measurement signals of the thermal fluid thermometer 56 and the thermal fluid flowmeter 57 are supplied to the arithmetic unit 26 .
In the arithmetic unit 26 , a control signal for controlling the opening degree of a water supply valve 20 , that is, the flow rate of water supply is outputted to the water supply valve 20 so as to make the outlet side thermal fluid temperature of the low-temperature heating device 52 not higher than 300° C.
The reason why the outlet fluid temperature of the low-temperature heating device 52 is thus limited to 300° C. or less is similar to that in the aforementioned third embodiment, and redundant description thereof will be omitted. In addition, the other configuration is the same as that in each of the aforementioned embodiments, and redundant description thereof will be omitted likewise.
In the eighth embodiment, solar heat is used in the low-temperature heating device 51 for generating and heating steam indirectly through a thermal fluid heated by the solar collector 52 formed separately. In the high-temperature heating device 14 , steam is heated directly by the solar heat collected in the same manner as in each of the aforementioned embodiments. The eighth embodiment may be referred to as a so-called hybrid heating type.
According to the eighth embodiment, the problem described in the beginning of the description of the seventh embodiment can be suppressed surely while suppressing and necessarily minimizing the configuration and scale of sections relating to a circulating system of the thermal fluid, such as the heat exchanger, the thermal fluid circulating pump 55 , etc. which complicate the configuration of the boiler device. Thus, the eighth embodiment is effective.
Although a configuration for heating supplied water with a thermal fluid such as steam is used as the water supply heater 12 in each of the aforementioned embodiments, the water supply heater 12 may be also designed to heat the supplied water using the solar heat.
According to the invention, as described above, the low-temperature heating device and the steam-water separation device are placed on the ground surface or near the ground surface. A structure (for example, a supporting base) for supporting a heavy substance holding saturated water is not necessary, or the structure can be placed to be low enough to easily install and maintain the low-temperature heating device and the steam-water separation device. In addition, it is possible to simplify a structure by which the high-temperature heating device which holds only steam and is comparatively light in weight can be installed in a high site.
Further, when the low-temperature heating device and the high-temperature heating device are separated functionally and the steam-water separation device is placed therebetween, the risk of damage to the heat transfer tube can be reduced.
Furthermore, when the high-temperature heating device is installed in a high site, heat exchange can be performed with high thermal density, so that high-temperature steam can be obtained efficiently.
In addition, when the amount of extracted steam on the steam turbine side is adjusted in accordance with a fluctuation in the steam temperature or the steam flow rate when the amount of collected heat in the high-temperature heating device is controlled, the output of the steam turbine can be kept constant.
Although this embodiment has been described in the case of a solar heat integrated type electric power generation plant, the invention can be also applied to a solar heat stand-alone type electric power generation plant.
REFERENCE SIGNS LIST
4 : steam-water separation device
6 : heliostat
7 : sun
8 : steam turbine
9 : electric power generator
10 : boiler plant
11 : water supply pump
12 : water supply heater
13 : low-temperature heating device
14 : high-temperature heating device
15 : circulating pump
16 : tower
17 : steam extraction valve
18 : steam valve
21 : superheater heat transfer tube
24 : trough type low-temperature heating device
25 : thermometer
26 : arithmetic unit
27 : heat transfer tube panel
28 : flowmeter
30 , 35 : reflecting mirror
31 : heat transfer tube
32 : light of the sun
33 : water
34 : two-phase flow of water and steam
37 : circulating flow rate control valve
38 : horizontal heat transfer tube
51 : low-temperature heating device
52 : solar collector
53 : thermal fluid channel
54 : thermal fluid
55 : thermal fluid circulating pump
56 : thermal fluid thermometer
57 : thermal fluid flowmeter
|
A solar heat boiler is provided which is capable of avoiding damage to heat transfer tubes without increasing facility cost and construction cost. The solar heat boiler includes: a low-temperature heating device by which water supplied from a water supply pump is heated by heat of sunlight; a steam-water separation device by which two-phase fluid of water and steam generated in the low-temperature heating device is separated into water and steam; a high-temperature heating device by which the steam separated by the steam-water separation device is heated by the heat of sunlight; and a circulation pump by which the water separated by the steam-water separation device is supplied to the low-temperature heating device.
| 5
|
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation application and claims priority under 35 U.S.C. 120 of international application PCT/EP2007/062970, filed Nov. 28, 2007 and published in English as WO/2008/065153, the content of which is hereby incorporated by reference in its entirety.
BACKGROUND
[0002] The discussion below is merely provided for general background information and is not intended to be used as an aid in determining the scope of the claimed subject matter.
[0003] Aspects of the invention concern a lubrication seal. Such a seal is known from FR 2742837. The disadvantage of the known seal is that the second seal ring has to seal on the same sealing area as the first seal ring. The lubrication barrier is meant to have a long life expectancy and over a long operation period there might develop damage to the first sealing area. This means that if the lubrication barrier is leaking and the cause of leaking is damage to the first sealing area replacing the first seal ring by the second seal ring does not stop the leaking and does not bring the desired improvement.
SUMMARY
[0004] This Summary and Abstract are provided to introduce some concepts in a simplified form that are further described below in the Detailed Description. This Summary and Abstract are not intended to identify key features or essential features of the claimed subject matter, nor are they intended to be used as an aid in determining the scope of the claimed subject matter. In addition, the description herein provided and the claimed subject matter should not be interpreted as being directed to addressing any of the short-comings discussed in the Background.
[0005] A lubrication seal such as an oil seal is described for providing a lubrication barrier to confine lubrication in a bearing with a first bearing ring and second bearing ring, comprising a support ring that rotates with one of the bearing rings, mounted in the support ring are a first seal ring and a second seal ring which seal rings are suitable for forming the lubrication barrier with a sealing surface that rotates with the other bearing ring and which support ring is displaceable from a first sealing position in which the first seal ring forms the lubrication barrier with a first sealing area and the second seal ring does not engage the sealing surface to a second sealing position in which the second seal ring forms the lubrication barrier. The sealing surface comprises a second sealing area that only cooperates with the second seal ring after the support ring is displaced into the second sealing position. By creating a new lubrication barrier with a new seal ring that seals on a new sealing area the lubrication barrier will function as completely new.
[0006] In accordance with an embodiment the lubrication seal is according to claim 2 . In this way the second sealing area is protected from outside influences by the lubrication barrier so that damage to the second sealing area is prevented.
[0007] In accordance with an embodiment the lubrication seal is according to claim 3 . In this way the first seal ring and the second seal ring can have the same dimensions which makes the support ring more compact and reduces costs.
[0008] In accordance with an embodiment the lubrication seal is according to claim 4 . In this way it is avoided to make a groove m the sealing surface and the first seal ring can remain sealing against the sealing surface.
[0009] In accordance with an embodiment the lubrication seal is according to claim 5 . This material reduces friction between the sealing surface and the seal ring and so obtains an increased service life of the seal ring. In accordance with an embodiment the lubrication seal is according to claim 6 . This lengthens the service life of the sealing surface.
[0010] In accordance with an embodiment the lubrication seal is according to claim 7 . This makes it possible to make a compact bearing with a lubrication seal whereby the sealing areas can be made to the same quality as the surfaces of the bearing or if applicable the ball or roller track(s) of the bearing.
[0011] An aspect of the invention also concerns a wind turbine in accordance with claim 8 . The maintenance costs of a wind turbine with a main bearing for supporting the blades are strongly influenced by the service costs of the main bearing. In the known wind turbines replacing the main bearings or the lubrication seals there of is very expensive. By using in the main bearing lubrication seals with increased life expectancy the service costs of the wind turbine are considerably improved.
BRIEF DESCRIPTION OF THE DRAWING
[0012] Hereafter the invention is explained by describing various embodiments of the invention with the aid of a drawing. In the drawing
[0013] FIG. 1 shows a side view of a wind turbine,
[0014] FIG. 2 shows a detailed section of a main bearing of the wind turbine of FIG. 1 with a first embodiment of an oil seal device,
[0015] FIG. 3 shows a detail of a second embodiment of an oil seal device in a first position, and
[0016] FIG. 4 shows a detail of the second embodiment of an oil seal device in a second position.
DETAILED DESCRIPTION
[0017] FIG. 1 shows a wind turbine that is placed on a tower 1 and that has a housing 2 . The housing 2 is rotatable around a vertical axis. A housing ring 4 is with one side attached to the housing 2 and at the other side to a main bearing 9 . A rotor R, comprising a hub 11 with blades 10 is attached to the main bearing 9 and can rotate around a centreline 3 . At the front side the hub 11 is covered by a cap 12 . A generator rotor 6 with permanent magnets 5 is attached via a generator flange 8 to the main bearing 9 and rotates with the rotor R. A generator stator 7 is mounted on the housing ring 4 . The permanent magnets 5 move along the windings of the generator stator 7 to generate electrical power. The housing 2 can rotate around the vertical axis so that the rotor R can be directed towards the wind.
[0018] The wind turbine is designed with a direct drive generator and the generator rotor 6 is directly driven by the rotor R. The main bearing is located between the housing ring 4 and the rotor R and is designed to absorb the gravitational and aerodynamic loads on the rotor R. The service life of the main bearing 9 determines to a large extend the service life of the wind turbine as replacing the main bearing 9 leads to high costs. In circumstances whereby the wind turbine is placed m difficult accessible locations, for instance at sea, replacing the main bearing 9 during service life must be avoided. The service life of the main bearing 9 depends to a large extend on the service life of the oil seals between the rotating parts and the stationary parts of the main bearing 9 . These oil seals are required to ensure that sufficient lubrication means such as oil remains in the main bearing 9 . For this application, only oil seals that are mounted as a full ring between a rotating part and a stationary part have a service life that is long enough. Oils seals that are assembled and welded to a full ring around a part always have the weld as a weak spot. This weld reduces the service life to an unacceptable low level and this design is therefore not suitable. The assembly and disassembly of oil seals as full rings generally requires extensive dismantling of the equipment so that extension of the service life of the oil seal device is strongly desired.
[0019] FIG. 2 shows the main bearing 9 , which is a ball bearing with balls 18 , whereby an oil seal device is mounted between a stationary inner ring 17 and a rotating outer ring 16 on both sides of the balls 18 . The inner ring 17 is mounted on a flange 26 of the housing ring 4 . The generator flange 8 and the hub 11 are mounted on the outer ring 16 . A support ring 14 is coupled to the outer ring 16 by bolts 13 . A cylindrical part 27 of the support ring 14 is located between the inner ring 17 and the outer ring 16 . A static seal 19 is mounted on the outer circumference of the cylindrical part 27 and seals the opening between the outer ring 16 and the support ring 14 .
[0020] On the inner circumference of the support ring 14 an interior seal 20 and an exterior seal 21 are mounted, whereby the interior seal 20 is nearest to the parts to be lubricated such as the balls 18 and the exterior seal 21 is nearest to the surroundings. The outer circumference of the inner ring 17 near the support ring 14 has an exterior sealing surface 28 and an interior sealing surface 29 which is nearest to the parts to be lubricated and between the exterior sealing surface 28 and the interior sealing surface 29 a groove 22 . The groove 22 has a depth that ensures that the interior seal 20 or the exterior seal 21 are free when located above the groove 22 and do not have any contact with the inner ring 17 .
[0021] In the position shown in FIG. 2 there is a spacer 15 between the support ring 14 and the outer ring 16 (via the generator flange 8 and the hub 11 ) and the support ring 14 is m a first position. In this first position of the support ring 14 the exterior seal 21 seals with a flexible sealing lip against the exterior sealing surface 28 . The interior seal 20 is above the groove 22 so that there is no contact between the stationary inner ring 17 and the flexible sealing lip of the rotating interior seal 20 . As the interior seal 20 is behind the exterior seal 21 it has no influence from any contamination or light and there is no wear on the lip of the interior seal 21 . This way the interior seal 20 remains ready for use and as long as it is m this first position, there is no diminishing of its service life. Also the interior sealing surface 29 is protected by the exterior seal 21 and remains ready for use.
[0022] After a period the end of the service life of the exterior seal 21 is detected by observing oil leakage between the sealing lip of the exterior seal 21 and the exterior sealing surface 28 . After determining that the exterior seal 21 is at the end of its service life the spacer 15 is removed and the support ring 14 is pushed inwards and fastened to the outer ring 16 with the bolts 13 (via the generator flange 8 or the hub 11 ) . The support ring 14 is now in its second position.
[0023] In this second position, the flexible sealing lip of the interior seal 20 seals on the interior seal surface 29 and the flexible lip of the exterior seal 21 is free of the inner ring 17 as it is above the groove 22 . (In other embodiments it might be possible that the exterior seal 21 remains in sealing contact with the exterior sealing surface 28 .) As the service life of the interior seal 20 and the interior sealing surface 29 only starts after the support ring 14 is placed in the second position and the flexible sealing lip of the interior seal 20 contacts the interior seal surface 29 , the service life of the oil seal device is twice as long. In order to extend service life of the oil seals as much as possible the exterior sealing surface 28 and the interior sealing surface 29 are preferably from tempered steel and have a ground surface. This way the wear on the flexible sealing lip is reduced as much as possible. The interior seal 20 and the exterior seal 21 are made from flexible material such as rubber or preferably Teflon or similar material m order to obtain a service life that is as long as possible. The service life of an oil seal device that can be obtained m this application with a single seal is approximately 15-20 years, which is slightly less than its expected service life. By using the oil seal device with two oil seals that are in service one after the other the oil seal device is no longer a limiting factor on the service life of the wind turbine. It will be clear that m order to make it possible to displace the support ring 14 m axial direction towards the balls 18 the exterior sealing surface 28 and the interior sealing surface 29 must be provided with a gradual transition such as sloped and/or rounded surfaces in order to avoid damage to the flexible sealing lips of the interior seal 20 or the exterior seal 21 . Also the outer ring 16 must be provided with a sloped surface in order to avoid damage to the static seal 19 when the support ring 14 is brought between the inner ring 17 and the outer ring 16 . In the embodiment shown m FIG. 2 the main bearing 9 is shown as a double row ball bearing. It will be clear to the skilled man that the invention is applicable for other types of ball bearings and for roller bearings or for any other type of bearing. Also aspects of the invention is applicable for other applications such as an oil seal device between a rotating shaft and a housing, whereby the rotating shaft rotates in roller bearings or ball bearings or in any other type of bearing.
[0024] FIGS. 3 and 4 show a sealing between an inner ring 25 and an outer ring 23 which rotate relative one another. In this embodiment the support ring 14 is coupled to the outer ring 23 and the exterior sealing surface 28 and the interior sealing surface 29 are on the inner ring 25 . It will be clear that this situation is preferred, as grinding an outer surface is easier. However there might be embodiments whereby it is preferred to have the exterior sealing surface 28 and the interior sealing surface 29 on the inside surface of the outer ring 23 . In the embodiment shown in FIGS. 3 and 4 the support ring 14 is movable in axial direction m a chamber 24 which is in open connection with space in which the parts to be lubricated such as one or more bearings, gears etc. are located. By using the support ring 14 with the interior seal 20 and exterior seal 21 , a doubling of the service of the oil seal device is obtained.
[0025] In situations whereby an even longer service life is desirable it is possible to use three or more seal rings with two or more grooves, so that seal rings can be used one after the other. The different grooves will then have an increasing width, seen from the exterior, in order to ensure that after moving the support ring over a small distance to a next position a next seal ring contacts a next sealing surface that has not been used by any other seal ring.
[0026] In the described embodiments the interior sealing surface 28 and the exterior sealing surface 29 have the same diameter and also the interior seal 20 and the exterior seal 21 have the same diameter. The same effect of using one oil seal after the other can be obtained without a groove 22 when the interior seal 20 and the interior sealing surface 29 have a slightly larger diameter than the exterior seal 21 and exterior sealing surface 28 . In this way the support ring 14 also has a first position in which the exterior ring 21 seals and a second position in which also the interior ring 20 seals.
[0027] Although the subject matter has been described in language specific to certain compositions, structural features and/or methodological acts, it is to be understood that the subject matter defined in the appended claims is not necessarily limited to the specific compositions, features or acts described above as has been determined by the courts. Rather, the specific compositions, features and acts described above are disclosed as example forms of implementing the claims. Furthermore, the description herein is provided for purposes of understanding and that the components or functions performed described can be separated or grouped in other ways, if desired.
|
A lubrication seal such as an oil seal is described for providing a lubrication barrier to confine lubrication in a bearing with a first bearing ring and second bearing ring, comprising a support ring that rotates with one of the bearing rings, mounted in the support ring are a first seal ring and a second seal ring which seal rings are suitable for forming the lubrication barrier with a sealing surface that rotates with the other bearing ring and which support ring is displaceable from a first sealing position in which the first seal ring forms the lubrication barrier with a first sealing area and the second seal ring does not engage the sealing surface to a second sealing position in which the second seal ring forms the lubrication barrier. The sealing surface comprises a second sealing area that only cooperates with the second seal ring after the support ring is displaced into the second sealing position.
| 5
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a stirrer which is useful particularly in pharmaceutical, food and chemical industries for mixing, dissolving, kneading and diffusing a liquid or other material in a container.
2. Discussion of the Background
Illustrated in FIG. 30 is a known mixer which is provided with a stirring vessel a, a rotational transmission c located externally under the bottom wall of the stirring vessel a and driven from an electric motor b, and an impeller shaft e which protrudes from below into a lower portion of the vessel a and having impeller vanes d. The impeller shaft e and the transmission c are coupled to each other through a magnetic coupling f to rotate the impeller wheel d.
This sort of conventional stirrer is required to separately provide a rotational drive like the motor b for rotating the impeller vanes d which invariably have drawbacks in that they are of complex construction and are large in size.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a stirrer which is capable of stirring a liquid in a container in a completely closed state with no slide portions of rotary components nor a shaft seal portion being required.
It is another object of the invention to provide a stirrer which is compact construction and is reduced in size.
In accordance with the present invention, the foregoing objects are achieved by the provision of a stirrer for stirring a liquid in a container, which essentially includes a cylindrical housing of nonmagnetic material having the peripheral wall portion thereof interposed between a stator and a rotor with stirring vanes for supporting the rotor rotatably through intervention of the liquid from the container.
BRIEF DESCRIPTION OF THE DRAWINGS
A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:
FIG. 1 is a plan view of a first embodiment of the invention;
FIG. 2 is a front view of the embodiment of FIG. 1;
FIG. 3 is a cross-sectional view taken on line III--III of FIG. 2;
FIG. 4 is a perspective view of a rotor;
FIG. 5 is a plan view of a second embodiment of the invention;
FIG. 6 is a partly cutaway front view of the embodiment of FIG. 5;
FIG. 7 is a partly cutaway plan view of a third embodiment of the invention;
FIG. 8 is a partly cutaway front view of the embodiment of FIG. 7;
FIG. 9 is a plan view of a fourth embodiment of the invention;
FIG. 10 is a vertical section of a fifth embodiment of the invention;
FIG. 11 is a sectional view taken on line XI--XI of FIG. 10;
FIG. 12 is a sectional view taken on line XII--XII of FIG. 11;
FIG. 13 is a view similar to FIG. 12 but showing a sixth embodiment of the invention;
FIG. 14 is a vertical section of a rotor of a seventh embodiment of the invention;
FIG. 15 is a vertical section of a rotor of an eighth embodiment of the invention;
FIG. 16 is a vertical section of a ninth embodiment of the invention;
FIG. 17 is a vertical section of a tenth embodiment of the invention;
FIG. 18 is an enlarged sectional view taken on line XVIII--XVIII of FIG. 17;
FIG. 19 is a vertical section of a rotor;
FIG. 20 is a vertical section of a modification of the stirrer of the tenth embodiment arranged in the fashion of the ninth embodiment;
FIG. 21 is a partly cutaway sectional view of an eleventh embodiment of the invention;
FIG. 22 is a partly cutaway sectional view of a twelfth embodiment of the invention;
FIG. 23 is a partly cutaway sectional view of a thirteenth embodiment of the invention;
FIG. 24 is a vertical section of a fourteenth embodiment of the invention;
FIG. 25 is a partly cutaway sectional view of a fifteenth embodiment of the invention;
FIG. 26(a) and (b) are diagrammatic views explanatory of the operation of the rotor in the fifth to fifteenth embodiments;
FIG. 27 is a vertical section of a sixteenth embodiment of the invention;
FIG. 28 is a cross-sectional view of a stator;
FIG. 29(a)through (e) are diagrammatic views explanatory of the operation of the rotor; and
FIG. 30 is a partly cutaway elevation of a conventional stirrer.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Now, the invention will be described more particularly, firstly by way of the first embodiment shown in FIGS. 1 through 4.
In these figures, indicated at 10 is a rectangular liquid container and at 1 is a cylindrical housing of a nonmagnetic material which is projectingly provided in a lower portion of one side wall of the liquid container 10. The housing 1 is hermetically closed at opposite ends thereof, and provided with first communication ports 11a at opposite end portions of the peripheral wall thereof and a second communication port 11b in a center portion of the peripheral wall. Thus, the housing 1 is communicable with the liquid container 10 through the just-mentioned first and second communication ports 11a and 11b. Received in the housing 1 is a hollow cylindrical rotor 3 which is open at the opposite ends and which leaves a small clearance or gap g therearound as shown in FIG. 3. The rotor 3 has cylindrical opposite end portions 3a which comprise a coated magnetic material such as SS41 or the like and a conductive body of copper, aluminum or the like, as well as a cylindrical center portion 3b which is constituted by stainless steel, engineering plastics or the like. As shown in FIGS. 3 and 4, a large number of inclined openings or slots 3c are provided in the center portion 3c to function as a stirring portion. The rotor 3 as a whole is coated with Teflon or other corrosion-resistant material.
Rotating field devices, namely, stators 2, are located on the outer side of the housing 1 opposingly to the cylindrical end portions 3a of the rotor 3. In this instance, each one of the stators 2 is constituted by a multi-layered iron core of silicon steel sheets or the like and a winding wound around the core.
With the above-described arrangement, rotating fields are induced in the cylindrical portions 3a of the rotor 3 as soon as current is conducted through the stator 2, whereupon the liquid is drawn into the gap g by the rotor 3 to produce a bearing effect, rotating the rotor 3 smoothly in a noncontacting state in the direction of arrow A in FIG. 3 by the balancing action between the attraction of the rotating fields and gravity acting on the rotor 3. At this time, since the rotor 3 is provided with the slots 3c in the center portion 3b, the liquid which flows in through the first communicating ports 11a of the housing 1 is sucked into the rotor 3 through the openings at the opposite ends thereof, while the liquid in the rotor 3 is stirred as it is discharged through the slots 3c to return to the container 10 through the second communication port 11b. This is repeated to stir the liquid in the container 10.
Referring now to FIGS. 5 and 6, there is shown a second embodiment of the invention which employs a vertical type cylindrical liquid container 10 with a rectangular open frame 11c projecting from a lower portion of its side wall, and a cylindrical housing 1 fixedly connected in a hermetically sealed state to the frame 11c along the edges of a rectangular opening formed on one side of the housing 1. In the same manner as in the foregoing first embodiment, upon rotating the rotor 3 by supplying current to the stator 2, the liquid flowing toward the opposite end portions of the open frame 11c from the container 10 is sucked into the openings at the opposite ends of the rotor 3 and then discharged through the slots 3c into the center portion of the open frame 11c to return to the container 10. The liquid in the container 10 is thus stirred by repeated circulation through the rotor 3. This embodiment has an advantage in that the housing 1 is easily detachable from the container 10 to facilitate their transportation or maintenance and service.
FIGS. 7 and 8 illustrate a third embodiment of the invention, which employs a vertical type cylindrical liquid container 10 with a housing 1 hermetically and integrally connected to an opening in the side wall of the container 10 for effective use of the installation space. This embodiment is suitable for application, particularly in a case where only a limited floor space is available, and can perform the stirring operation in substantially the same manner as the foregoing second embodiment.
Shown in FIG. 4 is a fourth embodiment of the invention, wherein a housing 1 is spaced more from a container 10 than in the above-described second embodiment and communicated with the latter through three ducts 11d, more specifically, a couple of side ducts 11d and a center duct 11d. The stirring operation is substantially the same as in the first embodiment. With this fourth embodiment, the stator 2 can circumvent the rotor 3 to a greater degree to enhance the rotational efficiency.
Referring to FIGS. 10 to 12, there is shown a fifth embodiment of the invention, which is of a type having a housing 1 formed within an indented bottom wall portion of a stirring container 10. More specifically, the housing 1 is formed of a nonmagnetic material at least in those portions which oppose the rotor 3 as will be described hereinafter, and in this case formed by an indented portion which is provided in a center portion of the bottom wall of the container 10 in such a manner as to circumvent the stator 2. Denoted at 3 is a rotor which is formed in a cap-like shape and which has its peripheral wall portion formed of a magnetic material such as SS41 or the like and a conducting body of copper, aluminum or the like. The top wall of the rotor 3 is formed of stainless steel, engineering plastics or the like. The rotor 3 as a whole is coated with a corrosion-proof material sold under the TEFLON trademark. The rotor 3 is fitted on the housing 1 which circumvents the stator 2, and is provided with an aperture 3d at the center of its top wall and with a plurality of stirring vanes 3e on the peripheral and top wall surfaces. As shown particularly in FIGS. 11 and 12, a plurality of radial strip-like grooves 4 are cut into the inner surface 3f of the top wall of the rotor 3 at uniform angular intervals in the circumferential direction. Each groove 4 is connected to stepped surfaces 5a to 5c of a sectoral shape. Indicated at 6 is a fixed base for mounting the housing 1 and stator 2.
This embodiment operates as follows.
Upon supplying current to the stator 2 to produce shifting fields, the rotor 3 is rotationally driven in the direction of arrow X for stirring the liquid A with the vanes 3e on the rotor 3.
In this instance, since the rotor 3 is provided with aperture 3d at the center of its top wall, the liquid A which is urged to flow into the grooves 4 through the aperture 3d by rotation of the rotor 3 is firstly supplied to the peripheral portions of the respective grooves 4. As the liquid proceeds successively from the first to third sectoral stepped surfaces 5a to 5c, the liquid pressure is increased stepwise, producing a pressure which acts upwardly on the rotor 3 to float the same upward, while part of the liquid A is forced to flow downward through the small gap g between the housing 1 and rotor 3.
In this manner, the gap g is constantly maintained and the rotor 3 is rotated smoothly in a balanced state with the reaction forces of the top stirring vanes 3e and circumferential stirring vanes 3e.
As is clear from the foregoing description, the stirring apparatus of this embodiment employs a noncontacting rotor for the stirring operation, so that it can be applied to either a sealed or nonsealed type container and facilitates stirring operations under high pressure or in a vacuum, free of abrasive wear as would result from sliding movements and free from the generation of vibrations. Moreover, the liquid A in the container 10 can be discharged more easily after stirring operation.
Referring to FIG. 13, there is illustrated a sixth embodiment of the invention, in which the stepped surfaces 5a to 5c of the foregoing fifth embodiment are replaced by an infinite number of stepped surfaces, namely, by a linearly inclined surface 5c to obtain the same effects as in the fifth embodiment.
Illustrated in FIG. 14 is a seventh embodiment of the invention, in which stepped surfaces 5e to 5g are formed on the rotor 3 in the circumferential direction and concentrically in a manner so as to minimize the gap toward the outer periphery. FIG. 15 shows an eighth embodiment in which the number of the stepped surfaces 5e to 5g is increased infinitely to present a linearly inclined surface 5h. In the seventh and eighth embodiments, the liquid which is urged to flow into the aperture 3d by rotation of the rotor 3 is forced outward in the gap between the top wall of the rotor 3 and the top surface of the housing 1 under the influence of the centrifugal force. Since the gap is narrowed toward the outer periphery, the liquid pressure is increased outwardly, generating a pressure which pushes up the rotor 3 into a floating state for smooth rotation.
Although the grooves and stepped surfaces are formed on part of the rotor 3 in the fifth to eighth embodiments, they may be formed on the top surface of the housing 1 if desired.
Shown in FIG. 16 is a ninth embodiment of the invention, in which a closed type housing 1 of a nonmagnetic material is formed separately from the container 10 for the liquid A, and receives therein a stator 2. A rotor 3 is fitted on the housing 1, and grooves and stepped surfaces or a linearly inclined surface are formed on the inner surface of the top wall of the rotor or on the top surface of the housing 1 as in the fifth to eighth embodiments. This stirrer can be placed in an ordinary container. Reference number 7 indicates a lead wire.
Referring to FIGS. 17 to 19, there is illustrated a tenth embodiment of the invention, wherein pumping vanes 3g which are curved in the circumferential direction are projectingly provided on the inner surface of the top wall of a rotor 3 as shown particularly in FIGS. 18 and 19. In addition, a number of labyrinths 8 are formed on the inner periphery at the lower end of the peripheral wall of the rotor 3.
Thus, supplying current to the stator 2 to generate shifting fields which drive the rotor 3 to rotate in the direction of arrow X, the liquid A which is urged to flow into the gap between the opposing surfaces of the rotor 3 and the housing 1 through the aperture 3d is forcibly pushed outward by the pumping vanes 3g on the inner surface 3f of the top wall of the rotor 3 with an outwardly increasing liquid pressure to push up the rotor 3 before flowing down through the gap between the opposing peripheral wall surfaces of the housing 1 and rotor 3. Due to the existence of the labyrinths 8 at the lower end of the rotor 3, downward flow of the liquid A is blocked there to a substantial degree so as to float the rotor 3 upward securely while in rotation. Accordingly, the rotor 3 is rotated smoothly, balancing with the reaction forces of the stirring vanes 3e on its peripheral wall, and consequently the liquid A is stirred by the vanes of the rotor 3.
Although the pumping vanes 3g are provided on part of the rotor 3 in this embodiment, of course they may be formed on the top wall of the housing 1.
Further, the labyrinths 8 which are formed on the inner peripheral surface at the lower end of the rotor 3 may be provided at an intermediate portion on the inner periphery of the rotor 3 or on the outer peripheral surface of the housing 1 if desired.
Moreover, instead of forming the housing 1 by part of the container 10 as in the present embodiment, a closed type housing 1 may be formed separately from the container 10 as shown in FIG. 20 in a manner similar to the ninth embodiment, receiving a stator 2 in the housing 1 and fitting a rotor 3 over the housing 1. In this case, pumping vanes 3g are provided either on part of the rotor 3 or on the opposing surface of the top wall of the housing 1. Further, labyrinths 8 may be provided on the rotor 3 or on the opposing peripheral surface of the housing 1.
Referring to FIG. 21, there is shown an eleventh embodiment of the invention, in which a housing 1 is fixed by screws to a lower portion of a stirring container 10 through an O-ring 9a or other suitable seal member. Indicated at B is an incompressible fluid in liquid form which is filled in the housing 1 and in the gap space around a stator 2. Lead wire 7 from the stator 2 is passed through a seal 9b. Thus, when the container 10 is under high pressure, the compressive force which acts on the housing 1 through the liquid A is sustained by the incompressible fluid B filled in the housing 1. It follows that the wall thickness of the housing 1, particularly, the thickness of the peripheral wall portion can be reduced to enhance the efficiency of the motor.
Illustrated in FIG. 22 is a twelfth embodiment of the invention, in which a housing 1 is suspended from the top wall of a stirring container 10 by means of a hollow cylindrical support member 12. The housing 1 is in communication the cylindrical support member 12 which is filled with an incompressible fluid B. A seal 9b is provided at the upper end of the support member 12. In this embodiment, the rotor 3 is formed in C-shape in section.
The incompressible fluid B may be filled in the housing 1 alone, locating the seal 9b in the position indicated by broken line in FIG. 22.
FIG. 23 shows a thirteenth embodiment of the invention, in which a communication hole 13 is formed in an upper portion of a hollow cylindrical support member 12 and the fluid B is filled in a housing 1 and only in lower portion of the support member 12, leaving an empty space thereabove. Accordingly, when stirring the container 10 under high pressure, the upper empty space in the support member 12 is raised to the same pressure level by communication with the upper empty space in the container 10 through the communication hole 13, as a result zeroing on equalizing the pressure difference between inside and outside of the housing 1 and the cylindrical support member 12. This permits a reduction in their wall thicknesses so as to enhance the motor efficiency.
Alternatively, the hollow spaces in the casing 1 and support member 12 may be entirely emptied and filled with the high pressure gas in the upper space of the container 10 by communication therewith through the communication port 13, instead of the fluid B.
Although a situation where a high pressure prevails in the container 10 has been described as an example in each one of the foregoing eleventh to thirteenth embodiments, there occurs almost no pressure difference between inside and outside of the housing 1 even under low pressure or vacuum condition, permitting a reduction in the wall thickness of the housing 1. The housing 1 which has been shown as being fixed in the container 10 in the eleventh to thirteenth embodiments may be provided as an independent closed type which can be set in an arbitrary position within an existing container.
Referring to FIG. 24, there is illustrated a fourteenth embodiment of the invention, wherein a pipe 14 is inserted in a center aperture of a stator 2 to form an air passage 15. The lower end of the pipe 14 is passed through and fixed to a support plate 16 which supports the container 10, the side walls of the pipe 14 being spread into a trumpet-like shape under the support plate 16 to accommodate a fan 17. Indicated at 18 are openings which are formed in the support plate 16, namely, in the bottom wall of the housing 1 beneath the peripheral wall portions of the stator 2, and indicated at 19 are legs which support the container 10.
Upon generating shifting fields by supplying current to the stator 2, the rotor 3 is rotated on the liquid bearing which is formed in the small clearance between the rotor 3 and the housing 1, stirring the liquid A with the vanes 3e which are provided on the rotor 3. As the fan 17 is actuated, the air which is drawn by the fan 17 is sent into the air passage 15 and circulated through the housing 1 and along the peripheral wall portions of the stator 2 before being discharged through the openings 18. As a result of this air circulation, the housing 1 is cooled and the stator is smoothly rotated so as to stir the liquid A efficiently.
By reversing the rotation of the fan 17, the air circulation can be changed so as to draw air through the openings 18 and discharge it through the air passage 15.
Shown in FIG. 25 is a fifteenth embodiment of the invention, in which a housing 1 is provided in an upper portion of a container 10 and supported on a tubular support member 20 which is pendant from the top wall of the container 10. A pipe 14 is inserted centrally in the support member 20. The lower end of the pipe 14 is fitted in the center hole of the stator 2, while the upper end is spread into a trumpet-like shape to accommodate a fan 17. This embodiment operates in the same manner as the foregoing fourteenth embodiment.
Instead of employing an air-cooled type stator 2 as in the fourteenth and fifteenth embodiments, arrangements may be made to cool the stator by feeding thereto cooling water or other cooling liquid with the use of a pump.
In any of the foregoing fifth to fifteenth embodiments, there may arise the following problem in a situation where the winding is wrapped around the entire circumference of the stator 2.
Namely, as power is supplied to the winding of the stator 2, an attracting force F 1 is generated in a certain direction by the magnetic field of the winding as shown in FIG. 26a, exerting a pulling force on the rotor 3 and producing on the outer side of the housing 1 a liquid film of a wedge-like shape in the direction of rotation. As a result, the liquid between the rotor 3 and housing 1 is pulled in due to its viscosity and generates a liquid pressure with an overall reaction force F 2 in the opposite direction. By vector addition of the attracting force F 1 and the reaction force F 2 , a combined force F 3 acts on the peripheral wall in the rotational direction. Consequently, as shown in FIG. 26b, the rotor is pulled in the direction of the combined force F 3 , and in this state the attracting force F 1 and overall reaction force F 2 of the liquid pressure occur in the manner as described hereinabove. Therefore, next the rotor 3 is pulled in the direction of the combined force of the attracting force F1 1 and overall reaction force F 2 . Since the stator 2 has the winding wrapped 360° around its entire circumference, the position where the rotor 3 approaches the housing 1 is shifted sequentially, putting the rotor 3 into eccentric rotational motions and sometimes causing the rotor 3 to hit against the circumference of the housing 1. This makes it difficult to ensure smooth rotation of the rotor.
In order to overcome this problem, the sixteenth embodiment shown in FIGS. 27 and 28 has stator windings 2A, 2A'; 2B, 2B' and 2C, 2C' wrapped over an angle of 150° in slots 2a, 2a'; 2b, 2b' and 2c, 2c'. Upon supplying current to the windings 2A, 2A'; 2B, 2B' and 2C, 2C', shifting fields are generated in the stator 2 and thereby the rotor 3 on the opposite side of the housing 1 is urged to rotate in the direction of arrow W and at the same time pulled toward stator 2. As a result, the rotor 3 is moved into an eccentric position as shown in FIG. 29a, forming a small gap g 0 between the rotor 3 and housing 1 with a fluid bearing constituted by the inflowing liquid film. The overall force P 1 of the attracting forces Pa 1 to Pz 1 of the stator windings acts on the rotor 3 across the small gap g 0 in the direction of <α short of the small gap position. At this time, pressures Pa 2 to Pz 2 of the wedge-shaped liquid film act on the rotor 3 and housing 1, and their overall pressure P 2 acts as shown in FIG. 29b. Accordingly, the combined vector force P 3 of the overall attracting force P 1 and the overall pressure P 2 acts on the rotor 3 as shown in FIG. 29c, shifting the small gap g 0 through an angle of θ to g' 0 . In this state, the small gap g' 0 is located in the vicinity of the end of the stator windings where the attracting forces P'a 1 to P'z 1 of the windings are interrupted in the direction of the rotation as shown in FIG. 29d. Therefore, the overall attracting force P'1 is maintained substantially in the same direction as the aforementioned overall force P 1 . However, as a result of the shift of the small gap from g 0 to g' 0 , the overall pressure P' 2 is shifted in the direction of rotation as shown in FIG. 29e. Therefore, the combined vector P' 3 of the overall attracting force P' 1 and the overall pressure P' 2 are almost extinguished as shown in FIG. 29c to maintain a constant small gap g' 0 , while the rotor 3 is rotated by the shifting fields of the stator windings. Thus, the rotor 3 tends to move into the eccentric position to form a narrow gap g 0 only through a rotational angle of 150° where it is associated with the windings 2A, 2A' to 2C, 2C', and the eccentric displacement does not occur through the remaining angle of rotation. Namely, as the rotor 3 continues its rotation, the eccentric circular movements due to the eccentric displacement are extinguished so as to allow the rotor to smoothly rotate while keeping a constant gap g' 0 from the housing and efficiently stirring the liquid A with the vanes 3e.
The stator windings 2A, 2A' to 2C, 2C' may be increased or reduced suitably to cover an arbitrary rotational angle, for example, to cover an angle of 180° or 120° if desired.
Needless to say, the rotor can be more smoothly rotated in the fifth to fifteenth embodiments by adopting the partial wrapping of the windings as in the sixteenth embodiment.
Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
|
A stirrer for stirring a liquid in a container, which includes a stator; a rotor disposed in the container and provided with stirring vanes; and a cylindrical housing of nonmagnetic material having a peripheral wall thereof interposed between the stator and rotor and rotatably supporting the rotor through intervention of the liquid. This arrangement provides a stirrer of simple and compact construction, which can stir the liquid in a container completely in a closed state free of sliding portions of rotary components or shaft seal portions.
| 8
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a retractable needle, and in more particular, to a retractable needle that uses rotating knob-operated cooperating disc stacks and hydrostatic pressure from the needle's fluid reservoir to permanently withdraw the needle.
2. Background of the Prior Art
Needles are a routine part of any medical setting. It is standard medical practice to use a needle once and then discard it. Such practice prevents the spread of disease. However, with the recent spread of diseases such as HIV and Hepatitis, not only is the use-once-and-discard procedure mandatory, the spread has called for further precautions.
When a needle is used, the needle's end has the patient's blood and other bodily fluids on it. If another person, such as a health care worker, comes in contact with this end, and thereby contracts the disease, the experience may prove fatal. Therefore, it has become necessary to shield people from a used needle's contaminated end.
Many examples of non-reusable shielded needles are found in the prior art. Examples of such devices include U.S. Pat. No. 5,242,402 and U.S. Pat. No. 5,232,458 issued to Chen, U.S. Pat. No. 5,242,400 issued to Blake III et al., U.S. Pat. No. 5,222,944 issued to Harris, U.S. Pat. No. 5,279,581 and U.S. Pat. No. 5,108,378 issued to Firth et al., U.S. Pat. No. 5,215,533 issued to Robb, U.S. Pat. No. 5,211,628 issued to Marshall, U.S. Pat. No. 5,188,601 issued to King, and many others.
There are two main approaches to shielding the needle tip in order to prevent accidental pricks. The first method involves a sheath, encompassing the needle body, being slid into place over the needle after use. The other approach involves retraction of the needle into the needle body after use. Some retraction methods permanently lock the needle into its retracted mode. As an additional safety measure, many devices have a break-off plunger to further eliminate the potential for reuse or reloading of the needle.
While the devices presently found in the art work with differing levels of success, they suffer from complexity over a standard needle. Such complexity renders the needle expensive to manufacture to the point of being cost-prohibitive to purchase. In a setting having high needle use, substantial additional expense may be the critical factor in deciding to use a regular non-shielded needle. Furthermore, the complexity increases the potential for failure of the needle shielding means.
A needle is needed that Will shield the needle tip after use and will permanently render the needle non-reusable. Such a needle must be relatively simple and inexpensive to manufacture and must have a very low potential for failure.
SUMMARY OF THE INVENTION
The device of the present invention meets the above mentioned need in the art. The present invention comprises a syringe assembly that can be permanently disabled and thereafter the needle can be safely and permanently withdrawn into the interior of the syringe body, preventing accidental pricking from a used needle.
The device comprises a syringe body having plunger slidably disposed within one end and a needle assembly rotatably disposed within the other. Rotation of the needle assembly will selectively enable and disable fluid flow between the needle and the syringe's fluid reservoir.
The needle assembly comprises a cylindrical body having a top, middle and bottom section with a needle attached to the bottom section. A fluid passage, having a top portion laterally offset from the central axis of the cylindrical body, and a bottom portion, extends through the cylindrical body placing the needle in fluid connection with the reservoir. One or more slotted portions extends through the middle section. One or more sealing discs are disposed within each of the slotted portions. A pair of generally semi-circular plates wrap around the middle section and receive the ends of the sealing discs. One or two protrusion slots, located between the plates, receive one or two rectangular protrusions located on the inside of the syringe body and hold the plates rotatably fixed. Rotation of the cylindrical body causes an aperture on the seal disc to either align or mis-align the top portion of the fluid passage with the bottom portion of the fluid passage for enabling fluid connection between reservoir and needle or disabling fluid connection respectively.
One or two slotted portions are located on the bottom section and align with the respective rectangular protrusions only when the user places the device into a permanently disabled state. By being so aligned, the cylindrical body may be retracted into the interior of the syringe body.
Alternatively, one of the plates has a fluid passage located therein. Rotation of the cylindrical body causes this fluid passage to align or mis-align with the top portion and the bottom portion.
Alternatively, the cylindrical body may have a slotted portion having a round section, a vertical section, and a horizontal section integrally disposed therebetween. A tumbler having an aperture and an extension passing through the cylindrical body and received within a diagonal slot located on one of the plates. Rotation of the cylindrical body causes the aperture to either align or mis-align with the top portion of the fluid passage (in this case located on the central axis of the cylindrical body) and the bottom portion of the fluid passage.
In each case, rotation of the cylindrical body is accomplished by the use of an open-ended knurled ring having a base with a non-symmetric aperture located thereon. The aperture engages a protrusion, in corresponding shape to the knurled ring aperture, located on the base of the bottom section. One or more windows located on the knurled ring correspond with one or more color bands located on the syringe body for determining the state of enablement of the device.
One or more tabs are located on the inner circumference of the syringe body. Each tab is received in one of four notches located on the outer circumference of the bottom section. The notch within which each tab is located determines device state. One and two way ramps either permit or prohibit return to a prior state.
For added security, the plunger can be permanently locked in place when the plunger is fully retracted.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an isometric of the syringe assembly device of the present invention.
FIG. 2 is an isometric view of syringe body.
FIG. 3 is a side view of the syringe body.
FIG. 4a is an isometric view of the single disc needle assembly.
FIG. 4b is a side view of the single disc needle assembly.
FIG. 4c is an isometric view of the needle attached prior to use.
FIG. 5a is an isometric view of the multiple disc needle assembly.
FIG. 5b is a side view of the multiple disc needle assembly.
FIG. 6a is a side view of the knurled ring.
FIG. 6b is a side view of the knurled ring without the knurled surface.
FIG. 6c is a cutaway view of the knurled ring.
FIG. 7a is an isometric view of the tumbler needle assembly.
FIG. 7b is a side view of the tumbler needle assembly.
FIG. 8 is an isometric view of the external fluid passage needle assembly.
FIG. 9a is an isometric view of the syringe assembly in a new state.
FIG. 9b is an isometric view of the syringe assembly in use.
FIG. 9c is an isometric view of the syringe assembly with the needle assembly withdrawn into the syringe body.
FIG. 10a is a cutaway syringe body and needle assembly view of the syringe assembly in a new state.
FIG. 10b is a cutaway syringe body and needle assembly view of the syringe assembly in use.
FIG. 10c is a cutaway syringe body and needle assembly view of the syringe assembly with the needle assembly withdrawn into the syringe body.
FIG. 11a is a cutaway syringe body view of the needle assembly in a new state.
FIG. 11b is a cutaway syringe body view of the needle assembly in use.
FIG. 11c is a cutaway syringe body view of the needle assembly withdrawn into the syringe body.
FIG. 12 is a cutaway syringe body and plunger view of the first plunger retention means.
FIG. 13 is a cutaway syringe body and plunger view of the second plunger retention means.
Similar reference numerals refer to similar parts through out the several views of the drawings.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention is comprised of a plunger 10, a syringe body 12, a retractable, sealable needle assembly 14, and a rotatable knurled ring 16. The syringe body 12 is hollow. The open ends of the syringe body 12 are located at the top or plunger end 18 and at the bottom or needle assembly end 20 and a fluid reservoir 22 therebetween.
Slidably disposed within the top end 18 of the syringe body 12 is the plunger 10 comprised of, from top to bottom, a handle 24, a shaft 26, and a base 28. The handle 24 may be open 30 and nominally flat or it may be close-looped 32 to facilitate single-finger aspiration. Encompassing the outer perimeter of the base 28 is an O-ring or other suitable sealing means 34 for preventing fluid flow between the outer perimeter of the base 28 and the inner perimeter of the syringe body 12. The base 28 is solid to prevent fluid flow therefrom.
Extending outwardly from the top edge of the exterior syringe body 12 surface is a finger grip flange 36. The flange 36 extends sufficiently far from the exterior syringe body 12 surface to prevent fingers from sliding over it while gripping the syringe body 12.
Located along the inner perimeter of the bottom edge of the syringe body 12, in proximity to the needle end 20, are one or more spaced apart cantilever tabs 38 having tab protrusions 40. One or more vertically disposed spaced apart rectangular protrusion 42 are disposed within the hollow inner region of the syringe body 12.
Located on the outside of the syringe body 12 adjacent to the bottom edge of the syringe body 12 are one or more spaced apart multi-colored strips 44. The colored strips 44 have a green portion 46, a first yellow portion 48, a second yellow portion 50 (in a different shade from the shade of the first yellow portion 48), and a red portion 52.
Encompassing the outer perimeter of the syringe body 12, above the color strips 44, is a projecting ring 54. The top side 56 of the projecting ring 54 projects squarely from the syringe body 12. The bottom side 58 of the projecting ring 54 is ramped. Located above the projecting ring 54 on the outer perimeter of the syringe body 12 are one or more spaced apart series of fluid graduation marks 60 for gauging the quantity of fluid in the inner hollow region of the syringe body 12.
Disposed principally within the bottom of the inner hollow region of the syringe body 12 is the retractable, lockable, and sealable needle assembly 14 having a top 64, cylindrical middle section 66, and bottom 68. The top 64 of the needle assembly body 14 is flat or shaped in similar fashion to the relief of the bottom end of the plunger base 28. The bottom 66 of the needle assembly 14 has a non-symmetric geometric protrusion 70. Extending from either the geometric protrusion 70 or directly from the bottom of the needle assembly 14 is either a needle 72 or a threaded needle base 74 bearing a needle 72. The sides of the needle assembly 14 follow the cylindrical shape of the hollow inner region of the syringe body 12.
The needle assembly 14 has a top flange 76, and a bottom flange 78. The axis of symmetry of the cylindrical middle section 66 extends from top 64 to bottom 68 and lies at the center of the cylindrical syringe body 12. Encompassing the outer perimeter of the top flange 78 is an O-ring or other suitable sealing means 80 for preventing fluid from flowing between the needle assembly 14 and the inner perimeter of the syringe body 12. The bottom flange 78 and the seal-wrapped top flange 76 fit snugly within the inner surface of the inner hollow region of the syringe body 12. On the surface of the cylindrical middle section 66 of the needle assembly body 14 are a plurality of round protrusions 82.
Located on the bottom flange 78 are one or more ramp assemblies 84, one ramp assembly 84 for each of the cantilever tabs 38. Each ramp assembly 84 comprises a first one-way ramp 86, a two-way ramp 88, and a second one-way ramp 90. The tab protrusions 40 at the free ends of the cantilever tabs 38 extend into, and can slide along, the ramp assemblies 84. Also located on the bottom flange 78 are one or more flange slots 92 that extend from top to bottom, one flange slot 92 for each of the rectangular protrusion 42 extending from the inner syringe body surface. The flange slots 92 are cut into the bottom flange 78 to the depth of the cylindrical middle section 66 of the needle assembly 14.
A horizontally disposed slot 94 passes through the center of the cylindrical middle section 66 of the needle assembly 14. A sealing disc 96, having an aperture 98, is disposed in the horizontal slot 94, fitting snugly within the top and bottom of the horizontal slot 94. A fluid passage 100, which is a hollow portion, extends from the top of the needle assembly 14 to the needle 72 or the bottom center of the threaded needle base 74. The fluid passage 100 extends from top to bottom through the needle assembly 14 and the aperture 98 of the sealing disc 96. The bottom portion 102 of the fluid passage 100 extending from the bottom of the horizontal slot 94 may be centered on the needle 72 or threaded needle base 74 while the top portion 102 of the fluid passage 100 extending from the top of the needle assembly 14 to the horizontal slot 94 may be laterally offset from the bottom portion 102 of the fluid passage 100. The aperture 98 in the sealing disc 96 fluid connects the top portion 104 and bottom portion 102. Rotating the needle assembly 14 about the sealing disc 96 in the horizontal slot 94 can mis-align the slot aperture 98 and disconnect the top portion 104 and the bottom portion 102. The snug fit between the sealing disc 96 and the top and bottom surfaces of the horizontal slot 94 prevents fluid from flowing between the sealing disc 96 and the top and bottom surfaces of the horizontal slot 94. Tabs 106 on the sealing disc 96 extend from one or both ends of the horizontal slot 94 such that the ends of the sealing disc tabs 106 are even with the outer edges of the top flange 76 and the bottom flange 78.
One or more generally semi-circular plates 108 are placed around the cylindrical middle section 66 of the needle assembly 14 between the bottom of the top flange 76 and the top of the bottom flange 78. The generally semi-circular plates 108 extend from one flange slot 92 to the next flange slot 92 (if more than one slot is present). The generally semi-circular plates 108 have sufficient circumference to span the unslotted lengths of the bottom flange 78. The generally semi-circular plates 108 have rounded depressions 110 along their inner surfaces.
Disc tab holes 112 penetrate the generally semi-circular plates 108 from the inside to the outside. The sealing disc tabs 106 are received into the disc tab holes 112. The fluid passage 100 extending through the horizontal slot 94 in the needle assembly 14 is connected or disconnected by rotating the needle assembly 14 within the semi-circular plates 108 and around the sealing disc 96.
The needle assembly 14 is assembled by placing the sealing disc 96 into the horizontal slot 94 and placing the generally semi-circular plates 108 around the exterior of the cylindrical middle section 66. The sealing disc tabs 106 fit into the semi-circular plates' disc tab holes 112. The gaps between the semi-circular plates are aligned with the flange slots 92. The multiple rounded protrusions 82 on the surface of the cylindrical middle section 66 of the needle assembly 14 are received into the rounded depressions 110 to keep the semi-circular plates 108 aligned during assembly. The device of the present invention is assembled by slidably inserting the needle assembly 14 needle end down into the top of the syringe body 12. The needle assembly 14 slides into the syringe body so the rectangular protrusions 42 on the inner surface of the syringe body 12 slide into the flange slots 92 and the gaps between the semi-circular plates 108. The bottom of the top flange 76 rests against the top of the rectangular protrusions 42. The cantilever tabs 38 and ramp assemblies 84 are located such that the tab protrusions 40 on the free ends of the cantilever tabs 38 slide into notches at the non-ramped sides of the second one-way ramps 90. The sealing disc 96 in this configuration does not fluid connect the top portion 104 and the bottom portion 102. The rectangular protrusions 42 on the inner surface of the syringe body 12 extend down to the top of the bottom flange 78 when the needle assembly 14 is fully inserted into the syringe body 12.
The free ends of the cantilever tabs 38 are now lifted and the needle assembly 14 is rotated until the cantilever tabs 38 are positioned in the notches at the non-ramped side of the first one-way ramps 86. Now the sealing disc 96 fluid connects the top portion 104 and the bottom portion 102. Fluid is free to move through the continuous fluid passage 100 and the plunger 10 may be fully inserted. Rotating the needle assembly 14 has mis-aligned the flange slots 92 and the rectangular protrusions 42 on the inner surface of the syringe body 12. The needle assembly 14 can not be slidably moved along the hollow inner region of the syringe body 12 in this configuration. The free ends of the cantilever tabs 38 are now lifted and the needle assembly 14 is rotated until the cantilever tabs 38 are positioned in the notches at the ramped side of the first one-way ramps 86. Now the sealing disc 96 does not connect the top portion 104 and the bottom portion 102. The flange slots 92 and the rectangular protrusions 42 on the inner surface of the syringe body 12 are still mis-aligned. The needle assembly 14 can not be slidably moved along the hollow inner region of the syringe body 12 in this configuration.
A knurled ring 114 comprises an open-ended tube 116, having a knurled outer circumference 118, and a plate 120 attached to its bottom. A flange 122 extends outwardly from the exterior knurled ring surface as a finger guard to prevent fingers from sliding over the bottom end of the syringe body 12 and contacting the needle 72. The middle of the plate 122 contains an aperture 124 in corresponding shape to the shape of the relief of the non-symmetric protrusion 70 on the bottom of the needle assembly 14. The top edge of the knurled ring 114 is multiply split from the top of the ring to the middle portion of the ring into numerous cantilever ring tabs 126.
Assembly of the device is completed by sliding the knurled ring 114 upwards over the needle 72 or threaded needle base 74 so that the aperture 124 in the knurled ring plate 122 aligns with the non-symmetric protrusion 70 on the bottom of the needle assembly 14. The cantilever ring tabs 126 have small protrusions 128 along the inside of their top edges. These protrusions 128 slide up the sloped bottom surface of the projecting ring 54 on the syringe body 12 exterior surface and snap over the non-sloped upper surface of the projecting ring 54 to hold the knurled ring 114 in place. The knurled ring 114 cannot be removed without damage to and probable disablement of the device. The knurled ring 114 engages the needle assembly 14 via the non-symmetrical protrusion 70 so that rotating the knurled ring 114 causes corresponding rotation of the needle assembly 14. The generally semi-circular plates 108 are fixed in place by the rectangular protrusions 42 on the syringe body 12 inner surface. The sealing disc 96 remains motionless as it is connected to the generally semi-circular plates 108. Rotating the knurled ring 114 and the needle assembly 14 about the sealing disc allows the top portion 104 and bottom portion 102 to be connected and disconnected.
The knurled ring 114 has a smooth surface at several windows 129 along is periphery. A single portion of each multi-colored strip 44 is viewable through each of the windows 129.
The complete syringe assembly is now ready for use. The complete assembly has four operating configurations, each denoted by a different color showing through the knurled ring windows 129. Initially, windows 129 with the green colored strips 46 showing through the windows 129. The green strips 46 denotes that the syringe has not been used. In this configuration the top portion 104 and the bottom portion 102 are disconnected by the sealing disc 96. The flange slots 92 are mis-aligned with the rectangular protrusions 42 so the needle assembly can not be slidably moved. Hydrostatic pressure in the fluid reservoir 22 (hollow inner region of the syringe body 12 between the top of the needle assembly 14 and the bottom of the plunger base 28) does not allow the plunger 10 to be slidably moved. Rotating the knurled ring 114 causes the cantilever tabs 38 to ride over the first one-way ramp 86 and the windows 129 show the first yellow portions 48. The knurled ring 114 can not be turned back to the initial green portion state without harming the device. In the first yellow portion state the needle assembly 14 has been rotated about the sealing disc 96 so the top portion 104 is now fluid connected with the bottom portion 102. Fluid can pass from the needle 72 or threaded needle base 74 to the fluid reservoir or vice versa. The flange slots 92 remain mis-aligned with the rectangular protrusions 42 so the needle assembly can not be slidably moved.
If the knurled ring 114 is rotated further until the windows 129 are positioned over the second yellow portions 50, the needle assembly 14 will again rotate, with the cantilever tabs 38 passing over the two-way ramp. This causes the sealing disc to fluid disconnect the top portion 104 and the bottom portion 102. The flange slots 92 remain mis-aligned with the rectangular protrusions 42 so the needle assembly can not be slidably moved. Hydrostatic pressure again does not allow the plunger 10 to be slidably moved. The syringe is now disabled, but can be re-enabled as the knurled ring can be counter-rotated back to the first yellow portion position. The two-way ramp 88 assure this maneuver.
This functionality is especially useful when the fluid introduced into the fluid reservoir in the syringe body 12 is a medicine such as a vaccine. The knurled ring 114 can be temporarily rotated to disable the device, and the health professional can re-enable the device when the patient is present.
When the syringe is used and is to be discarded, the knurled ring 114 is rotated so the windows 129 are positioned over the red color portions 52. This causes the cantilever tabs 38 to pass over the second one-way ramp 90. The knurled ring can no longer be rotated in either direction. In this configuration the top portion 104 and the bottom portion 102 are fluid disconnected by the sealing disc 96. The flange slots 92, however, are aligned with the rectangular protrusions 42 so the needle assembly can be slidably moved upwardly. Hydrostatic pressure in the fluid reservoir allows the plunger 10 and the needle assembly 14 to be slidably moved.
Pulling on the plunger 10 generates a hydrostatic pressure in the fluid reservoir. This hydrostatic pressure transfers part of the pulling (or pushing) force to the needle assembly 14, causing it to move with the plunger movement. Contact between the top flange 76 and the rectangular protrusions 42 prevents the needle assembly 14 from being pushed out the bottom end of the syringe body 12. The needle 72 or threaded needle base 74 is shielded from incidental contact by being withdrawn into the syringe body 12. The aperture 124 in the knurled ring's base plate 124 is small enough to prevent finger insertion into the syringe body 12. The suitable sealing means on the plunger base 28 and top flange 76 prevent fluid leakage from the fluid reservoir 22 as the reservoir 22 moves in the syringe body 12.
As seen in FIGS. 5a and 5b, multiple sealing discs 96, each having an aperture can disposed within multiple horizontal slots 94 can be utilized. Each sealing disc 96 has a sealing disc tab 106 on either end with each sealing disc tab 106 received within a respective disc tab hole 112 located on the generally semi-circular disc plates 108. In all other respects, the multiple sealing disc tab assembly would function in identical fashion to the single sealing disc 96 configuration.
As seen in FIGS. 7a and 7b, in an alternate embodiment of the needle assembly 14 the cylindrical middle section 66 has a slotted portion 130 having a rounded section 132, a horizontal section 134, and a vertical section 136. One of the generally semi-circular plates 108' has a diagonally disposed slotted portion 138. A cylindrical rotating tumbler 140, having an extension 142 and an aperture 98' passing through the tumbler 140, is disposed within the rounded section 132 of the slotted portion 130. The extension 142 passes through the vertical section 136 and through the diagonally disposed slotted portion 138.
When the device is initially assembled (view window 128 over the green portion 46), the extension 142 is located at the top of the diagonally disposed slotted portion 138. In this position, the aperture 98' is mis-aligned with the top portion 104 and the bottom portion 102 thereby fluid disconnecting the two portions. When the knurled ring 114 is rotated (view window over first yellow portion 48), the cylindrical body rotates thereby causing the extension 142, to travel partially down the diagonally disposed slotted portion 138. This causes the tumbler 140 to rotate and to align with the aperture with the top portion 104 and the bottom portion 102 thereby fluid connecting the two portions. When the knurled ring 114 is further rotated (view window 128 over the second yellow portion 50), the needle assembly 14 further rotates thereby causing the extension 142, to travel further down the diagonally disposed slotted portion 138. This causes the tumbler 140 to rotate and to once again mis-align the aperture with the top portion 104 and the bottom portion 102 once again fluid disconnecting the two portions. Further rotation of the knurled ring 114 (view window over red portion 52) will continue the mis-alignment of the aperture with the top portion 104 and the bottom portion 102.
As seen in FIG. 8, in a second alternate embodiment of the needle assembly, one of the generally semi-circular plates 108' has a fluid passage 144 located therein. The fluid passage 144 of the generally semi-circular plate 108 is either aligned (view window over first yellow portion) or mis-aligned (view window over green portion 46, second yellow portion 50 or red portion 52), with the top portion 104 and the bottom portion 102 of the cylindrical middle section 66. When the fluid passage 144 of the plate 108 is aligned with the top portion 104 and the bottom portion 102 fluid connection is enabled between the fluid reservoir 22 and the needle 72, otherwise fluid connection is disabled.
As seen in FIGS. 10 and 11, the plunger 10 can be permanently locked into an extended position. As seen, the base 28 of the plunger 10 has one or more inwardly facing springed hooks 146. The end of each hook 146 have a ramped portion 148. When the plunger 10 is pulled near the end of its slide path, the ramped portion 148 passes over a hooked lip 150 of the syringe body 12. Once the ramped portion 148 clears the hooked lip 150, the hooked end clicks into place with the hook 146 grasping the hooked lip 150 and thereby prevents retreat of the plunger 10.
As seen in FIG. 12 an alternate embodiment of the plunger assembly, the plunger 10 has a one or more hooks 146 each with an outwardly extending hooked end 152, located on the plunger base 28. When the plunger 10 is pulled near the end of its slide path, the hooked ends 152 pass over a hooked lip 151 of the syringe body 12. Once the hooked ends 152 clears the hooked lip 150, the hooked end clicks into place with the hooked end 152 grasping the hooked lip 150 and thereby prevents retreat of the plunger 10.
As seen in FIG. 13 a second alternate embodiment of the plunger assembly the plunger 10 has a plurality of one way ramps 154 located on its shaft 26. When the plunger 10 is pulled near the end of its slide path, the one way ramps 154 pass over the end of the syringe body 12. Once the one way ramps 154 clear the end of the syringe body 12, the base of the one way ramp 154 prevents retreat of the plunger.
While the invention has been particularly shown and described with reference to an embodiment thereof, it will be understood by those skilled in the art that various changes in form and detail may be made without departing from the spirit and scope of the invention.
|
A retractable needle assembly is disclosed. The needle assembly consists of a syringe body, having a needle assembly on one end and a plunger assembly on the opposing end. The needle assembly, which enables and disables fluid communication between the needle and fluid reservoir, comprises a generally cylindrical body sealably disposed within the lower interior of the syringe body. The cylindrical body is rotatable, facilitated by a knurled ring, within the syringe body. Rotation of the cylindrical body causes either enablement or disablement of the needle assembly. Tabs, located on the syringe body are received within notches, separated by one-way and two-way ramps, located on the cylindrical body, such that the ramps facilitate either temporary or permanent disablement of the device. Plunger lock means are also disclosed.
| 0
|
BACKGROUND OF THE INVENTION
The present invention is directed to a class of bipolar membranes possessing both low electrical resistance and superior performance properties and durability. In particular, the invention relates to single film bipolar membranes comprising an organic polymer matrix intimately containing a substantial amount of a cross-linked aromatic polymer, and having highly dissociable functional groups of opposite electrical charges, chemically bonded to the aromatic nuclei on opposite sides of the film. More specifically, the invention relates to the compositions of such structures and to the methods for preparing them.
Various ion exchange membranes, cationic and anionic, individually as well as laminae membranes, are well known in the art. Styrene-divinylbenzene copolymers with sulfonic acid ion exchange groups (cation-type) are fully disclosed, e.g. in U.S. Pat. No. 2,731,411. The anion-type, for example a styrene-divinylbenzene vinylpyridine membrane, is disclosed in U.S. Pat. No. 2,860,097. Cation and anion membranes based on polyethylene-styrene copolymers bonded together in a hydraulic press under heat and pressure to form two-ply membrane structures are also known as shown, for example in U.S. Pat. No. 3,372,101. Such membranes generally have the disadvantage of high electrical resistance, incurred during fusion; are prone to bubble or blister; and only operate at relatively low current densities, for short time periods, all of which render them unattractive for commercial electrodialysis operations.
Some single film bipolar membranes have also been disclosed. For example, some have been obtained by hydrolyzing one side and aminating the other side of a chlorosulfonated polyethylene sheet, as disclosed in U.S. Pat. No. 3,388,080. Membranes thus prepared, however, are relatively inefficient in that they have high voltage drops across them due to their relatively low ion exchange capacity. Another single film bipolar membrane, of the polyethylene-styrene divinylbenzene type, is disclosed in the Leitz U.S. Pat. No. 3,562,139. The latter membranes are designed specifically for desalination by electrodialysis, wherein, the direction of electrical current flow is periodically reversed. Such membranes behave asymmetrically transferring mainly cations when the cationic lamina of the membrane faces the cathode and transferring mainly anions when the anionic lamina faces the cathode. To the degree that any water splitting could be effected using the membrane described by Leitz in U.S. Pat. No. 3,562,139, the current efficiency of the contemplated desalination process would be decreased. Moreover, the membranes of U.S. Pat. No. 3,562,139 have only a relatively low level of cross-linking (approximately 0.5% active divinylbenzene) which results in relatively inferior ion selectivity. Also membranes of the kind disclosed in U.S. Pat. No. 3,562,139 possess design features, such as (a) a cation exchange group internal molality less than the anion exchange group internal molality, and (b) an anionic layer which is thinner than the cation layer, both of which aid the transport of the electrolyte through forbidden areas, i.e., against the Donnan exclusion forces, and possess only relatively low current efficiencies (50-70% desalination) at low electrolyte concentrations (.03- .06N) and current densities (8-25 amp/ft 2 ).
Thus, while the preparation of low cross-linked, low ion-selective polyethylene-polystyrene bipolar membranes has been achieved, it is particularly difficult to obtain bipolar membranes with a relatively high number of cross-linking bonds, high functional group concentrations, high ion-selectivities, and yet have low membrane voltage drops and long operational capabilities at relatively high current densities and electrolyte concentrations. This invention discloses methods for obtaining single film bipolar membranes with these advantages.
SUMMARY OF THE INVENTION
The primary object of this invention is to prepare single film bipolar membranes which comprise a matrix of a polymeric film in intimate dispersed relationship with a relatively high amount of an aromatic polymer, which is suitably crosslinked such as with a di- or poly-functional compound. Highly dissociable cation exchange groups are chemically bonded to the aromatic nuclei from one side of the film, while highly dissociable anion exchange groups are subsequently chemically bonded to the remaining aromatic nuclei on the opposite side. The membrane so composed functions particularly advantageously as a durable water-splitting membrane to generate acid and base from dissolved salts by electrodialysis with substantially improved efficiency at both high electrolyte concentrations, i.e. several molar and current densities, such as 100-400 amp./ft. 2 or above.
Another object is to prepare more densely structured membranes, wherein counter-ion transport in opposition to Donnan exclusion forces is greatly decreased, but nevertheless does permit sufficient hydraulic permeability to prevent the membrane from dehydrating.
A further object is to prepare highly cross-linked membranes which are less prone to blister, are substantially less porous, and permit only low salt diffusion across them.
Another object is to prepare bipolar membranes having ion exchange capacities between about 1-6 meq/g of dry membrane, with cation-exchange groups and anion-exchange groups of about equal concentration, and which have very low potential drops across the membrane.
Still another object of the invention is to prepare membranes which are less brittle, have little or no degradation, have excellent strength and durability, and which are stable under conditions and for time periods not previously attainable.
Additional objects will become apparent from the disclosure which follows.
The single film bipolar membrane compositions of the present invention are prepared from a single polymeric film, such as, polyethylene, polypropylene, etc., as a matrix and intimately contains at least 15% by weight, based on the total weight of dry membrane, of an aromatic nuclei containing polymer, such as polystyrene, poly-α-methylstyrene, etc., which is suitably cross-linked with a di- or poly-functional crosslinking agent, such as, divinylbenzene or its equivalent. Subsequently, highly dissociated cation exchange groups, e.g. sulfonic acid, are chemically bonded to about 50 to 98 percent of the aromatic nuclei from one side of the film only, and later highly dissociated anion exchange groups, e.g. quaternary ammonium groups are chemically bonded to the remaining, i.e., 2 to 50 percent, aromatic nuclei. Performance characteristics of the final membrane depend greatly on the relative amounts of matrix film, aromatic polymer, and cross-linking agent used in their fabrication. Disclosed herein are the conditions and procedures used to obtain compositions which not only have improved performances as water-splitters during electrodialysis, but also possess excellent strength and durability.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a magnified illustration of a cross-section of a single film bipolar membrane positioned schematically in a typical electrodialysis cell in combination with conventional "single" charge anion and cation permeable ion exchange membranes.
FIG. 2 depicts a chlorosulfonation apparatus which may be used to functionalize the styrenated polyethylene film from one side only in preparing the bipolar membrane of the invention.
FIG. 3 shows the potential drop, Em, as a function of current density for an illustrative single film bipolar membrane with various polystyrene contents (i.e. ion exchange capacity) prepared according to the invention.
DETAILED DESCRIPTION OF THE INVENTION
In FIG. 1 of the drawing a typical arrangement utilizing the bipolar membrane prepared in accordance with the invention is illustrated. As shown, a bipolar membrane 2 is depicted schematically as a water-splitter in an electrodialysis cell. Acid and base flow through compartments on opposite sides 5 and 6 of the bipolar membrane 2, which are also bounded by anion permeable and cation permeable ion exchange membranes 3 and 4, respectively. Salt solution, KF, passes through the adjacent compartments 7 and 8 which are separated from the electrode compartments 9 and 10, containing K 2 SO 4 solution, by additional cation exchange membranes 4. Under the influence of a direct electric current, anions (F - ) and cations (K + ) within the bipolar membrane migrate out of the membrane toward the anode and cathode, respectively, and in the vicinity of the interface their concentrations rapidly decline. At this point continued passage of the electric current can only occur by the transfer of OH + and H + ions produced by the dissociation of water ("water-splitting") at the interface. Naturally, the membranes must be sufficiently water permeable in order to replace water molecules consumed by the reaction; otherwise the membrane will "burn-out". Current efficiencies for the production of acid and base using membranes of the invention varied from 79-92% and 66-82% respectively, at a current of 163 ma/cm 2 (150 amp/ft 2 ) and electrolyte concentration of about 9-11% acid and base. These are higher ranges than have been normal in the prior art, e.g. 24 amp/ft 2 and 0.1N solutions or less. In addition, in the use of membranes of the invention only negligible amounts of salt, KF, were found in the acid, indicating very low diffusion of base through the membrane.
Uniformly impregnated sheets with wide ranges in both their aromatic polymer content and cross-linking content, which subsequently functionalize homogeneously to low resistance membranes, were prepared and compared. Films with low cross-linking contents, i.e. about 2% DVB in the styrenating mixture, were found to blister easily. Those with polystyrene contents of about 23% had potential drops which depended greatly on the relative thicknesses of the two layers. Potentials approached 1 volt (at 100 amp./ft 2 ) only as the cationic layer became about 90% of the films' thickness. Increasing the cross-linking content of the films was found to eliminate blistering and styrenation mixtures containing 5-15% DVB were of common use. At these higher cross-linking contents, however, potential drops became even more sensitive to the relative thickness of the oppositely charged layers and it was difficult to obtain membranes of 1 volt (at 100 amp./ft. 2 ) regardless of the thickness of its cation permeable layer. This is depicted in FIG. 3. When the ion exchange capacity is increased by increasing the vinyl aromatic, e.g. the polystyrene content to 35 -50%, potentials less than 1 volt are realized. In addition, the potentials are less sensitive to the relative thicknesses of the layers and at 43% styrene, for example, potentials of 1 volt and less are obtained with membranes having 54% or more cation exchange layer as seen by reference to Table I and FIG. 3.
Prior to the functionalization of the cross-linked film of the present invention, the film is advantageously preswollen in a solvent such as carbon tetrachloride, dichloroethane, etc., for a period of time sufficient to render the aromatic nuclei readily accessible to the reagent. The swelling solvent must be inert to the reagent but miscible with it or its mixture. As will be noted hereafter, and by way of examples, preswelling permits the reaction to proceed under milder, more controlled conditions, with no significant degradation or embrittlement of the film. Both the sulfonation and subsequent chloromethylation and amination are properly controlled and occur extensively at the para-position, yielding relatively high and about equal concentrations of both ion exchange groups which minimizes salt leakage, due to Donnan exclusion forces. Since only very low amounts of salt, KF, are found in the acid, HF, negligible base diffusion through the membrane is indicated. Also, the durability is attested to by the fact that some of the membranes have run continuously in electrodialysis cells for over a year at 71-83 amp/ft 2 with no lessening in performance and only modest increases in potentials.
The bipolar membranes of the present invention are prepared from single sheets of aromatic nuclei containing cross-linked, polymeric films. The sheets are preswollen prior to appending the cation exchange groups from one side, followed by appending anion-exchange groups to the opposite side.
The resulting membranes possess lower resistances which allow the use of higher current densities (100-150 amp./ft 2 or above) and electrolyte concentrations and exhibit higher current efficiencies. The membranes are particularly suited for industrial water-splitting applications in which high performance is a prerequisite.
The matrix film employed in preparing the bipolar membrane of the present invention may comprise any of the polymers derived from monomers selected from the group consisting of ##STR1## wherein R 1 to R 7 are substituents selected from the group consisting of hydrogen, chlorine, fluorine, alkyl radicals of 1 to 5 carbon atoms and phenyl radicals and copolymers thereof, and chlorinated and fluorinated polymers and copolymers thereof. Typical of polymers derived from the formulae (I) and (II) are polyethylene, polypropylene, polybutene-1, poly-3-methyl-1-butene, poly-4-methyl-1-pentene, poly-4-methyl-1-hexene, polyvinyl chloride, polyvinyl fluoride, polystyrene, polyvinylidene chloride, polyvinylidene fluoride, polyisobutylene, polytrifluorochloroethylene, polytetrafloroethylene, polybutadiene, polyisoprene, polychloroprene, poly-2,3-dichlorobutadiene, poly-1,3-pentadiene, and the like and copolymers thereof, and chlorinated and fluorinated polymers and copolymers thereof.
Films of various densities, such as low density, high density, or ultra-high molecular weight polyethylene may be used, but it is important that the film have a homogeneous rheological structure in order to obtain uniform membranes. To afford active sites the film is impregnated with a mixture of an aromatic nuclei containing monomer and a suitable cross-linking agent or in lieu of a chemical cross-linking agent subjected to well known cross-linking conditions. Prior to polymerization all of the excess liquid polymerizate should be removed from the film's surface in order to ensure subsequent uniform functionalization.
The aromatic monomers which are intimately dispersed and polymerized on the matrix film composed of the monomeric compounds of the above formulae (I) and (II) are those of the formula ##STR2## wherein R 8 , R 9 and R 10 are substituents selected from the group consisting of hydrogen, alkyl radicals of 1 to 4 carbon atoms, phenyl substituted alkyl radicals of 2-4 carbon atoms, phenyl, phenoxy-, thiophenoxy, and naphthyl radicals and the hydroxyl-, alkoxyl-, and halo-substituted phenyl, phenoxy, thiophenoxy, and naphthyl radicals and mixtures thereof and wherein at least one substituent is an aromatic radical. Illustrative of such compounds are styrene or its nuclear and/or alpha substituted derivatives, such as α-methyl styrene, α-ethyl styrene, α,β-dimethyl styrene, 4-phenyl-butene-1, α-chloro-styrene, α-bromostyrene, 2-chloro-styrene, 2-bromostyrene, 2-fluorostyrene, 2-hydroxy-styrene, 2-methoxy-styrene, vinyl naphthalene, vinyl phenylethers, and vinyl phenyl sulfides. The weight ratio of the matrix film and the aromatic component should be adjusted so as to ensure an ion exchange capacity of the final membrane of about 1.4-6.0 meq/g. In the case of styrene from about 15 to 70% of the impregnated film should preferably be cross-linked polystyrene.
The aromatic polymer on the substrate is cross-linked sufficiently to prevent substantial dissolution or swelling of the membrane when it is immersed in solvents in which the membrane is to be primarily used,. e.g. aqueous acid and base solutions. Cross-linking methods which may be used include any of the well known mechanisms, such as chemical or radiation, either singly or in combination; illustrative of cross-linking systems are the use of polyvinyl compounds, such as divinylbenzene, and substituted derivatives thereof, such as nuclear and/or alpha-substituted derivatives, e.g., divinyl toluene, α, α'-dimethyl divinylbenzene, α, α'-dimethyl divinyltoluene, divinylnaphthalene, divinylxylene, divinylethylbenzene, divinylchlorobenzene, trivinylnaphthalene, divinylphenylether, divinylsulfone, divinylacetylene, and also radiation, such as electron beam. Preferably a cross-linking agent such as divinylbenzene (DVB) may be used. DVB is available commercially as a mixture containing 55% divinylbenzene isomers and about 45% ethyl vinylbenzene as the main components. The mole ratio of the aromatic compound to the cross-linking agent can vary from about 112:1 to 9:1, corresponding to about 2-20% commercial divinylbenzene in the styrene mixture.
Preswelling of the cross-linked film prior to the sulfonation reaction, may be effected by the use of any suitable solvent which is inert to but miscible with the sulfonation agent or mixture. Suitable solvents are carbon tetrachloride, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, dimethyl acetamide, dimethylformamide, decalin, tetralin, and cyclohexane.
A preferred membrane in the present invention is that prepared from the polyethylene-polystyrene-divinylbenzene system; utilized as a typical composition in describing the preparation of membranes according to the invention.
EXAMPLES 1 -21
General Procedure - In preparing the membrane the initial polyethylene film was first examined between crossed polaroid sheets for non-uniformities, such as gels, strains, disorientations or the like. The uniformity of the film's thickness was measured with a micrometer. The films were supported in stainless steel troughs containing the aromatic vinyl monomer mixture of the selected mole ratio of vinyl aromatic monomer and cross-linking agent, e.g. styrene/divinylbenzene/benzoyl peroxide (initiator), and at the desired temperature. Immersion in the vinyl aromatic monomer, e.g., styrenation is conducted for a time period necessary to attain sufficient impregnation of the film, which is dependent upon its thickness and morphology, as well as, the styrenating temperature.
In impregnating the substrate film with the vinyl aromatic monomer, temperatures at or above which the film softens to an undesirable degree are to be avoided. Generally for mixtures containing 5-15% DVB, styrenations were carried out at 70°-94° C. for time periods of about 10 minutes to 1 hour. Following styrenation, the film is removed from the bath, excess styrene removed from its surface, and it is then pressed between aluminum foil covered glass plates and polymerized at 70-85° C for 18-24 hours. In order to obtain styrene contents of about 40-60% the procedure may be repeated. After each polymerization, surface polystyrene is easily removed with a suitable solvent, e.g. CCl 4 , dichloroethane, etc., if required.
Prior to sulfonation, the cross-linked film is preswollen in a solvent, inert to, but at least partially miscible with the sulfonating agent or mixture for about 24 hours. The solvent swells the film, making the aromatic nuclei more accessible for reaction, hence, the reaction rate is increased and the sulfonation will proceed faster and under milder conditions. The films suffer no apparent degradation, and yield membranes which are not embrittled and display much enhanced stability and durability. Chlorosulfonations may be run at room temperature with chlorosulfonic acid-solvent mixtures ranging from 10-100% chlorosulfonic acid.
The reaction is started on one side of the film only and its progress through the film toward the opposite side is controlled and may be followed by microscopic examination of stained (methylene blue), microtomed, cross-sections. The interface betweem the reacted and unreacted layers is linear, parallel to the sides of the film, and very sharp, attributed to both the homogeniety of the film and that the reaction is apparently diffusion-controlled. Extensive chlorosulfonation and chloromethylation plus quaternization may be observed by both chemical analysis and microscopic examination and indicates the concentrations of both functional groups in the final membrane are nearly equal.
In addition, it is observed from resistance measurements (1 kc, AC bridge) of sections removed at various time intervals, that the resistance is relatively high, ranging from 1000 to 10,000 ohm-cm 2 . due to the remaining unfunctionalized layer, until just before the reaction reaches the opposite side, at which point it suddenly falls to very low values, indicating the membrane is becoming wholly cation permeable as determined by microscopic examination of stained thin sections. It is apparent that one skilled in the art may use any fraction of this time interval to locate the interface at any desirable position across the film's thickness.
Once the partially chlorosulfonated film is hydrolyzed with dilute (1N) sulfuric acid, neutralized with a 0.1N KOH and 5% KCl mixture, rinsed free of excess electrolyte with distilled water, and dried, it is then ready for chloromethylation. In lieu of drying, the film may be treated with several portions of solvent, such as carbon tetrachloride. The chloromethylation is conducted by immersing the films into chloromethylmethylether containing 2.5% by weight, SnCl 4 , and refluxing (59° C.) for about 6 hours under nitrogen. The film is then removed and quaternized in a 25% solution of trimethylamine in acetone at 25° C. for about 20 hours. The single film bipolar membrane so obtained is equilibrated in 1N potassium fluoride at 25° C. for 48 hours, with stirring. Microtomed thin sections may be stained with either a cationic dye (methylene blue) and/or an anionic dye (methyl orange), and have been observed to compliment each other, with a sharp interface between them.
Sulfonations may also be accomplished by means of such known reagents as (a) sulfuric acid, (b) sulfur trioxide, or (c) oleum, or (d) mixtures thereof. Chloromethylation may also be conducted by the following reagents (a) SO 2 Cl 2 with methylal and a Friedel-Crafts catalyst or (b) formaldehyde and hydrochloric acid.
Electrical sensitivity - The voltage drop across the bipolar membrane is determined in a six-cell electrodialysis cell, FIG. 1, containing platinum electrodes in each end compartment, across which a direct current may be applied from a D.C. power source, (e.g. Hewlitt-Packard Model No. 6289A). The bipolar membrane is mounted between the two center cells with its anion permeable side contacted with a 1N KOH electrolyte solution and facing the anode and its cation permeable side contacted with 1N HCl solution and facing the cathode. 1N KCl is used in the two adjacent cells, with 5%, K 2 SO 4 in the two end electrode compartments. Two Luggin tips (saturated KCl in agar-agar) are positioned in the center of the two middle cells, about 2 mm from the opposite faces of the bipolar membrane. The other ends of the Luggin tips are immersed in saturated KCl solutions containing two Calomel electrodes which are connected to a voltmeter. The voltage drop across the 1N HCl and 1N KOH solutions between the Luggin tips was determined in separate measurements, averaged, and subtracted from the voltage drop measured with the bipolar membrane in position. The voltage drop across the bipolar membrane was measured at various current dentisites, e.g. 1.8-165 ma/cm 2 (1.7-154 A/ft 2 ) and the results plotted. Since about 0.75 volts are required to split water, voltages in excess of this value are due to the resistance of the bipolar membrane itself. In addition, at no current flow the voltage drop, Eo, across the bipolar membrane is generally about 0.75-0.80 volts, but as the anionic layer gets thinner, e.g. less than about 0.5 mils in a 10 ml film, and as the interface approaches the opposite surface, as observed by microscopic examinations of stained thin sections the Eo rapidly falls below this value to about zero, which is the Eo for a wholly cationic membrane.
Bipolar membranes having a total styrene content about 15% or higher with relatively low cross-linking, for example a membrane with 2% or less of a commercial cross-linking agent, such as divinylbenzene, in the initial styrenation mixture, are prone to have blisters form on their surfaces. The size and number of such blisters vary over a wide range and are believed to be due to strains or ruptures below the surface of the relatively loose (i.e. low cross-linked) structures. Although with such low cross-linking, some smaller, blister-free specimens may be obtainable by selective sampling for evaluation purposes, the fabrication of large, blister-free sheets appears unlikely.
In accordance with the invention, blister-free membranes are obtained by providing a polymeric film with substantially increased cross-linking. Increasing the cross-linking content also tightens the structure, adding dimensional stability and decreasing its porosity. As will be apparent from the examples provided hereafter, data for Examples 1-21 being summarized in Table I, membranes prepared from styrene mixtures containing about 7.5% or higher concentration of divinyl benzene, in addition to having higher current efficiencies, had only trace amounts of salt (e.g. KF) in the acid.
When using a styrenation mixture with divinylbenzene in amounts from about 10% to about 15%, or higher, the styrene content of the membrane preferably should be at least 25% (by weight) or more, otherwise the curves obtained by plotting their potential drops against current density as shown in FIG. 3 will bend upward especially at the higher current values. This consequence is due to the fact that these structures offer more resistance to the increased flow of electrolyte, which may be adjusted by increasing the ion exchange capacity, i.e., the polystyrene content, of the membrane. For example, a bipolar membrane made from 9 mil HDPE film, containing 23% polystyrene with 2% divinylbenzene, has a potential drop ranging from 3.41 to 1.07 volts, at current densities of 109 ma/cm 2 , depending upon the chlorosulfonation time, i.e. the relative thickness of the cationic layer (see Examples 1 to 5 in Table I). The last column shows Sample 5 was 88% cationic by microscopic examination of stained, thin sections, and apparently a voltage drop of about 1.1 volts is the best one may expect to obtain with membranes of this composition. In addition, as noted hereinabove, these membranes blister relatively easily. Bipolar membrane made from 10 mil ultra-high molecular weight polyethylene (UHMW-PE) containing 25% polystyrene, but with 15% DVB (Examples 6-9, Table I) show a similar dependence of the potential drop upon the relative thickness of the cationic layer. In both cases, as the cationic layer approaches and begins to appear on the opposite surface, the membrane begins to lose bipolarity as indicated by the rapid decrease of its Eo value, until it is nearly zero, at which point the membrane is completely cationic.
When the polystyrene content is increased to 37% (Examples 9-14), potential drops as low as 0.86 volts at current densities of 109 ma/cm 2 are obtained with membranes which are 94% cationic. The former values are very close to the theoretical limiting value of a water-splitter. With these higher polystyrenated membranes it is seen that their potential drops are becoming less sensitive to the relative thickness of the cationic layer. This trend is even more evident in the final series (Examples 15-21), where the films contain 43% polystyrene. Here it is seen that potential drops ranging from 1.03-0.86 volts are obtained with membranes whose cationic layer varies from 54% to about 90%. This is clearly an advantage if one is considering the fabrication of such films.
TABLE I__________________________________________________________________________POTENTIAL DROPS FOR SINGLE FILM BIPOLAR MEMBRANESWITH VARIED POLYSTYRENE CONTENTS__________________________________________________________________________ COMPOSITION ** % CATIONICEX. INITIAL % % .sup.t ClSO.sub.3 H Em (volts) LAYERNO. FILM POLYSTY. DVB* (min.) Eo 1.8 ma/cm.sup.2 1.09 ma/cm.sup.2 (MICROSCOPIC)__________________________________________________________________________1 9 mil 23 2 30 .79 0.83 3.412 HDPE 60 .79 0.79 2.233 90 .81 0.79 1.254 180 0.78 0.75 1.10 735 240 0.81 0.78 1.07 886 10 mil 25 15 120 .80 0.88 4.867 UHMW-PE 165 .81 0.81 1.388 210 .79 0.79 1.239 9 mil 37 15 180 .78 0.76 1.80 4810 UHMW-PE 210 .78 0.75 1.26 6411 240 .79 0.77 1.43 6612 270 .79 0.76 1.03 8113 300 .79 0.75 1.03 8114 330 .79 0.75 0.86 9415 9 mil 43 7.5 100 .70 3.80 36 ma/cm.sup.2 3316 UHMW-PE 220 .78 0.75 1.03 5417 240 .78 0.74 1.00 5618 260 .78 0.75 0.88 7719 280 .78 0.74 0.90 8620 300 .78 0.76 0.87 7421 320 .78 0.75 0.86 79__________________________________________________________________________ *weight percent commercial (55%) divinylbenzene in the styrenation mixture. **chlorosulfonation time, minutes HDPE --high density polyethylene UHMW-PE = ultrahigh molecular weight polyethylene
Examples 22 to 28, summarized in Table II further illustrate the invention. It is evident that membranes prepared in accordance with the invention herein described exhibit significantly higher current efficiencies, while operating at both higher current densities and higher electrolyte concentrations, than heretofore previously disclosed. The initial films were styrenated with mixtures containing from 2-15% commercial divinylbenzene and the final sheets contained from 23-46% polystyrene. They had potential drops of about 1 volt or less at current densities as high as 163 ma/cm 2 (152 amp/ft 2 ), and electrolyte concentrations of 9-11.5% acid and base, were found to produce base and acid at current efficiencies (%N B , %N A ) from 66-82% and 79-92%, respectively. In addition, as further evidence of the tightness of these structures, only negligible amounts of salt, KF, was found in the acid, HF (%N SA ) i.e. by diffusion of base through the membrane. Two of the membranes, examples 22 and 25, ran continuously for over one year, with no loss in their performance characteristics, and only modest increases in their voltage drops. The examples, therefore, serve not only to illustrate the substantial improvement in membrane performance, but also, their superior stability and durability over a wider range of operating conditions and for longer time periods than previously demonstrated attainable. It must be understood that such examples and previous descriptions are not intended as a limitation upon the scope of the invention.
EXAMPLE 22
A styrenation mixture consisting of 2 parts commercial divinyl benzene and 98 parts of freshly distilled styrene was heated in a beaker, with stirring, to 80° C. To this mixture was then added 0.5 parts benzoyl peroxide as catalyst. After mixing for one minute, the mixture was poured into a 9 × 14 × 1-1/4 inch stainless steel trough, immersed in a 80° C. constant temperature water bath. Immediately thereupon, a 7 × 23 inches sheet of high density polyethylene film, 0.009 inch thick, folded in half, was immersed into the styrenating mixture and supported by two stainless steel rods. The film was impregnated with the mixture for one-half hour before removing from the trough, wiping off the excess surface styrene with a squeegee, and then clamping between three aluminum foil covered 8 × 12 × 1/8 inch glass plates. The ensemble was then immersed into a saturated sodium sulfate salt solution at 70° C. and left to polymerize for 18 hours. The styrenated sheet was then removed, rinsed with distilled water for 3 hours at 40°-50° C, and dried overnight in a vacuum oven at 45° C over P 2 O 5 . The final dried, polystyrenated sheet was found to contain 22.7 weight percent polystyrene. The styrenated sheet was swollen for one day in carbon tetrachloride, free polystyrene wiped from its surface with dichloroethane and 7 × 11 inch sections were cut from it.
Sections prepared as above were functionalized by supporting them in a two cell arrangement as shown by reference to FIG. 2. The arrangement of FIG. 2 comprises relatively thick brackets 12 and 15 formed of polytetrafluoroethylene containing inlet and outlet ports 13 and 16 and 14 and 17 respectively. Central and outer stainless steel plates 18, 19 and 20 respectively are provided and a polytetrafluoroethylene liner 21 is positioned on the inner sides of each of the outer plates 19 and 20 and on both sides of the central plate 18. The styrenated polyethylene film 22 is secured between the brackets and one of the polytetrafluoroethylene liners so that the face is exposed to acid and rinse solutions pumped into the chamber formed by the interior of brackets 12 and 15. This two-cell apparatus was used for chlorosulfonation where it was desired that the reaction proceed from one side only until it had penetrated to a certain depth of the films thickness. It is apparent that a second styrenated polyethylene film may be positioned on the other side of the brackets 12 and 15. CCl 4 was pumped from a storage tank under a nitrogen atmosphere, through the two cells in series, until the reaction was to be started. At this point, the CCl 4 was quickly drained from the cells and at a recorded time a 56/44 (by volume) mixture of chlorsulfonic acid/carbon tetrachloride was pumped through each cell at room temperature (also under a nitrogen atmosphere). After 1-1/2 hours, at which point the chlorosulfonation had proceeded about 90-95 % across the films thickness, the reaction mixture was quickly drained, the sheets rinsed rapidly with CCl 4 , and then removed and placed in a 1N H 2 SO 4 solution. The sheets were left in the hydrolyzing mixture at 55° C with mixing for 18 hours. The resistance of the sheets was determined with an A.C. conductivity bridge (1 kc) and found to be 18,000 ohm-cm 2 (1N H 2 SO 4 ), indicating that a section of unfunctionalized polystyrenated polyethylene still exists. The sulfonic acid groups were then neutralized and converted to their potassium salt with a 0.1N KOH/5% KCl solution and the excess electrolyte leached out with distilled water. The sheets were now blotted dry with paper towels and placed in a vacuum oven over P 2 O 5 at 40° C. Alternatively, the sheets may be stirred in carbon tetrachloride, overnight.
The remaining unfunctionalized styrene groups were thereafter chloromethylated by placing the partially reacted film into a mixture of chloromethyl methyl ether containing 2.5% (by weight) SnCl 4 and refluxing at 57° C. for 6 hours. The chloromethylene groups were then quaternized in a solution of 25% (by volume) trimethylamine in acetone for 18 hours at 25° C. prior to equilibrating in a 1N KF solution for 24 hours at room temperature. The final single film bipolar membrane had a potential drop across it of 1.07 at 109 ma/cm 2 (DC) when measured in an electrodialysis cell with 1N KOH and 1N HCl next to its anion and cation permeable sides, respectively. Its potential drop at zero current flow (Eo) was 0.81 volts, indicative of the fact that it is bipolar and functions as a water-splitter. In an electrodialysis cell with 8.7-9.1% HF and 9.4-11.0% KOH on opposite sides, at 163 ma/cm 2 (DC) it was found to have a base current efficiency of 74% and an acid current efficiency of 83% and KF in the acid at only 0.5%, i.e. N SA = 0.5%. This membrane was run continuously for 371 days as a water-splitter at 77-91 ma/cm 2 (DC) at 30° C. between 9% HF and 7% KOH with no loss in its performance characteristics and only a modest increase in its potential drop.
Microtomed cross-sections of the membrane had their cationic regions stained with methylene blue or their anionic region stained with methyl orange. In either case, microscopic examination of such sections clearly show the exact location of the interface and also its sharpness. Generally, the lower the potential drop of the membrane the closer the cationic permeable layer approaches the opposite face, up to about 95%; whereupon the film begins to lose some of its bipolarity (Eo falls below 0.78) and assumes more and more pure cationic character, e.g., Eo approaches zero.
EXAMPLE 23
A styrenation mixture consisting of 7.5 parts commercial divinyl benzene and 92.3 parts of freshly distilled styrene was heated in a beaker, with agitation to 80° C. Then 0.2 parts of benzoyl peroxide was added, as catalyst, and after mixing for 1 minute, the solution was poured into a 9 × 14 × 1 1/4 inch stainless steel trough, immersed in an 80° C constant temperature bath. Immediately thereupon, a 7 × 23 inch sheet of 9 mil high density polyethylene was folded in half and immersed in the sytrenating mixture, supported by two stainless steel rods. After impregnating the film for 35 minutes, it was removed from the trough, excess styrene squeegeed off its surface and then it was clamped securely between three aluminum foil covered, 8 × 12 × 1/8 inch glass plates. The ensemble was completely immersed in a saturated sodium sulfate salt solution at 80° C. for 18-22 hours to complete the polymerization. After removing, rinsing with distilled water for 3 hours at 45° C. and drying in a vacuum oven overnight at 40° C over P 2 O 5 , the film was found to contain 16.7 weight percent polystyrene. Excess polystyrene was removed with dichloroethane. The above described process was repeated on the same films yielding a product containing 33.5 percent polystyrene. This higher polystyrene content was required due to the higher divinyl benzene content if one wishes to maintain a low voltage drop across the final membrane.
After swelling the polystyrenated sheet 24 hours in CCl 4 , and removing free polystyrene from its surface, 7 × 11 inch sections were mounted in the chlorosulfonation apparatus described in Example 22. Chlorosulfonation was conducted with a 65/35 (by volume) chlorosulfonic acid/carbon tetrachloride mixture from one side only for 210 minutes at 25° C. After rinsing with CCl 4 and hydrolyzing at 40° C. in 1N H 2 SO 4 for two days, the partially functionalized sheet was found to have a resistance of 8,600 ohm-cm 2 in 1N H 2 SO 4 (A.C. conductivity bridge, 1 kc) indicating that part of the sheet remained unfunctionalized. The sulfonic acid groups were neutralized and converted to their potassium salt with 0.1N KOH/5%KCl solution and the excess electrolyte leached out with distilled water. The sheets were blotted dry with paper towels and placed in a vacuum oven over P 2 O 5 at 40° C.
The remaining unfunctionalized styrene groups were thereafter chloromethylated by placing the film into a mixture of chloromethyl methyl ethere containing 2.5% (by weight) SnCl 4 and refluxing (57° C) for six hours. Next, the chloromethylene groups were quaternized in a solution of 25% (by volume) trimethylamine in acetone for 18 hours at 25° C. prior to equilibrating in a 1N KF solution for 2 days at room temperature. The final single film bipolar membrane was found to have a potential drop of 1.04 volts at 109 ma/cm 2 when mounted between 1N KOH and 1N HCl in an electrodialysis cell. At no current flow its potential drop was 0.78 (Eo). In addition, it was found to perform as a watersplitter at an acid current efficiency of 78.9% and a base current efficiency of 66% when mounted between 5.0% KOH and 5.4% HF and at a current of 163 ma/cm 2 . The membrane produced salt (KF) in the acid (HF) solution at a current efficiency of only 0.48%, i.e. N SA = 0.48%.
EXAMPLE 24
A styrenation mixture consisting of 15 parts of commercial divinyl benzene and 84.5 parts of freshly distilled styrene was heated in a beaker with agitation to 90° C. To this mixture was then added 0.5 parts of benzoyl peroxide as catalyst, and after mixing for one-half minute, the solution was poured into 9 × 14 × 1-1/4 inch stainless steel trough, immersed in a 90° C constant temperature bath. Immediately thereupon a 7 × 23 inch sheet of 9 mil high density polyethylene film, folded in half, was immersed in the styrenating mixture and supported by two stainless steel rods. After impregnating the film for 17 minutes it was removed, squeegeed free of excess surface styrene and clamped tightly between three aluminum foil covered 8 × 12 × 1/8 inch glass plates. The entire ensemble was quickly immersed in a saturated sodium sulfate salt solution at 75° C and left for 20 hours to complete the polymerization. After removing, rinsing with distilled water for 3 hours at 45° C and drying overnight in a vacuum oven over P 2 O 5 at 40° C, the film was found to contain 16.3% (by weight) polystyrene. The above described process was repeated on the same film yielding a product with contained 38.1% polystyrene.
After swelling the sheet 24 hours in carbon tetrachloride and removing excess free polystyrene from its surface, 7 × 11 inch sections were mounted in the chlorosulfonation apparatus described in Example 22.Chlorosulfonation was conducted with a 56/44 (by volume) chlorosulfonic acid/carbon tetrachloride mixture from one side only for 180 minutes at 25° C. After rinsing with CCl 4 and hydrolyzing at 55° C. in 1N H 2 SO 4 for two days the partially functionalized sheet was determined to have a resistance (A.C. conductivity bridge, 1 kc) of 4,700 ohm-cm 2 in 1N H 2 SO 4 , indicating that part of the sheet still remains unfunctionalized. The sulfonic acid groups were neutralized and converted to their potassium salt with a 0.1N KOH/5%KCl solution and the excess electrolyte leached out with distilled water. The sheets were blotted dry with paper towels and placed in a vacuum oven over P 2 O 5 at 40° C overnight.
The remaining unfunctionalized styrene groups were now chloromethylated by placing the film into a mixture of chloromethyl methyl ether containing 2.5% (by weight) SnCl 4 and refluxing at 57° C for 6 hours. The chloromethylene groups were then quaternized in a solution of 25% (by volume) trimethylamine in acetone for 18 hours at 25° C prior to equilibrating in a 1N KF solution for two days at room temperature. The final single film bipolar membrane was found to have a potential drop of 0.84 volts at 91 ma/cm 2 with 1N KOH and 1N HCl adjacent to its anion and cation permeable sides, respectively. At no current flow its potential drop was 0.78 (Eo). It performed with a base current efficiency of 74% and an acid current efficiency of 92% when tested in an electrodialysis cell at 163 ma/cm 2 , between 9.1-9.5% HF and 9.8-11.3% KOH, and N SA = 1.6%. In addition, it was used in continuous operation as a water-splitter in an electrodialysis cell for 126 days at 47° C and 91 ma/cm 2 while mounted between 1% NaOH and 0.8N HCl.
Microscopic examination of stained thin cross-sections of similar membranes (40% polystyrene) show that chlorosulfonation for 150 minutes yields a single film bipolar membrane which is 67% cationic and has a potential drop of 0.97 volts at a current density of 163 ma/cm 2 (Eo = 0.78 volts). Chlorosulfonation for 210 minutes yields films with a resistance of 9.3 ohm-cm 2 (1N H 2 SO 4 ) and which are 97% cationic and yield subsequent bipolar membranes with Eo = 0.70 volts, indicating it has lost some of its bipolarity.
EXAMPLE 25
A styrenation mixture consisting of 15 parts commercial divinyl benzene and 84.5 parts of freshly distilled styrene was heated in a beaker with agitation at 80° C. Then 0.5 parts of benzoyl peroxide as catalyst was added and after mixing for 1 minute, the solution was poured into a 9 × 14 × 1-174 inch stainless steel trough immersed in an 80° C constant temperature bath. Immediately thereupon, a 7 × 23 inch sheet of 10 mil ultra high molecular weight polyethylene was immersed in the styrenating mixture and supported by stainless steel rods. After impregnating the film for 25 minutes, it was removed from the trough, excess styrene squeegeed from its surface and then it was clamped securely between three aluminum foil covered, 8 × 12 × 1/8 inch glass plates. The ensemble was completely immersed in a saturated sodium sulfate salt bath at 70° C for 18 hours to complete the polymerization. After removing, rinsing with distilled water for 3 hours at 45° C and drying in a vacuum oven overnight at 40° C over P 2 O 5 , the film was found to contain 25 weight percent polystyrene. After swelling the polystyrenated sheet 24 hours in CCl 4 , and removing any free polystyrene from its surface, 7 × 11 inches sections were mounted in the chlorosulfonation apparatus described in Example 22. Chlorosulfonation was conducted with 56/44 (by volume) chlorosulfonic acid/carbon tetrachloride mixture from one side only for 210 minutes at 25° C. After a quick CCl 4 rinse, the film were hydrolyzed in 1N H 2 SO 4 for two days at 60° C. The resistance of the partially functionalized sheet was measured with an A.C. conductivity bridge at 1 kc and found to be 17,700 ohm-cm 2 in 1 N H 2 SO 4 . The sulfonic acid groups were then neutralized and converted to the potassium salt with 0.1N KOH/5%HCl solution. After leaching out excess electrolyte with distilled water, the sheets were blotted dry with paper towels and placed in a vacuum oven at 40° C over P 2 O 5 overnight.
The remaining, unfunctionalized styrene groups were now chloromethylated by placing the film into a solution of chloromethyl methyl ether containing 2.5% (by weight) SnCl 4 and refluxing at 57° C for 6 hours. The chloromethylene groups so formed were then quaternized by reacting in a solution of 25% trimethylamine in acetone at 30° C for 24 hours prior to equilibration for 48 hours in 1N KF. The final single film bipolar membrane was found to have a potential drop of 1.14 volts at 91 ma/cm 2 (DC) when used between 1N KOH and 1N HCl solution. At zero current it had a potential drop (Eo) of 0.79 volts. In an electrodialysis cell between 9.5-10.0% HF and 9.9-11.5% KOH at a current density of 163 ma/cm 2 it was found to perform as a water-splitter with a base current efficiency of 72% and an acid current efficiency of 83% and no KF salt was found in the HF. In addition, the membrane was operated as a water-splitter continuously for 380 days at 47° C and 91 ma/cm 2 when kept between 9% HF and 7% KOH solutions. Its performance was then remeasured and found to be unchanged, i.e. 74.6% base current efficiency and 84.9% acid current efficiency.
EXAMPLE 26
A styrenation mixture consisting of 15 parts commercial divinyl benzene and 84.5 parts of freshly distilled styrene was heated in a beaker, with agitation to 80° C. Then 0.5 parts of benzoyl peroxide as catalyst was added and after mixing for 1 minute, the solution was poured into a 9 × 14 × 1-1/4 inches stainless steel trough, immersed in an 80° C constant temperature bath. Immediately thereafter, a 7 × 23 inches sheet of 10 mil ultra-high molecular weight polyethylene was folded in half and immersed in the styrenating mixture, supported by two stainless steel rods. After impregnating the film for 30 minutes, it was removed from the trough, excess styrene squeegeed off its surface and then it was clamped securely between three aluminum foil covered, 8 × 12 × 1/8 inch glass plates. The ensemble was completely immersed in a saturated sodium sulfate salt solution at 75° C for 20 hours to complete the polymerization. The film was removed, rinsed with distilled water for 3 hours at 45° C and dried overnight in a vacuum oven at 40° C over P 2 O 5 . It was found to contain 18.0% polystyrene and the above described process was repeated once more yielding a sheet containing 36.8 percent polystyrene.
After swelling the polystyrenated sheet overnight in CCl 4 , and removing free polystyrene from its surface, 7 × 11 inches sections were mounted in the chlorosulfonation apparatus described in Example 22. Chlorosulfonation was conducted with a 56/44 (by volume) chlorosulfonic acid/carbon tetrachloride mixture from 1 side only for 330 minutes at 30° C. After rinsing with CCl 4 and hydrolyzing at 40° C in 1N H 2 SO 4 for 2 days, the partially functionalized sheet was determined to have a resistance of 48 ohm-cm 2 in 1N H 2 SO 4 . Microscopic examination of a stained thin section indicated that 94% of the film was cationic. The sulfonic acid groups were neutralized and converted to their potassium salt with a 0.1N KOH/5%KCl solution and the excess electrolyte leached out with distilled water. The sheets were blotted dry with paper towels and placed in a vacuum oven overnight at 40° C over P 2 O 5 .
The remaining unfunctionalized styrene groups were now chloromethylated by placing the film into a mixture of chloromethyl methyl ether containing 2.5% (by weight) SnCl 4 and refluxing at 57° C for 6 hours. The chloromethylene groups were then quaternized in a solution of 25% (by volume) trimethylamine in acetone for 24 hours at 30° C prior to equilibrating in a 1N KF solution for 2 days at room temperature. The final single film bipolar membrane was found to have a potential drop of 0.86 volts at 109 ma/cm 2 (D.C.) when placed between a 1N KOH and 1N HCl solution. At no current flow the potential drop across it was found to be 0.79 volts (Eo). In an electrodialysis cell between 9.1-9.5% HF and 9.8-11.4% KOH it performed as a water-splitter with a base current efficiency of 76% and an acid current efficiency of 87% at a current density of 163 ma/cm 2 , and N SA = 0.1%.
Specimens of the same initial styrenated polyethylene sheets which were chlorosulfonated from one side only from 270-300 minutes yielded subsequent single film bipolar membranes which were determined to be 81% cationic and had potential drops of 1.03 volts at 109 ma/cm 2 and an Eo = 0.79 volts. Evidently, the greater the polystyrene content of the membrane not only is its potential drop lower but it is also less sensitive to its degree of cationic character. Specimens chlorosulfonated for shorter time periods (210-240 minutes) had smaller cationic regions (64-66%) and slightly higher potential drops (1.25-1.43 volts at 109 ma/cm 2 .
EXAMPLE 27
A styrenation mixture consisting of 15 parts commercial divinyl benzene and 84.5 parts of freshly distilled styrene was heated in a beaker, with agitation, to 85° C. Then 0.5 parts of benzoyl peroxide was added, as catalyst, and after mixing for one-half minute the solution was poured into a 9 × 14 × 1-1/4 inches stainless steel trough, immersed in a 85° C constant temperature bath. A 7 × 23 inches sheet of 10 mil ultra-high molecular weight polyethylene was folded in half and immersed in te styrenating mixture supported on two stainless steel rods. After impregnating the film for 30 minutes, it was removed from the trough, excess styrene squeegeed off its surface and then it was clamped securely between three aluminum foil covered, 8 × 12 × 1/8 inch glass plates. The entire assembly was then completely immersed in a saturated sodium sulfate salt solution at 75° C for 20 hours to complete the polymerization. After removing, rinsing with distilled water for 3 hours at 45° C and drying in a vacuum oven overnight at 40° C over P 2 O 5 , the film was found to contain 22.8% polystyrene. The above described process was repeated once more on the same styrenated sheet yielding a final sheet containing 45.9% polystyrene.
After swelling the polystyrenated sheet for 24 hours in CCl 4 , and removing any free surface polystyrene, 7 × 11 inches sections were cut out and mounted in the chlorosulfonation apparatus described in Example 22. Chlorosulfonation was conducted with a 56/44 (by volume) chlorosulfonic acid/carbon tetrachloride mixture from one side only for 270 minutes at 25° C. After rinsing with CCl 4 and hydrolyzing at 55° C for 48 hours, the partially functionalized sheet was determined to have a resistance of 1,000 ohm-cm 2 (A.C. conductivity bridge, 1 kc) in 1N H 2 SO 4 . The sulfonic acid groups were then neutralized and converted to their potassium salt with a 0.1N KOH/5% KCl solution and the excess electrolyte was leached out with distilled water. The sheets were blotted dry with paper towels and placed in a vacuum oven over P 2 O 5 at 40° C overnight.
The remaining unfunctionalized styrene groups were now chloromethylated by placing the film into a mixture of chloromethyl methyl ether containing 2.5% (by weight) SnCl 4 and refluxing at 57° C for 6 hours. The chloromethylene groups were then quaternized in a solution of 25% (by volume) trimethylamine in acetone for 18 hours at 25° C prior to equilibrating in a 1N KF solution for two days at room temperature. The final single film bipolar membrane was found to have a potential drop of 0.80 volts at 91 ma/cm 2 (D.C.) when mounted between 1N KOH and 1N HCl in an electrodialysis cell. At no current flow, it had a voltage drop of 0.79 volts. It performed as a water-splitter between 9.3-9.7% HF and 9.7-11.5% KOH at 163 ma/cm 2 with a base current efficiency of 73% and an acid current efficiency of 86% and no KF was found in the acid, i.e., N SA = O. In addition, it was run continuously for 167 days in an electrodialysis cell at 47° C and 91 ma/cm 2 while mounted between 9% HF and 9% KOH without any loss in its performance efficiencies.
Samples from the same initial styrenated polyethylene film were chlorosulfonated as described above for times ranging from 210 to 300 minutes and yielded subsequent single film bipolar membranes with potential drops of about 0.80 volts at 109 ma/cm 2 .
EXAMPLE 28
A styrenation mixture consisting of 7.5 parts of commercial divinyl benzene and 92.3 parts of freshly distilled styrene was heated in a beaker, with agitation, to 85° C. Then 0.2 parts of benzoyl peroxide was added, as catalyst, and after mixing for 1 minutes the solution was poured into a 9 × 14 × 1-1/4 inches stainless steel trough, immersed in an 85° C constant temperature bath. Immediately thereafter, a 7 × 23 inches sheet of 10 mil ultra-high molecular weight polyethylene film, supported by two stainless steel rods, was immersed into the styrenated mixture. After impregnating the film for 30 minutes, it was removed from the trough, excess styrene squeegeed from its surface, and then it was clamped securely between three aluminum foil covered, 8 × 12 × 1/8 inch glass plates. The entire assembly was completely immersed in a saturated sodium sulfate salt solution at 85° C for 20 hours to complete the polymerization. After removing, rinsing with distilled water for 3 hours at 45° C, and drying in a vacuum oven overnight at 40° C over P 2 O 5 , the film was found to contain 19.6% polystyrene. The above process was once more repeated on the same styrenated sheet and yielded a final product containing 43.3% polystyrene.
After swelling the polystyrenated sheet 24 hours in CCl 4 , and removing the free polystyrene from its surface, 7 × 11 inches sections were cut out and mounted in the chlorosulfonation apparatus described in Example 22. Chlorosulfonation was conducted with a 65/35 (by volume) chlorosulfonic acid/carbon tetrachloride mixture from one side only for 280 minutes at 25° C. After rinsing with CCl 4 and hydrolyzing at 55° C in 1N H 2 SO 4 for two days, the partially functionalized sheet was determined to have a resistance of 4,800 ohm-cm 2 in 1N H 2 SO 4 (A.C. conductivity bridge, 1 kc). The sulfonic acid groups were then neutralized and converted to their potassium salt with a 0.1N KOH/5% KCl solution and the excess electrolyte leached out with distilled water. The sheets were blotted dry with paper towels and placed in a vacuum oven over P 2 O 5 at 40° C overnight.
The remaining unfunctionalized styrene groups were now chloromethylated by placing the film into a mixture of chloromethyl methyl ether containing 2.5% (by weight) SnCl 4 and refluxing at 57° C for 6 hours. The chloromethylene groups were then quaternized in a solution of 25% (by volume) trimethylamine in acetone for 18 hours at 30° C prior to equilibrating in a 1N KF solution for 2 days at room temperature. The final single film bipolar membrane was found to have a potential drop of 0.90 volts at 109 ma/cm 2 (DC) when mounted between 1N KOH and 1N HCl. At no current flow its potential drop was 0.78 volts (Eo). It performed as a water-splitter between 5.1% HF and 5.4% KOH at 163 ma/cm 2 with a base current efficiency of 82% and an acid current efficiency greater than 90% and N SA = 0.34%.
Sections of the same initial styrenated polyethylene film were chlorosulfonated as described above for times ranging from 220 to 320 minutes. The single film bipolar membranes subsequently obtained had potential drops ranging from 1.03 to 0.86 volts at a current density of 109 ma/cm 2 . Microscopic examination of stained, thin cross-sections of these same bipolar membranes show the cationic regions range from 54-79%.
The bipolar membranes of the invention will find a variety of advantageous applications as will be apparent to those skilled in the art. A typical application is that illustrated by the cell 1 of FIG. 1 wherein a bipolar membrane 2 is employed between two inner components 5 and 6 of a four compartment unit formed in conjunction with conventional anion and cation permeable membranes 3 and 4, respectively. The unit includes outer compartment 7 and 8 and is provided with a cathode 9 and anode 10.
TABLE II__________________________________________________________________________PERFORMANCE DATA FOR SINGLE FILM BIPOLAR MEMBRANESFilm Composition ElectrolyteExampleInitial % Poly- % Divinyl Voltage Drop i.sub.d Concentrations Current EfficiencyNo. Film styrene benzene.sup.(1) E.sub.o E.sub.m (ma/cm.sup.2) %HF %KOH %N.sub.B %N.sub.A %N.sub.SA__________________________________________________________________________22 8.6 mil 23 2 0.81 1.07v 109 9.5-9.8 3.7-5.3 80 82.6 0.98HDPE at 109 ma/cm.sup.2 163 8.7-9.1 9.4-11.0 74 83 0.523 8.6 mil 33.5 7.5 0.78 1.04v 109 -- -- -- -- --HDPE at 109 ma/cm.sup.2 163 5.4 5 66 78.9 0.4824 8.6 mil 38.1 15 0.78 0.84v 109 -- -- -- -- --HDPE at 91 ma/cm.sup. 2 163 9.1-9.5 9.8-11.3 74 92 1.625 10 mil 25.1 15 0.79 1.14v 109 10.1-10.3 4.3-5.7 78 77 0.4UHMW-PE at 91 ma/cm.sup.2 163 9.5-10.0 9.9-11.5 72 83 --26 10 mil 36 15 0.79 0.86v 109 -- -- -- -- --UHMW-PE at 109 ma/cm.sup.2 163 9.1-9.5 9.8-11.4 76 87 0.127 10 mil 45.9 15 0.79 0.80v 109 ˜10 7.5-8.5 68 (74) --UHMW-PE at 91 ma/cm.sup.2 163 9.3-9.7 9.7-11.5 73 8628 10 mil 43.3 7.5 0.78 0.90v 109 -- -- -- -- --UHMW-PE at 109 ma/cm.sup.2 163 5.1 5.4 82 >90 0.34__________________________________________________________________________ .sup.(1) Weight percent commercial 55% divinylbenzene in the styrenation mixture. .sup.(2) %N.sub.B = current efficiency for the production of base, KOH. .sup.(3) %N.sub.A = current efficiency for the production of acid, HF. .sup.(4) %N.sub.SA = current efficiency for the production of salt, KF, i acid, HF.
Employing the procedure of Example 22 the bipolar membranes of Examples 29 to 31 were prepared, the data therefor is set forth in TABLE III.
TABLE III__________________________________________________________________________Ex. Chloromethylation EmNo. Film Styrenation Polymerization Chlorosulfonation and Quaternization__________________________________________________________________________29 8 Mil 89.5% styrene 18 Hrs. at 75° C 150 min. at 25° C 6 Hrs. at 58° C (109 ma/cm.sup.2) Polypropylene 10% Divinyl- 2 stages to 65/35:ClSO.sub.3 H/ chloro-methyl- 0.92 volt benzene 41% polystyrene CCl.sub.4 methyl ether 0.5% Benzoyl- 2.5% SnCl.sub.4 peroxide 20 Hrs. at 25° C. 20 min. at 85° C 25/75: trimethyl- amine/acetone30 9 Mil 94.5% 2-chloro- 18 Hrs. at 75° C. 180 min at 25° C. " 1.10 volt polyethylene styrene 25% poly-2- 65/35:ClSO.sub.3 H/ polypropylene 5% divinyl chloro-styrene CCl.sub.4 co-polymer toluene 0.5% Benzoyl- peroxide 30 min. at 85° C.31 8 Mil poly- 92% 2-chloro- 18 Hrs. at 25° C 180 min. at 75° C. " 1.05 volt chlorotri- styrene 2 stages to 36% 65/35:ClSO.sub.3 H/ fluoro 7.5% α,α'-di- polystyrene CCl.sub.4 ethylene methyl divinyl benzene 0.5% Benzoyl- peroxide 25 min. at 80° C__________________________________________________________________________
|
Novel single film bipolar membranes, of substantially improved efficiency and durability, i.e. having an ion selectivity above 80% in an electrolyte medium of about one mole, are prepared from pre-swollen films containing a relatively high amount, i.e. at least 15% of an insoluble cross-linked aromatic polymer. Under controlled conditions, high dissociable cationic-exchange groups are chemically bonded to the aromatic nuclei to a desired depth of the film from one side only; subsequently, highly dissociable anion-exchange groups are chemically bonded to the unreacted aromatic nuclei on the other side of the film. The functionalized, densely structured single film ion exchange membrane undergoes negligible degradation, is blister free, and is uniquely suited for electrodialysis particularly water-splitting operations due to its low electrical resistance and low salt leakage. The membrane operates with improved current efficiencies at both high electrolyte concentrations and high current densities, for time periods not previously achievable.
| 2
|
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is the U.S. National Phase of PCT Appln. No. PCT/EP2013/076993 filed Dec. 17, 2013, the disclosure of which is incorporated in its entirety by reference herein.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a modified silicone composition, and to the silicone elastomers produced therefrom by curing, which delay or prevent the formation of a biofilm on their surface.
[0004] 2. Description of the Related Art
[0005] In the medical sector, numerous products made from silicone are used, for example face masks, valves, hoses, catheters, lining materials, bandages, prostheses, dressing materials, implants, etc. For all applications, in the course of the use period, an occupation of the surface with bacteria can take place which, in some cases, can lead to infections. In this connection, antibiotic-resistant bacterial strains are a growing problem since they lead to infections that are difficult to treat. The first step for an occupation is the adhesion of the bacteria to the exogenous surface. Following colonization, biofilm formation can result which is particularly problematic because the endogenous immune system or antibiotics can only attack the bacteria with very great difficulty through the protection of the biofilm.
[0006] The admixing or coating of bactericidally effective substances forms part of the prior art for medical products, with the very administration of non-lethal antibiotic doses promoting the replication of resistant bacteria. Often, antibiotics, quaternary ammonium compounds, silver ions or silver or iodine are added, where the solubility in water leads to the washing out of the active substances, which, in the case of a controlled release system, leads to the killing of bacteria in the surrounding area of the implant and/or the component. As a result of the leaching out, the active substance is gradually used up, such that the entire system can no longer be antibacterially effective after some time.
[0007] WO2009/019477A2 describes, as a further option, the coating of a medical implant with a biodegradable layer which consists of a polymer and an acid-acting additive which is mixed into the polymer. A disadvantage of this technology is the ineffectiveness at a damaged site if the coating is detached from the substrate. Moreover, the active substance is here too washed out as a result of contact with bodily fluids and loses its effectiveness over a certain period.
[0008] In WO98/50461, elemental silver is mixed into a coating in the form of a powder in order to achieve an antimicrobial effect. In the case of silver-containing products, there is the risk that contact with bodily fluids containing S—H groups will reduce the effective concentration of the silver ions, and the lethal dose will no longer be able to be achieved which in turn leads to a product which is antimicrobially ineffective.
[0009] EP0022289B1 describes antimicrobial polymer compositions which are used in the medical sector. Here, a releasable amount of a carboxylate agent is added to the polymer base materials. This too leads to the disadvantages specified above.
[0010] The patent specification WO2008/140753A1 describes an implant which is antimicrobially and fungicidally equipped through impregnation with parabens. On account of the lack of covalent bonding to the matrix of the implant, the active substance is released to the surrounding area within a short period in the case of this application too (drug-release system).
[0011] All of the solutions proposed hitherto in the prior art for the antibacterial equipping of medical products for preventing the formation of biofilms exhibit the major disadvantage that the antimicrobial substances are washed out as a result of the contact with media such as water or bodily fluids. As a result, the active groups or ions or molecules on the surface of the medical products become depleted and the surface inhibition of the biofilm formation is reduced in its effect.
SUMMARY OF THE INVENTION
[0012] It was therefore an object of the present invention to provide silicone compositions which are able to suppress or to inhibit bacteria and/or fungus or algae growth on the surface of crosslinked silicone elastomers produced therefrom, and without leaching or extraction of the active component taking place. Such crosslinked products are consequently protected against the occupation and the attack of microorganisms. This object was achieved by a crosslinkable silicone composition which comprises at least one silicone compound (X) of the general formula (I)
[0000]
[0013] where
R 1 is hydrogen, or a monovalent radical optionally containing heteroatoms, such as alkyl-, aryl-, arylalkyl-, alkylaryl-, SiR 7 3 —, polydimethylsiloxane-, R 2 identical or different, are hydrogen, or a monovalent radical optionally containing heteroatoms, such as alkyl-, aryl-, arylalkyl-, alkylaryl-, R 8 COOR 1 , R 3 identical or different, are a hydrogen, a monovalent radical optionally containing heteroatoms, such as alkenyl-, alkenylaryl-, alkyl-, aryl-, arylalkyl-, alkylaryl-, —OSiR 7 3 , R 7 is a monovalent radical optionally containing heteroatoms, such as alkenyl-, alkenylaryl-, alkyl-, aryl-, arylalkyl-, alkylaryl-, —OSiR 7 3 , R 8 is a bivalent alkyl radical, n is a number between 1 and 30, m is a number between 0 and 6000,
[0021] with the proviso that, per molecule of the compound (X), at least one R 3 is an aliphatically unsaturated double bond or a hydrogen atom; preferably at least two R 3 are an aliphatically unsaturated double bonds or hydrogen atoms, and more preferably at least three R 3 are aliphatically unsaturated double bonds or hydrogen atoms, and
[0022] with the proviso that the silicone compound (X) is used in amounts such that the silicone composition comprises between 0.005 mmol/g and 2 mmol/g of carboxylic acid groups, carboxylic acid esters, or carboxylic anhydrides hydrolyzable to give carboxylic acids, based on the acid group; preferably between 0.01 mmol/g and 1 mmol/g, more preferably between 0.02 mmol/g and 0.085 mmol/g and most preferably between 0.04 mmol/g and 0.7 mmol/g.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0023] The silicone compound (X) contains at least one functional group in the siloxane moiety which completes a bonding to the silicone matrix during the crosslinking. The product of the crosslinking reaction is therefore a silicone elastomer, for example a polydimethylsiloxane network modified by acidic groups. The antimicrobially effective groups or agents are covalently bonded to the silicone matrix and the silicone elastomer consequently does not exhibit the specified disadvantages detailed in the prior art. Consequently, the leaching out or extraction of the active component is no longer possible. It is a further advantage that an undesired contamination of objects or media which come into contact with the silicone elastomer is prevented.
[0024] The acidic effect of the compound (X) is based on the fact that it contains a carboxylic acid function which can be present either in unprotected form or in the form of a carboxylic acid ester.
[0025] Examples of R 1 for alkyl radicals are the methyl, ethyl, propyl, isopropyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-octyl, 2-ethylhexyl, 2,2,4-trimethylpentyl, n-nonyl and octadecyl radicals; cycloalkyl radicals such as the cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, adamantylethyl or bornyl radicals; aryl or alkaryl radicals such as the phenyl, ethylphenyl, tolyl, xylyl, mesityl or naphthyl radicals; and aralkyl radicals such as the benzyl, 2-phenylpropyl or phenylethyl radical. Examples of R 1 with heteroatoms are derivatives of the above radicals that are halogenated and/or functionalized with organic groups, such as the 3,3,3-trifluoropropyl, 3-iodopropyl, 3-isocyanatopropyl, aminopropyl, methacryloxymethyl or cyanoethyl radicals, silyl radicals such as trimethylsilyl, tert-butyldimethylsilyl, tetraethylsilyl, triisopropylsilyl, and tert-butyldiphenylsilyl, polydimethylsiloxane radicals such as trimethylsilyl- or vinyldimethyl-terminated polydimethylsiloxanes, trimethylsilyl- or vinyldimethyl-terminated polydimethylsiloxane-vinylmethylsiloxane copolymers, trimethylsilyl- or vinyldimethyl-terminated polydimethylsiloxane-hydrogenmethylsiloxane copolymers, trimethylsilyl- or vinyldimethyl-terminated polydimethylsiloxane-phenylmethylsiloxane copolymers or trimethylsilyl- or vinyldimethyl-terminated polydimethylsiloxane-phenylmethylsiloxane-methylhydrogensiloxane copolymers. If R 1 is hydrogen and at the same time one R 2 contains a carboxyl group, the anhydride of the two carboxyl groups can be formed and/or used. If R 1 is hydrogen and at the same time one R 2 contains a hydroxyl group, the internal ester (=lactone) possible from the two functionalities can be formed and/or used.
[0026] Preferred radicals R 1 are the methyl, ethyl, phenyl, silyl and polydimethylsiloxane radicals, and anhydrides or lactones of further carboxyl or hydroxyl groups present in the same molecule. Particularly preferred radicals R 1 are the silyl and polydimethylsiloxane radicals, and anhydrides or lactones of further carboxyl or hydroxyl groups present in the same molecule.
[0027] Examples of R 2 for alkyl radicals are the methyl, ethyl, propyl, isopropyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-octyl, 2-ethylhexyl, 2,2,4-trimethylpentyl, n-nonyl and octadecyl radicals; cycloalkyl radicals such as the cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, adamantylethyl or bornyl radical; aryl or alkaryl radicals such as the phenyl, ethylphenyl, tolyl, xylyl, mesityl or naphthyl radicals; and aralkyl radicals such as the benzyl, 2-phenylpropyl or phenylethyl radicals. Examples of R 2 with heteroatoms are derivatives of the above radicals that are halogenated and/or functionalized with organic groups, such as the 3,3,3-trifluoropropyl, 3-iodopropyl; 3-isocyanatopropyl, aminopropyl, methacryloxymethyl or cyanoethyl radicals, alkylcarboxy radicals such as —(CH 2 ) n —COOH, —(CH 2 ) n —COOSiMe 3 , —(CH 2 ) n —COOSiEt 3 , —(CH 2 ) n —COOSi i Pr 3 , —(CH 2 ) n —COOSi t Bu 3 , —(CH 2 ) n —COO-trimethylsilyl- or vinyldimethyl-terminated polydimethylsiloxanes, —(CH 2 ) n —COO-trimethylsilyl- or vinyldimethyl-terminated polydimethylsiloxane-vinylmethylsiloxane copolymers, —(CH 2 ) n —COO-trimethylsilyl- or vinyldimethyl-terminated polydimethylsiloxane-hydrogenmethylsiloxane copolymers, —(CH 2 ) n —COO-trimethylsilyl- or vinyldimethyl-terminated polydimethylsiloxane-phenylmethylsiloxane copolymers, —(CH 2 ) n —COO-trimethylsilyl- or vinyldimethyl-terminated polydimethylsiloxane-phenylmethylsiloxane-methylhydrogensiloxane copolymers, hydroxyalkyl radicals such as —(CH 2 ) n —OH, where n can assume the values listed above.
[0028] If R 1 is hydrogen and at the same time one R 2 contains a carboxyl group not converted to carboxylic acid esters, the anhydride of the two carboxyl groups can be formed and/or used. If R 1 is hydrogen and at the same time one R 2 contains a hydroxyl group, the internal ester (=lactone) possible from the two functionalities can be formed and/or used.
[0029] Preferred radicals R 2 are the hydrogen, methyl, ethyl, phenyl, silyl and polydimethylsiloxane radicals, and anhydrides or lactones of further carboxyl or hydroxyl groups present in the same molecule. Particularly preferred radicals R 2 are silyl and polydimethylsiloxane radicals, and anhydrides or lactones of further carboxyl or hydroxyl groups present in the same molecule.
[0030] Examples of R 3 for alkyl radicals are the methyl, ethyl, propyl, isopropyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-octyl, 2-ethylhexyl, 2,2,4-trimethylpentyl, n-nonyl and octadecyl radicals; cycloalkyl radicals such as the cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, adamantylethyl or bornyl radicals; aryl or alkaryl radicals such as the phenyl, ethylphenyl, tolyl, xylyl, mesityl or naphthyl radicals; and aralkyl radicals such as the benzyl, 2-phenylpropyl or phenylethyl radicals. Examples of R 3 with heteroatoms are derivatives of the above radicals that are halogenated and/or functionalized with organic groups, such as the 3,3,3-trifluoropropyl, 3-iodopropyl, 3-isocyanatopropyl, aminopropyl, methacryloxymethyl or cyanoethyl radicals, alkenyl and/or alkynyl radicals such as the vinyl, allyl, isopropenyl, 3-butenyl, 2,4-pentadienyl, butadienyl, 5-hexenyl, undecenyl, ethynyl, propynyl and hexynyl radicals; cycloalkenyl radicals such as the cyclopentenyl, cyclohexenyl, 3-cyclohexenylethyl, 5-bicycloheptenyl, norbornenyl, 4-cyclooctenyl or cyclooctadienyl radicals; alkenylaryl radicals, such as styryl or styrylethyl radical, and also derivatives of the above radicals that are halogenated and/or contain heteroatoms, such as the 2-bromovinyl, 3-bromo-1-propynyl, 1-chloro-2-methylallyl, 2-(chloromethyl)allyl, styryloxy, allyloxypropyl, 1-methoxyvinyl, cyclopentenyloxy, 3-cyclohexenyloxy, acryloyl, acryloyloxy, methacryloyl or methacryloyloxy radicals, and also —O—SiR 3 . Preferred radicals R 3 are the hydrogen, methyl, phenyl, vinyl and 3,3,3-trifluoropropyl radicals, with the —O—SiR 3 radical of these radicals also being preferred. Particularly preferred radicals R 3 are the methyl and vinyl radicals, with the —O—SiR 3 radical also being preferred.
[0031] Examples of R 7 are alkyl radicals such as the methyl, ethyl, propyl, isopropyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-octyl, 2-ethylhexyl, 2,2,4-trimethylpentyl, n-nonyl and octadecyl radicals; cycloalkyl radicals such as the cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, adamantylethyl or bornyl radicals; aryl or alkaryl radicals such as the phenyl, ethylphenyl, tolyl, xylyl, mesityl or naphthyl radicals; and aralkyl radicals such as the benzyl, 2-phenylpropyl or phenylethyl radicals. Further examples of R 7 are derivatives of the above radicals that are halogenated and/or functionalized with organic groups, such as the 3,3,3-trifluoropropyl, 3-iodopropyl, 3-isocyanatopropyl, aminopropyl, methacryloxymethyl or cyanoethyl radicals, alkenyl and/or alkynyl radicals such as the vinyl, allyl, isopropenyl, 3-butenyl, 2,4-pentadienyl, butadienyl, 5-hexenyl, undecenyl, ethynyl, propynyl and hexynyl radicals; cycloalkenyl radicals such as the cyclopentenyl, cyclohexenyl, 3-cyclohexenylethyl, 5-bicycloheptenyl, norbornenyl, 4-cyclooctenyl or cyclooctadienyl radicals; alkenylaryl radicals such as the styryl or styrylethyl radicals, and derivatives of the above radicals that are halogenated and/or contain heteroatoms, such as the 2-bromovinyl, 3-bromo-1-propynyl, 1-chloro-2-methylallyl, 2-(chloromethyl)allyl, styryloxy, allyloxypropyl, 1-methoxyvinyl, cyclopentenyloxy, 3-cyclohexenyloxy, acryloyl, acryloyloxy, methacryloyl or methacryloyloxy radicals. Preferred radicals R 7 are the methyl, ethyl, isopropyl, tert-butyl, phenyl radicals. Particularly preferred radicals R 7 are the methyl, ethyl, and phenyl radicals.
[0032] Examples of R 8 are bivalent alkyl radicals such as methylene, ethylene, propylene, butylene, pentylene or hexylene radicals, as well as derivatives of the above radicals that are halogenated and/or functionalized with organic groups. Preferred radicals R 8 are the methylene and ethylene radicals. Particular preference is given to the methylene radical.
[0033] The index n is a number between 1 and 30, preferably between 1 and 18, and more preferably between 1 and 5. The index m refers to the degree of polymerization of the siloxane moiety, where m is a number between 0 and 6000, preferably between 0 and 1000 and more preferably between 1 and 100.
[0034] The preparation of the compound (X) can take place in various ways, with the synthesis route having no influence on the effectiveness. It is possible, for example, to use any synthesis routes which have hitherto been described in textbooks and/or publications.
[0035] As a class of starting substances for the synthesis of the compound (X), it is possible to use carboxylic acids and derivatives thereof, which are reacted in one or more stages to give the compound (X). Nonlimiting examples of suitable carboxylic acids and derivatives thereof are: formic acid, ethanoic acid, oxoethanoic acid, propanoic acid, propenoic acid, propynoic acid, butanoic acid, 2-butenoic acid, 2-butynoic acid, 3-butenoic acid, 3-butynoic acid, crotonic acid, fumaric acid, cyclopropanecarboxylic acid, 2-methylpropanoic acid, acetylenedicarboxylic acid, 2,4-pentadienoic acid, 2-pentenoic acid, 3-pentenoic acid, 4-pentenoic acid, 2-pentynoic acid, 3-pentynoic acid, 4-pentynoic acid, 2-pentenedioic acid, 2-methylenesuccinic acid, acrylic acid, methacrylic acid, 3,3-dimethylacrylic acid, maleic acid, methylmaleic acid, succinic acid, allylsuccinic acid, cyclobutanoic acid, ethylmalonic acid, ethenylmalonic acid, ethynylmalonic acid, glutaric acid, 2-methylglutaric acid, 2-ethenylglutaric acid, 2-ethynylglutaric acid, trimethylsilylacetic acid, vinyldimethylsilylacetic acid, 2,4-hexadienoic acid, propene-1,2,3-tricarboxylic acid, 1-cyclopentene-carboxylic acid, 3-cyclopentenecarboxylic acid, 2-hexynoic acid, sorbic acid, allylmalonic acid, allylmalonic anhydride, 3-methyl-4-pentenoic acid, 2-hexenoic acid, 3-hexenoic acid, 4-hexenoic acid, 3-(trimethylsilyl)propynoic acid, 3-(dimethylvinylsilyl)propynoic acid, 2-methylglutaric acid, 2-vinylglutaric acid, 3-allylglutaric acid, 3-vinylglutaric acid, 2-allylglutaric acid, dichlorobenzoic acid, dibromobenzoic acid, diiodobenzoic acid, bromochlorobenzoic acid, bromofluorobenzoic acid, bromoiodobenzoic acid, 6-heptynoic acid, 2,2-dimethyl-4-pentenoic acid, 6-heptenoic acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, heptanedioic acid, bromomethylbenzoic acid, chloromethylbenzoic acid, octenoic acid, phenylpropionic acid, sebacic acid, decanoic acid, decenoic acid, 10-bromodecanoic acid, 2-bromodecanoic acid, undecanoic acid, 10-undecenoic acid, 10-undecynoic acid, dodecanoic acid, dodecanedioic acid, 12-bromododecanoic acid, 2-bromododecanoic acid, 2-bromohexadecanoic acid, 16-bromohexadecanoic acid, linolenic acid, elaidic acid, oleic acid, arachidonic acid, erucic acid, 3-allyldihydrofuran-2,5-dione, 3-vinyldihydrofuran-2,5-dione, and also the methyl, ethyl, trimethylsilyl, triethylsilyl, and siloxy esters of the aforementioned carboxylic acids. Preferably, the carboxylic acid used contains an unsaturated group accessible to hydrosilylation. With the help of hydrosilylation catalysts, preferably those which contain platinum, reaction with Si—H-containing cyclo-, oligo- or polysiloxanes is performed. Preference is given to using carboxylic acid derivatives which no longer have an acidic hydrogen atom in the molecule (carboxylic acid esters and anhydrides, lactones). In a second reaction step, the vinyl group or vinyl groups can be introduced into compound (X) through suitable reactions. An example of this is the equilibration reaction between siloxanes known in the prior art. Through the selection of the siloxanes to be equilibrated, the compound from carboxylic acid or derivatives thereof obtained in the first step is reacted with a cyclo-, oligo- or polysiloxane which can carry both terminal and/or chain-position, aliphatically unsaturated groups.
[0036] In the silicone compositions according to the invention, it is possible to use peroxide-, addition- or condensation-crosslinking silicone compositions if they contain corresponding amounts of components (X).
[0037] In a preferred embodiment, silicone compositions according to the invention are addition-crosslinking, comprising, besides component (X)
at least one each of compound (A), (B) and (D), at least one compound each of (C) and (D), and at least one compound each of (A), (B), (C) and (D), where m(A) is an organic compound or an organosilicon compound, containing at least two radicals with aliphatic carbon-carbon multiple bonds, (B) is an organosilicon compound, containing at least two Si-bonded hydrogen atoms, (C) is an organosilicon compound, containing SiC-bonded radicals with aliphatic carbon-carbon multiple bonds and Si-bonded hydrogen atoms, and (D) is a hydrosilylation catalyst.
[0046] The addition-crosslinking silicone compositions according to the invention may be single-component silicone compositions or else two- or multi-component silicone compositions.
[0047] In two-component compositions, the individual components of the compositions according to the invention can contain all of the constituents in any desired combination, generally with the proviso that one component does not simultaneously comprise siloxanes with an aliphatic multiple bond, siloxanes with Si-bonded hydrogen and catalyst, i.e. essentially not simultaneously the constituents (A), (B) and (D) or (C) and (D). However, the compositions according to the invention are preferably single-component compositions.
[0048] As is known, the compounds (A) and (B) or (C) used in the compositions according to the invention are selected such that a crosslinking is possible. Thus, for example, compound (A) has at least two aliphatically unsaturated radicals and (B) has at least three Si-bonded hydrogen atoms, or compound (A) has at least three aliphatically unsaturated radicals and siloxane (B) has at least two Si-bonded hydrogen atoms, or else instead of compound (A) and (B), siloxane (C) is used which has aliphatically unsaturated radicals and Si-bonded hydrogen atoms in the aforementioned ratios. Mixtures of (A) and (B) and (C) with the aforementioned ratios of aliphatically unsaturated radicals and Si-bonded hydrogen atoms are also possible.
[0049] The compound (A) used according to the invention can be a silicon-free organic compound with preferably at least two aliphatically unsaturated groups, and can be an organosilicon compound with preferably at least two aliphatically unsaturated groups, or else mixtures thereof.
[0050] Examples of silicon-free organic compounds (A) are 1,3,5-trivinylcyclohexane, 2,3-dimethyl-1,3-butadiene, 7-methyl-3-methylene-1,6-octadiene, 2-methyl-1,3-butadiene, 1,5-hexadiene, 1,7-octadiene, 4,7-methylene-4,7,8,9-tetrahydroindene, methylcyclopentadiene, 5-vinyl-2-norbornene, bicyclo[2.2.1]hepta-2,5-diene, 1,3-diisopropenylbenzene, vinyl-group-containing polybutadiene, 1,4-divinylcyclohexane, 1,3,5-triallylbenzene, 1,3,5-trivinylbenzene, 1,2,4-trivinyl-cyclohexane, 1,3,5-triisopropenylbenzene, 1,4-divinylbenzene, 3-methyl-heptadiene-(1,5), 3-phenyl-hexadiene-(1,5), 3-vinyl-hexadiene-(1,5) and 4,5-dimethyl-4,5-diethyloctadiene-(1,7), N,N′-methylene-bisacrylamide, 1,1,1-tris(hydroxymethyl)propane triacrylate, 1,1,1-tris(hydroxymethyl)propane trimethacrylate, tripropylene glycol diacrylate, diallyl ether, diallylamine, diallyl carbonate, N,N′-diallylurea, triallylamine, tris(2-methylallyl)amine, 2,4,6-triallyloxy-1,3,5-triazine, triallyl-s-triazine-2,4,6(1H,3H,5H)-trione, diallyl malonate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, poly(propylene glycol)methacrylate.
[0051] Preferably, the silicon compositions according to the invention comprise, as constituent (A), at least one aliphatically unsaturated organosilicon compound, it being possible to use all of the aliphatically unsaturated organosilicon compounds used hitherto in addition-crosslinking compositions, such as, for example, silicone block copolymers with urea segments, silicone block copolymers with amide segments and/or imide segments and/or ester/amide segments and/or polystyrene segments and/or silarylene segments and/or carborane segments and silicone graft copolymers with ether groups.
[0052] The organosilicon compounds (A) that have SiC-bonded radicals with aliphatic carbon-carbon-multiple bonds used are preferably linear or branched organopolysiloxanes of units of the general formula (II)
[0000] R 4 a R 5 b SiO (4-a-b)/2 (II)
[0053] where
R 4 , independently of one another, are an organic or inorganic radical free from aliphatic carbon-carbon-multiple bonds, R 5 , independently of one another, are a monovalent, substituted or unsubstituted, SiC-bonded hydrocarbon radical with at least one aliphatic carbon-carbon-multiple bond, a is 0, 1, 2 or 3, and b is 0, 1 or 2, with the proviso that the sum a+b is less than or equal to 3 and at least 2 radicals R 5 are present per molecule.
[0059] Radicals R 4 may be mono- or polyvalent radicals, with the polyvalent radicals, such as, for example, bivalent, trivalent and tetravalent radicals, then joining together several, for example two, three or four, siloxy units of the formula (II).
[0060] Further examples of R 4 are the monovalent radicals —F, —Cl, —Br, OR 6 , —CN, —SCN, —NCO and SiC-bonded, substituted or unsubstituted hydrocarbon radicals which may be interrupted with oxygen atoms or the group —C(O)—, and also bivalent radicals Si-bonded on both sides according to formula (II). If radicals R 4 are SiC-bonded substituted hydrocarbon radicals, preferred substituents are halogen atoms, phosphorus-containing radicals, cyano radicals, —OR 6 , —NR 6 —, —NR 6 2 , —NR 6 —C(O)—NR 6 2 , —C(O)—NR 6 2 , —C(O)R 6 , —C(O)OR 6 , —SO 2 -Ph and —C 6 F 5 . Here, R 6 are, independently of one another, hydrogen or a monovalent hydrocarbon radicals having 1 to 20 carbon atoms, and Ph is the phenyl radical.
[0061] Examples of radicals R 4 are alkyl radicals such as the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and tert-pentyl radicals, hexyl radicals such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and isooctyl radicals such as the 2,2,4-trimethylpentyl radical, nonyl radicals such as the n-nonyl radical, decyl radicals such as the n-decyl radical, dodecyl radicals such as the n-dodecyl radical, and octadecyl radicals such as the n-octadecyl radical, cycloalkyl radicals such as the cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals, aryl radicals such as the phenyl, naphthyl, anthryl and phenanthryl radicals, alkaryl radicals such as the o-, m-, and p-tolyl radicals, xylyl radicals and ethylphenyl radicals, and aralkyl radicals such as the benzyl radical, and the α- and the β-phenylethyl radicals.
[0062] Examples of substituted radicals R 4 are haloalkyl radicals, such as the 3,3,3-trifluoro-n-propyl radical, the 2,2,2,2′,2′,2′-hexafluoroisopropyl radical, the heptafluoroisopropyl radical, haloaryl radicals, such as the o-, m- and p-chlorophenyl radical, —(CH 2 )—N(R 6 )C(O)NR 6 2 , —(CH 2 ) o —C(O)NR 6 2 , —(CH 2 ) o —C(O)R 6 , —(CH 2 ) o —C(O)OR 6 , —(CH 2 ) o —C(O)NR 6 2 , —(CH 2 )—C(O)—(CH 2 ) p C(O)CH 3 , —(CH 2 )—O—CO—R 6 , —(CH 2 )—NR 6 —(CH 2 ) p —NR 6 2 , —(CH 2 ) o —O—(CH 2 ) p CH (OH) CH 2 OH, —(CH 2 ) o (OCH 2 CH 2 ) p OR 6 , —(CH 2 ) o —SO 2 -Ph and —(CH 2 ) o —O—C 6 F 5 , where R 6 and Ph corresponds to the meaning given for them above and o and p are identical or different integers between 0 and 10.
[0063] Examples of R 4 being bivalent radicals Si-bonded on both sides according to formula (II) are those which are derived from the monovalent examples specified above for radical R 4 by virtue of the fact that an additional bonding takes place by substitution of a hydrogen atom. Examples of such radicals are —(CH 2 )—, —CH(CH 3 )—, —C(CH 3 ) 2 —, —CH(CH 3 )—CH 2 —, —C 6 H 4 —, —CH(Ph)—CH 2 —, —C(CF 3 ) 2 —, —(CH 2 ) o —C 6 H 4 —(CH 2 ) o —, —(CH 2 ) o —C 6 H 4 —C 6 H 4 —(CH 2 ) o —, —(CH 2 O) p , (CH 2 CH 2 O) o , —(CH 2 ) o —O x —C 6 H 4 —SO 2 —C 6 H 4 —O x —(CH 2 ) o —, where x is 0 or 1, and Ph, o and p have the meaning specified above.
[0064] Preferably, radical R 4 is a monovalent SiC-bonded, optionally substituted hydrocarbon radical having 1 to 18 carbon atoms free from aliphatic carbon-carbon-multiple bonds, more preferably a monovalent SiC-bonded hydrocarbon radical having 1 to 6 carbon atoms free from aliphatic carbon-carbon-multiple bonds, and in particular the methyl or phenyl radical.
[0065] Radical R 5 may be any desired groups accessible to an addition reaction (hydrosilylation) with an SiH-functional compound.
[0066] If radicals R 6 are SiC-bonded, substituted hydrocarbon radicals, the substituents are preferably halogen atoms, cyano radicals and —OR 6 , where R 6 has the aforementioned meaning.
[0067] Preferably, radicals R 5 are alkenyl and alkynyl groups having 2 to 16 carbon atoms, such as vinyl, allyl, methallyl, 1-propenyl, 5-hexenyl, ethynyl, butadienyl, hexadienyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, vinylcyclohexylethyl, divinylcyclohexylethyl, norbornenyl, vinylphenyl and styryl radicals, with vinyl, allyl and hexenyl radicals being most preferably used.
[0068] The molecular weight of the constituent (A) can vary within wide limits, for example between 10 2 and 10 6 g/mol. Thus, the constituent (A) can be, for example, a relatively low molecular weight alkenyl-functional oligosiloxane, such as 1,2-divinyltetramethyldisiloxane, but also a highly polymeric polydimethylsiloxane which has chain-positioned or terminal Si-bonded vinyl groups, e.g. with a molecular weight of 10 5 g/mol (number-average determined by means of NMR). The structure of the molecules forming the constituent (A) is also not fixed; in particular, the structure of a more highly molecular, i.e. oligomeric or polymeric siloxane, may be linear, cyclic, branched or else resin-like, network-like. Linear and cyclic polysiloxanes are preferably composed of units of the formulae R 4 3 SiO 1/2 , R 5 R 4 2 SiO 1/2 , R 5 R 4 SiO 1/2 and R 4 2 SiO 2/2 , where R 4 and R 5 have the meanings given above. Branched and network-like polysiloxanes additionally contain trifunctional and/or tetrafunctional units, with those of the formulae R 4 SiO 3/2 , R 5 SiO 3/2 and SiO 4/2 being preferred. Mixtures of different siloxanes satisfying the criteria of constituent (A) can of course also be used.
[0069] As component (A), particular preference is given to the use of vinyl-functional, essentially linear polydiorganosiloxanes with a viscosity of 0.01 to 500,000 Pa·s, more preferably from 0.1 to 100,000 Pa·s, in each case at 25° C.
[0070] As organosilicon compound(s) (B), it is possible to use all hydrogen-functional organosilicon compounds which have also hitherto been used in addition-crosslinkable compositions.
[0071] The organopolysiloxanes (B) that have Si-bonded hydrogen atoms are preferably linear, cyclic or branched organopolysiloxanes of units of the general formula (III)
[0000] R 4 c H d SiO (4-c-d)/2 (III)
[0072] where
R 4 has the aforementioned meaning, c is 0, 1, 2 or 3 and d 0, 1 or 2,
[0076] with the proviso that the sum of c+d is less than or equal to 3 and at least two Si-bonded hydrogen atoms are present per molecule.
[0077] Preferably, the organopolysiloxane (B) used according to the invention comprise Si-bonded hydrogen in the range from 0.04 to 1.7 percent by weight, based on the total weight of the organopolysiloxane (B).
[0078] The molecular weight of the constituent (B) can likewise vary within wide limits, for example between 10 2 and 10 6 g/mol. Thus, the constituent (B) can for example be a relatively low molecular weight SiH-functional oligosiloxane, such as tetramethyldisiloxane, but also a highly polymeric polydimethylsiloxane that has chain-positioned or terminal SiH-groups, or a silicone resin that has SiH-groups.
[0079] The structure of the molecules forming the constituent (B) is also not fixed; in particular, the structure of a more highly molecular, i.e. oligomeric or polymeric SiH-containing siloxane may be linear, cyclic, branched or else resin-like, network-like. Linear and cyclic polysiloxanes (B) are preferably composed of units of the formulae R 4 3 SiO 1/2 , HR 4 2 SiO 1/2 , HR 4 SiO 2/2 and R 4 2 SiO 2/2 , where R 4 has the meaning given above. Branched and network-like polysiloxanes additionally comprise trifunctional and/or tetrafunctional units, preference being given to those of the formulae R 4 SiO 3/2 , HSiO 3/2 and SiO 4/2 , where R 4 has the meaning given above.
[0080] It is of course also possible to use mixtures of different siloxanes meeting the criteria of constituent (B). In particular, the molecules forming the constituent (B) can optionally additionally also contain aliphatically unsaturated groups in addition to the obligatory SiH-groups. Particular preference is given to the use of low molecular weight SiH-functional compounds such as tetrakis(dimethylsiloxy)silane and tetramethylcyclotetrasiloxane, as well as more highly molecular, SiH-containing siloxanes, such as poly(hydrogenmethyl)siloxanes and poly(dimethylhydrogenmethyl)siloxanes with a viscosity at 25° C. of from 10 to 10,000 mPa·s, or analogous SiH-containing compounds in which some of the methyl groups are replaced by 3,3,3-trifluoropropyl or phenyl groups.
[0081] Constituent (B) is preferably present in the crosslinkable silicone compositions according to the invention in an amount such that the molar ratio of SiH-groups to aliphatically unsaturated groups from (A) is 0.1 to 20, more preferably between 1.0 and 5.0.
[0082] The components (A) and (B) used according to the invention are standard commercial products and/or can be prepared by processes customary in chemistry.
[0083] Instead of component (A) and (B), the silicone compositions according to the invention can comprise organopolysiloxanes (C) which simultaneously have aliphatic carbon-carbon-multiple bonds and Si-bonded hydrogen atoms. The silicone compositions according to the invention can also comprise all three components (A), (B) and (C).
[0084] If siloxanes (C) are used, these are preferably those of units of the general formulae (IV), (V) and (VI)
[0000] R 4 f SiO 4/2 (IV)
[0000] R 4 g R 5 SiO 3-g/2 (V)
[0000] R 4 h HSiO 3-h/2 (VI)
[0000] where
R 4 and R 5 have the meaning given for them above, f is 0, 1, 2 or 3, g is 0, 1 or 2 and h is 0, 1 or 2,
with the proviso that at least 2 radicals R 5 and at least 2 Si-bonded hydrogen atoms are present per molecule.
[0089] Examples of organopolysiloxanes (C) are those made from SO 4/2 , R 4 3 SiO 1/2 , R 4 2 R 5 SiO 1/2 and R 4 2 HSiO 1/2 units, so-called MP resins, where these resins can additionally contain R 4 SiO 3/2 and R 4 2 SiO units, as well as linear organopolysiloxanes essentially consisting of R 4 2 R 5 SiO 1/2 , R 4 2 SiO and R 4 HSiO units where R 4 and R 5 have the aforementioned meaning.
[0090] The organopolysiloxanes (C) preferably have an average viscosity of from 0.01 to 500,000 Pa·s, more preferably 0.1 to 100,000 Pa·s, in each case at 25° C. Organopolysiloxanes (C) can be prepared by methods customary in chemistry.
[0091] As hydrosilylation catalyst (D), it is possible to use all catalysts known to the prior art. Component (D) may be a platinum group metal, for example platinum, rhodium, ruthenium, palladium, osmium or iridium, an organometallic compound or a combination thereof. Examples of component (D) are compounds such as hexachloroplatinic(IV) acid, platinum dichloride, platinum acetylacetonate and complexes of these compounds which are encapsulated in a matrix or a core/shell-like structure.
[0092] Platinum complexes with low molecular weight organopolysiloxanes include 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complexes with platinum. Further examples are platinum phosphite complexes, platinum phosphine complexes or alkylplatinum complexes. These compounds may be encapsulated in a resin matrix.
[0093] To catalyze the hydrosilylation reaction of the components (A) and (B), the concentration of component (D) is sufficient upon activation in order to produce the heat required here in the described process. The amount of component (D) can be between 0.1 and 1000 parts per million (ppm), 0.5 and 100 ppm or 1 and 25 ppm of the platinum group metal, depending on the total weight of the component. The curing rate may be low if the constituent of the platinum group metal is below 1 ppm. The use of more than 100 ppm of the platinum group metal is uneconomical or can reduce the stability of the adhesive formulation.
[0094] In a further embodiment, the crosslinkable silicone compositions according to the invention can also be crosslinked peroxidically. In this case, the silicone composition consists at least of the components (A) and (H). In this connection, between 0.1 and 20% by weight of component (H) are preferably present in the silicone compositions according to the invention. As crosslinker in the context of component (H), it is possible to use all peroxides that are typical and correspond to the prior art. Examples of the component (H) are dialkyl peroxides, such as 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 1,1-di(tert-butylperoxy)cyclo-hexane, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclo-hexane, a-hydroxyperoxy-a′-hydroxydicyclohexyl peroxide, 3,6-dicyclohexylidene-1,2,4,5-tetroxane, di-tert-butyl peroxide, tert-butyl-tert-triptyl peroxide and tert-butyl-triethyl-5-methyl peroxide, diaralkyl peroxides such as dicumyl peroxide, alkylaralkyl peroxides such as tert-butylcumyl peroxide and a,a′-di(tert-butylperoxy)-m/p-diisopropylbenzene, alkylacyl peroxides, such as t-butyl perbenzoate, and diacyl peroxides, such as dibenzoyl peroxide, bis(2-methylbenzoyl peroxide), bis(4-methylbenzoyl peroxide) and bis(2,4-dichlorobenzoyl peroxide). Preference is given to using vinyl-specific peroxides, the most important representatives of which are the dialkyl and diaralkyl peroxides. Particular preference is given to using 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and dicumyl peroxide. It is also possible to use individual peroxides or mixtures of different peroxides (H). The content of constituent (H) in the silicone compositions according to the invention is preferably between 0.1 and 5.0% by weight, more preferably between 0.5 and 1.5% by weight. Preference is therefore given to the crosslinkable silicone compositions according to the invention characterized in that the crosslinker (H) is present from 0.1 to 5.0% by weight and is an organic peroxide or a mixture of organic peroxides.
[0095] In a further embodiment, the crosslinkable silicone compositions according to the invention can also be crosslinked by adding component(X) to condensation-crosslinking silicone compositions. Condensation-crosslinking silicone compositions have been known to the person skilled in the art for a long time. A more detailed description can be found, for example, in EP0787766A1.
[0096] All of the peroxide-, addition- and condensation-crosslinking silicone compositions according to the invention described above can optionally comprise strengthening fillers, as a component (E), such as fumed or precipitated silicas with BET surface areas of at least 50 m 2 /g, as well as carbon blacks and activated carbons such as furnace black and acetylene black, with preference being given to fumed and precipitated silicas with BET surface areas of at least 50 m 2 /g. The specified silica fillers can have a hydrophilic character or be hydrophobicized by known processes. The content of actively strengthening filler (E) in the crosslinkable composition according to the invention is in the range from 0 to 70% by weight, preferably 0 to 50% by weight.
[0097] Preferably, the crosslinkable silicone compositions according to the invention are characterized in that the filler (E) has been surface-treated. The surface treatment is achieved by processes known in the prior art for the hydrophobicization of finely divided fillers. The hydrophobicization can take place, for example, either prior to the incorporation into the polyorganosiloxane or else in the presence of a polyorganosiloxane according to the in situ process. Both processes can be carried out either in the batch process or else continuously. Hydrophobicizing agents preferably used are organosilicon compounds which are able to react with the filler surface to form covalent bonds or are permanently physisorbed onto the filler surface. Examples of hydrophobicizing agents are alkylchlorosilanes such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, octyltrichlorosilane, octadecyltrichlorosilane, octylmethyldichlorosilane, octadecylmethyldichlorosilane, octyldimethylchlorosilane, octadecyldimethylchlorosilane and tert-butyldimethylchlorosilane; alkylalkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane and trimethylethoxysilane; trimethylsilanol; cyclic diorgano(poly)siloxanes such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane; linear diorganopolysiloxanes such as dimethylpolysiloxanes with trimethylsiloxy end groups, and dimethylpolysiloxanes with silanol or alkoxy end groups; disilazanes such as hexaalkyldisilazanes, in particular hexamethyldisilazane, divinyltetramethyldisilazane, bis(trifluoropropyl)tetramethyldisilazane; cyclic dimethylsilazanes, such as hexamethylcyclotrisilazane. It is also possible to use mixtures of the hydrophobicizing agents specified above. In order to increase the rate of the hydrophobicization, catalytically active additives, such as, for example, amines, metal hydroxides and water, can also optionally be added.
[0098] The hydrophobicization can take place, for example, in one step using one hydrophobicizing agent or a mixture of several hydrophobicizing agents, but also using one or more hydrophobicizing agents in several steps.
[0099] As a consequence of a surface treatment, preferred fillers (E) have a carbon content of at least 0.01 to at most 20% by weight, preferably between 0.1 and 10% by weight, and more preferably between 0.5 to 5% by weight. Particular preference is given to crosslinkable silicone compositions which are characterized in that the filler (E) is a surface-treated silica having 0.01 to 2% by weight of Si-bonded, aliphatically unsaturated groups. For example, these may be Si-bonded vinyl groups. In the silicone composition according to the invention, the constituent (E) is used preferably as an individual filler or likewise preferably as a mixture of several finely divided fillers.
[0100] The silicone compositions according to the invention can, if desired, comprise as constituents further additives (F) in a fraction of up to 70% by weight, preferably 0.0001 to 40% by weight. These additives (F) may be e.g. inactive fillers, resin-like polyorganosiloxanes which are different from the siloxanes (A), (B), (C), (E) and (X), fungicides, fragrances, rheological additives, inhibitors and stabilizers for the targeted adjustment of processing time, onset temperature and crosslinking rate, corrosion inhibitors, oxidation inhibitors, light protection agents, flame retardants and agents for influencing the electrical properties, dispersion auxiliaries, solvents, adhesion promoters, pigments, dyes, plasticizers, organic polymers, heat stabilizers etc. These include additives such as quartz flour, diatomaceous earth, clays, chalk, lithopone, graphite, metal oxides, metal carbonates, metal sulfates, metal salts of carboxylic acids, metal dusts, fibers, such as glass fibers, plastic fibers, plastic powders, metal dusts, dyes, pigments etc.
[0101] Moreover, these fillers may be heat-conducting or electrically conducting. Examples of heat-conducting fillers are aluminum nitride; aluminum oxide; barium titanate; beryllium oxide; boron nitride; diamond; graphite; magnesium oxide; particulate metals such as, copper, gold, nickel or silver; silicon carbide; tungsten carbide; zinc oxide, and combinations thereof. Heat-conducting fillers are known in the prior art and are commercially available. For example, CB-A20S and Al-43-Me are aluminum oxide fillers in different particle sizes which are commercially available from Showa-Denko, and AA-04, AA-2 and AA18 are aluminum oxide fillers which are commercially available from Sumitomo Chemical Company. Silver fillers are commercially available from Metalor Technologies U.S.A. Corp. of Attleboro, Mass., U.S.A. Boron nitride fillers are commercially available from Advanced Ceramics Corporation, Cleveland, Ohio, U.S.A. It is also possible to use a combination of fillers with different particle sizes and different particle size distribution.
[0102] Inhibitors and stabilizers serve for the targeted adjustment of the processing time, onset temperature and crosslinking rate of the silicone compositions according to the invention. These inhibitors and stabilizers have been known for a long time in the prior art. Examples of customary inhibitors are acetylenic alcohols, such as 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol and 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-dodecyn-3-ol, polymethylvinylcyclosiloxanes such as 1,3,5, 7-tetravinyltetramethyltetracyclosiloxane, low molecular weight silicone oils with methylvinyl-SiO 1/2 groups and/or R 2 vinylSiO 1/2 end groups, such as divinyltetramethyldisiloxane, tetravinyldimethyldisiloxane, trialkyl cyanurates, alkyl maleates, such as diallyl maleates, dimethyl maleate and diethyl maleate, alkyl fumarates, such as diallyl fumarate and diethylfumarate, organic hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide and pinane hydroperoxide, organic peroxides, organic sulfoxides, organic amines, diamines and amides, phosphates and phosphites, nitriles, triazoles, diaziridines and oximes. The effect of these inhibitor additives (F) depends on their chemical structure, meaning that the concentration has to be determined individually. Inhibitors and inhibitor mixtures are preferably added in a quantitative fraction of from 0.00001% to 5%, based on the total weight of the mixture, preferably 0.00005 to 2% and more preferably 0.0001 to 1%.
[0103] The silicone composition can additionally optionally comprise a solvent (G). However, it should be ensured that the solvent (G) has no disadvantageous effects on the overall system. Suitable solvents (G) are known in the prior art and are commercially available. The solvent (G) can be, for example, an organic solvent having 3 to 20 carbon atoms. Non-limiting examples of solvents (G) include aliphatic hydrocarbons such as nonane, decalin and dodecane; aromatic hydrocarbons such as mesitylene, xylene and toluene; esters such as ethyl acetate and butyrolactone; ethers such as n-butyl ether and polyethylene glycol monomethyl ether; ketones such as methyl isobutyl ketone and methyl pentyl ketone; silicone fluids such as linear, branched and cyclic polydimethylsiloxanes, and combinations of these solvents. The optimum concentration of a specific solvent (G) in the silicone composition can be determined easily by means of routine experiments. Depending on the weight of the compound, the amount of solvent (G) can be between 0 and 95% or between 1 and 95%.
[0104] The crosslinkable silicone compositions according to the invention have the advantage that they can be prepared in a simple process using readily accessible starting materials and therefore in an economical manner. The crosslinkable silicone compositions according to the invention have the further advantage that they have good storage stability, even as a single-component formulation, at 25° C. and ambient pressure, and rapidly crosslink only at elevated temperature. The silicone compositions according to the invention have the advantage that, in the case of a two-component formulation, they produce, after mixing the two components, a crosslinkable silicone mass, the processability of which is retained over a long period at 25° C. and ambient pressure, i.e. exhibit extremely long pot life, and rapidly crosslink only at elevated temperature.
[0105] By means of processes known in the prior art, the silicone rubbers according to the invention are produced by crosslinking the silicone compositions according to the invention. Silicone rubbers that can be produced for medical products are, for example, face masks, valves, hoses, catheters, lining materials, bandages, prostheses, dressing materials. The medical products produced in this way have a long-lasting suppression of the occupation of their surfaces by bacteria and consequently a significantly reduced risk of infection for the patient during their use.
EXAMPLES
[0106] In the examples described below, all of the data for parts and percentages are based on weight, unless stated otherwise. Unless stated otherwise, the examples below are carried out at a pressure of the ambient atmosphere, i.e. at about 1000 hPa, and at room temperature, i.e. at about 20° C., or at a temperature which is established upon combining the reactants at room temperature without additional heating or cooling. Hereinbelow, all of the viscosity data refer to a temperature of 25° C. The examples below illustrate the invention without having a limiting effect.
[0107] The following abbreviations are used:
Cat. platinum catalyst Ex. example No. number PDMS polydimethylsiloxane LSR liquid silicone rubber HTC high-temperature-crosslinking % by weight percent by weight, w/w M unit monofunctional siloxane radical, R 3 SiO 1/2 D unit difunctional siloxane radical, R 2 SiO 2/2 T unit trifunctional siloxane radical, R 3 SiO 3/2 Q unit tetrafunctional siloxane radical, SiO 4/2
where R is an organic radical.
Example 1
Synthesis of the compound (X):
[0119] One possible synthesis route for incorporating functional groups which permit a bonding to the PDMS network is the equilibration reaction of suitable precursors that is widespread in silicone chemistry. This type of bonding constitutes, by way of example, one option to produce the compound (X) and should not have a limiting effect on the scope of protection of the application since the synthesis route exhibits no influence on the effectiveness.
[0120] Stage 1:
[0121] Preparation of an α,ω-succinic anhydride-functional silicone by hydrosilylation of 2-allylsuccinic anhydride and an α,ω-Si—H-terminal polydimethylsiloxane with an average chain length of 50 D units: under precious metal catalysis (metals of the platinum group, preference being given to platinum compounds), the reaction of the H-terminal silicone polymer with 2-allylsuccinic anhydride takes place preferably at about 90-110° C. The synthesis takes place with equimolar feed based on the functional groups (Si—H and allyl). An excess or deficit of the individual reactants is likewise possible.
[0122] Stage 2:
[0123] Functionalization for the bonding to silicone elastomers: the product from stage 1 is reacted with an Si-vinyl-functional polymer with the help of the equilibration reaction, where the vinyl-functional polymer can carry both chain-position and terminal vinyl groups. The molar ratio of the two starting materials can be selected between 1:100 to 100:1, where preferably a ratio between 1:20 to 5:1 and particularly preferably a ratio between 1:10 and 2:1 is selected. The equilibration itself can be carried out by all methods known in the prior art, such as, for example, acid- or base-catalyzed equilibration or using phosphazenes. For this example, 0.45 mol of α,ω-succinic anhydride-functional silicone is equilibrated with 4.5 mol of divinyldisiloxane with the help of a phosphazene with the average molecular formula PNCl 2 . After heating the mixture to 100° C. to 120° C., 400 ppm of equilibration catalyst (based on the total weight of the reactants) are added in two tranches of 200 ppm each. After stirring for two hours, the catalyst is quenched by adding divinyltetramethyldisilazane, and volatile constituents are removed by applying oil pump vacuum.
Example 2
Synthesis of the compound (X):
[0124] Stage 1: Preparation of an α,ω-functional silicone by hydrosilylation of acrylic acid trimethylsilyl ester (propenoic acid trimethylsilyl ester) and an α,ω-Si—H-terminal polydimethylsiloxane with an average chain length of 50 D units: under precious metal catalysis (Pt metals), the reaction of the H-terminal silicone polymer with acrylic acid trimethylsilyl ester takes place preferably at about 90-110° C. The synthesis takes place with equimolar feed based on the functional groups (Si—H and vinyl). An excess or deficit of the individual reactants is likewise possible.
[0125] Stage 2: Functionalization for the bonding to silicone elastomers analogously to example 1, where the ratio of carboxylic acid ester groups:vinyl groups=1:5.
Example 3
Synthesis of the compound (X):
[0126] Proceeding from undecenoic acid triisopropylsilyl ester, the compound (X) is prepared analogously to example 1, where, in stage 2, the ratio of carboxylic acid ester groups:vinyl groups=1:2.
Example C4 (Comparative Example)
[0127] Silicone base composition 1 (LSR silicone): commercially available LSR mixture ELASTOSIL® 3003/40 A/B. The crosslinking of the material takes place by compression at 165° C. for 10 min.
Example 5
[0128] Compound (X) and additional Si—H crosslinker is added to the commercially available LSR mixture ELASTOSIL® 3003/40 A/B from example 4. By incorporating the vinyl groups from compound (X), a balancing of the functional groups is required, for which reason a linear Si—H comb crosslinker with an Si—H content of 4.8 mmol of Si—H per gram is added, where the additionally added amount of Si—H corresponds approximately to the amount of vinyl groups from compound (X) (molar calculation). The crosslinking of the material takes place by compression at 165° C. for 10 min.
[0129] In table 1, different compounds (X) at various added amounts are varied and the results are shown.
Example C6 (Comparative Example)
[0130] Silicone base composition 2 (HTC silicone): commercially available, peroxidically crosslinking HTC mixture ELASTOSIL® 401/60 C6. The crosslinking of the material takes place by compression at 165° C. for 10 min, then the material is heated at 200° C. for 4 hours.
Example 7
[0131] Compound (X) is compounded into the commercially available, peroxidically crosslinking HTC mixture ELASTOSIL® R 401/60 C6. The crosslinking of the material takes place by compression at 165° C. for 10 min, then the material is heated at 200° C. for 4 hours. In table 1, different compounds (X) at various added amounts are varied and the results are shown.
Example C8 (Comparative Example)
[0132] Silicone base composition 3 (RTC-2-silicone): commercially available, addition-crosslinking RTC-2 mixture SILPURAN. The crosslinking of the material takes place by heating at 50° C. for 1 h.
Example 9
[0133] Compound (X) is mixed into the commercially available, addition-crosslinking RTC-2 mixture SILPURAN® 2420 A/B. By incorporating the vinyl groups from compound (X), a balancing of the functional groups is required, for which reason HD cyclic (primarily HD5 and HD6) are added, where the additionally added amount of Si—H corresponds approximately to the amount of vinyl groups from compound (X) (molar calculation). The crosslinking of the material takes place by heating to 50° C. for 1 h. In table 1, different compounds 1 at various added amounts are varied and the results are shown.
[0134] Test Method
[0135] As a result of the covalent bonding of the acid or acid ester groups to the PDMS matrix, test methods based on the diffusion of active substances are unsuitable for characterizing the surface (agar diffusion test or inhibitory zone test). On account of the manifold application options of antimicrobially equipped products, there is hitherto no national or international standard for the testing of products. The behavior of the crosslinked silicone rubber, however, should be tested as far as possible under conditions simulating those encountered in practice, for which reason the effectiveness tests on the occupation of the surface were carried out in accordance with the Japanese standard JIS Z 2801:2000. In this, bacteria are applied in a nutrient solution to the material under investigation and incubated. Following inoculation of the samples, a thin film is pressed on to the inoculum such that the bacteria suspension is spread on the test piece in the thinnest possible layer and consequently the activity of the surface can be tested. The specific effect is based on the difference in germ counts between a sample to which compound (X) has been added and the blank sample which consists of the same base material (without additive thus without compound (X)). The effectiveness of antimicrobial surfaces is defined via the germ reduction achieved within the contact time and is given in log stages. One log stage corresponds to the reduction of the germs by one power of ten (log10). The stated number of bacteria refers to the evaluation of the test by counting.
[0000]
TABLE 1
Carboxyl
equivalents
Silicone
from compound
Rounded
Ex.
from
(X) [mmol/g]/as
Number of
reduction
No.
Ex. No.
per Ex. No.
bacteria
[log10]
10
C4*
—
2*10 6
Blank sample
11
5
0.01/1
1*10 6
0
12
5
0.05/1
2*10 6
0
13
5
0.1/1
0
6
14
5
0.2/1
0
6
15
5
0.5/1
0
6
16
5
1/1
0
6
17
5
0.01/2
1*10 5
1
18
5
0.05/2
1*10 3
3
19
5
0.1/2
1*10 3
3
20
5
0.2/2
0
6
21
5
0.5/2
0
6
22
5
0.01/3
1*10 6
0
23
5
0.05/3
1*10 6
0
24
5
0.1/3
0
6
25
5
0.5/3
0
6
26
C6*
—
1*10 6
Blank sample
27
7
0.01/1
1.2*10 6
0
28
7
0.05/1
2*10 2
4
29
7
0.1/1
0
6
30
7
0.5/1
0
6
31
7
0.01/2
1*10 5
1
32
7
0.05/2
1*10 3
3
33
7
0.1/2
0
3
34
7
0.5/2
0
6
35
7
0.01/3
1*10 6
0
36
7
0.05/3
1*10 6
0
37
7
0.1/3
0
6
38
7
0.5/3
0
6
39
C8*
—
1.5*10 6
Blank sample
40
9
0.01/1
1.2*10 6
0
41
9
0.05/1
6*10 5
0
42
9
0.1/1
0
2
43
9
0.5/1
0
6
44
9
0.01/2
1*10 6
0
45
9
0.05/2
2*10 3
3
46
9
0.1/2
0
3
47
9
0.5/2
0
6
48
9
0.01/3
1*10 6
0
49
9
0.05/3
3*10 4
2
50
9
0.1/3
0
6
51
9
0.5/3
0
6
*not according to the invention
Example 52
Synthesis of the Compound (X)
[0136] Stage 1:
[0137] Preparation of a chain-positioned, succinic anhydride-functional silicone by hydrosilylation of 1,1,1,3,5,5,5-heptamethylsilane with allylsuccinic anhydride, preferably at about 90-110° C. The synthesis takes place with equimolar feed based on the functional groups Si—H and allyl. An excess or deficit of the individual reactants is likewise possible. Following the reaction, a purification, for example by distillation, of the reaction product can be performed.
[0138] Stage 2:
[0139] Functionalization for the bonding to silicone elastomers: the product from stage 1 is reacted with a 1,1,3,3-tetramethyl-1,3-divinyldisiloxane with the help of the equilibration reaction. The molar ratio between 1,1,3,3-tetramethyl-1,3-divinyldisiloxane and the reaction product from stage 1 is at least 2, preferably at least 3. The temperature of the solution must be no more than 138° C. During the equilibration, the products hexamethyldisiloxane and 1,1,2,2,2-pentamethyl-1-vinyldisiloxane are formed and are removed from the mixture during the reaction via the top of the column in order to shift the equilibrium in the direction of the divinyl-functionalized species. The reaction product consists at the end of the reaction of preferably at least 90% divinyl-functionalized monomers: 3-(3-(1,1,3,5,5-pentamethyl-1,5-divinyltrisiloxane-3-yl)propyl)dihydrofuran-2,5-dione. An enrichment of the anhydride-functionalized D-group can take place during the equilibration reaction, although this is unimportant for the intended use. In a preferred embodiment, purification takes place by means of distillation. The equilibration catalyst used is the catalyst with the average molecular formula PNCl 2 used in the examples hitherto.
Example 53
Synthesis of the Compound (X)
[0140] Introduction of D units into the product from example 52 by equilibration with an α,ω-vinyl-functional polydimethylsiloxane. The chain length of the polydimethylsiloxane used is selected such that the desired number of D groups is incorporated statistically into compound (X). In example 53, the product from example 52 is equilibrated in a ratio of 1:4 with an α,ω-vinyl-functional polydimethylsiloxane with an average chain length of 200 units. The result of this reaction is an inventive α,ω-vinyl-functional polydimethylsiloxane modified in the side position with one or more propyldihydrofuran-2,5-dione groups.
|
Silicone elastomers exhibiting non-transitory biofilm inhibiting properties are prepared from crosslinkable components which include an organopolysiloxane bearing at least one silicon-bonded hydrogen and/or at least one alkenyl group, and at least one carboxylic acid, carboxylic acid ester, or carboxylic acid anhydride group, which becomes covalently bonded to the polymer before or during curing.
| 2
|
[0001] This application claims the benefit of priority of U.S. Provisional Patent Application U.S. Ser. No. 62/300,385 filed Feb. 26, 2016, the specification and drawings thereof being incorporated by reference herein in their entirety.
FIELD OF THE INVENTION
[0002] This invention relates to the field of biodegradable laminates, processes, and uses.
BACKGROUND OF THE INVENTION
[0003] Single use disposable containers are ubiquitous in North America. One kind of single use container employs a liquid barrier layer in the form of a coating placed on a paper cardstock. Although such containers may be intended to be recyclable or biodegradable, this is not always the case in practice.
SUMMARY OF THE INVENTION
[0004] In an aspect of the invention there is a card stock laminate. It has a first layer and a second layer. The first layer is a lignocellulosic web. The second layer is a thermoplastic aliphatic polyester applied to the lignocellulosic web. The first layer has a binder. The binder is non-toxic and water soluble.
[0005] In a feature of that aspect of the invention, the lignocellulosic web is formed from a non-wood material. In another feature, the lignocellulosic material is formed from an agricultural plant waste product. In still another feature, the lignocellulosic material is chosen from the set of lignocellulosic materials consisting of: (a) non-staining fruit rinds; (b) non-staining nut rinds; and (c) grain husks. In a further feature, the lignocellulosic web is made at least predominantly of sunflower seed shells.
[0006] In another feature of the invention, the binder is chosen from (a) a protein glue; and (b) a polysaccharide. In a particular embodiment, the binder is a polysaccharide. In another feature, the binder is a vegetable oil-based gum. In another feature, the binder is a starch. In still another feature, the binder is a xanthan gum.
[0007] In yet another feature, the laminate has a thickness of greater than 0.25 mm (0.010 inches). In a further feature, the laminate if formed into the shape of a liquid containment vessel, the liquid containment vessel having an inside surface, and the liquid containment vessel has the thermoplastic aliphatic polyester applied to the inside surface. In another feature, the liquid containment vessel is a drinking cup. In another feature, the web is free of clays. In another feature, the first layer is made of a sunflower paper cardstock, the second layer is a thermoplastic aliphatic polyester applied to the sunflower paper cardstock, and the binder includes xanthan gum.
[0008] In another aspect of the invention there is a method of making a laminate card stock. The method includes converting an agricultural plant product waste to a paper-making input feedstock; mixing the feedstock with a binder, the binder being non-toxic and water-soluble; producing a slurry of the input feedstock and the binder; at least partially drying the slurry to produce a first web; and applying a thermoplastic aliphatic polyester to one side of the first web.
[0009] In a feature of that aspect of the invention, the method includes choosing the plant product waste to include at least one of: corn husks; corn stalks; chaff of any of wheat, oats, canola and barley; non-staining seed shells; straw; non-staining nut shells and husks. in another feature, the method includes choosing the binder to include at least one of (a) a protein; and (b) a polysaccharide. In still another feature, the method includes choosing the agricultural waste to include sunflower seeds shells. In yet another feature, the method includes choosing the binder to include a xanthate gum.
[0010] In still another feature, the method includes grinding the agricultural plant product waste to a powder. In a further feature, the method includes mixing a bleach with the slurry. In another feature, the bleach is less than ¼% by weight of the slurry. In yet another feature, the method includes forming the slurry on a screen and extracting moisture therefrom to form the first web. In still yet another feature, the method includes applying the thermoplastic aliphatic polyester to the first web while the web is moist.
[0011] In a further feature, the agricultural waste product is at least predominantly sunflower seed husks; the binder is a xanthate gum; the step of converting includes grinding the sunflower seed husks into a powder; the step of at least partially drying the slurry includes forming the slurry into a web and extracting moisture therefrom; and the thermoplastic aliphatic polyester is applied to one side of the web while the first web is moist. In another feature, the method includes forming the first web into a vessel and applying the thermoplastic aliphatic polyester to an inside surface of the vessel. In yet another feature, the first web if formed to a thickness of at least 0.25 mm thick (0.010 inches). In still another feature, the method includes forming the laminate into a paper cup.
[0012] In another aspect of the invention there is a cardstock that has a sunflower shell web with a thermoplastic aliphatic polyester coating applied to at least one side thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] These aspects and other features of the invention can be understood with the aid of the following illustrations of a number of exemplary, and non-limiting, embodiments of the principles of the invention in which:
[0014] FIG. 1 shows a side view of a container;
[0015] FIG. 2 shows a top view of the container of FIG. 1 ;
[0016] FIG. 3 is a sectional view of the wall structure of the container of FIG. 1 ;
DETAILED DESCRIPTION
[0017] The description that follows, and the embodiments described therein, are provided by way of illustration of an example, or examples, of particular embodiments of the principles of the present invention. These examples are provided for the purposes of explanation, and not of limitation, of those principles and of the invention. In the description, like parts are marked throughout the specification and the drawings with the same respective reference numerals. The drawings may be understood to be to scale and in proportion unless otherwise noted. The wording used herein is intended to include both singular and plural where such would be understood, and to include synonyms or analogous terminology to the terminology used, and to include equivalents thereof in English or in any language into which this specification may be translated, without being limited to specific words or phrases. “The term “polysaccharide” as used herein, is a broad term and is used in its ordinary sense, including, without limitation, saccharides having a plurality of repeating units, including, but not limited to polysaccharides having 50 or more repeat units, and oligosaccharides having 50 or less repeating units. Typically, polysaccharides have from about 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 repeating units to about 2,000 or more repeating units, and preferably from about 100, 150, 200, 250, 300, 350, 400, 500, 600, 700, 800, 900 or 1000 repeating units to about, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, or 1900 repeating units. Oligosaccharides typically have from about 6, 7, 8, 9, or 10 repeating units to about 15, 20, 25, 30, or 35 to about 40 or 45 repeating units.
[0018] Referring to FIGS. 1 and 2 , a containment vessel for holding liquids is identified generally as 20 . Containment vessel 20 has a generally upstanding sidewall 22 and a base 24 upon which it may sit on a supporting surface. Sidewall 24 may be tapered upwardly and outwardly in the manner of a cup. It may have an upper rim, as at 26 , and a bottom panel 28 . Bottom wall 28 and sidewall 22 co-operate to define a chamber, indicated generally as 30 , for containing liquids.
[0019] Containment vessel 20 is intended to be generic. That is, while it may have the general shape of a cup, the container could have a square or rectangular base, and could be straight sided. It could have a top, or cover, or lid, and it could have the shape of a folded carton, whether a milk carton or a folded rectangular cubic drink box, or juice box, or box for soup, and so on. Alternatively it could have the shape of a shallow container, such as a wide bowl or paper plate. In each case, the structure is intended to define a continuous geometric surface or shell such as may be used to contain a liquid, or to deter the migration of a liquid.
[0020] FIG. 3 shows a cross-section of a portion of upstanding wall 22 , or of bottom wall 28 . The thicknesses have been greatly exaggerated for the purposes of illustration. As can be seen, the wall structure is made of a sheet stock, or web, having a first layer indicated as 32 , and a second layer indicated as 34 . Rim 26 defines the periphery of an opening 36 through which materials may be placed in or withdrawn from chamber 30 . Such materials may be liquids, or materials from which liquids may tend to seep or drip.
[0021] First layer 32 may be the primary layer, or substrate of the web stock 40 . It may be a form of paper, or cardboard, or card stock, that is formed predominantly, or substantially entirely of a base material that is a lignocellulosic material. The materials are also water absorbent. In particular, the lignocellulosic material may be an unused discard, or waste, or by-product of an agricultural activity. In this specification, agricultural activities include food processing or food preparation or food serving processes or products or activities. These activities may include such processes as removing shells from seed or nuts, or husks from corn. Sunflower seed shells or husks are such a material. There are some agricultural products that may be avoided. For example, such materials as considered for use herein are non-toxic. In some embodiments it may be that materials tending to yield strong dyes, or stains, may be avoided, as may materials tending to have strongly undesirable colours. Although natural colouring may be applied to the as finished product, or may be mixed with the base material during processing, typical materials may be chosen that have a subdued, pale, or pastel colour, such as a gray, or beige, or light brown, and so on. Alternate materials may include pumpkin hulls (though they may be more prone to allergies than sunflowers), almonds and other seed hulls or nut shells that are fairly soft and high in cellulose. It may be desirable to avoid materials that may commonly cause allergic reactions.
[0022] The producers of waste agricultural or food processing materials may tend to view those materials as a cost, in terms of disposal. However, using a waste materials from such a process may be desired as it may solve a disposal problem for the first user, and provide economical feedstock for the cardstock producer. A further desirable feature may be the re-usability of the material. A still further desirable feature may be that such materials may be suitable for subsequent re-processing. Further, agricultural by-product feedstocks, being by definition organic, may be biodegradable or suitable for composting.
[0023] The base material of the card stock may be processed into small particulate, where “small” my be understood to be of a size to make a pulp or powder. The materials may be ground into a dry powder or may be processed mechanically into a pulp. The base material, once rendered into a fine form, may be stored until ready for use. A small amount of bleach may be added to discourage the growth of molds. In this context, “small” may be defined as less than 1/10of 1% by weight, where the bleach is, typically, common household bleach containing between 3-8% sodium hypochlorite and 0.01% to 0.05% sodium hydroxide.
[0024] A binder may be added to the base material. The binder may have the form of a resin. The binder may be a water-soluble binder. It may be a protein, such as a casein glue. Alternatively it may be a polysaccharide. It may by a carbohydrate. It may be a starch. In one embodiment it may be a gum, such as a xanthate, one of which is xanthan gum. As with the base material, the binder may be, or may be derived from, a discarded material, such as may be a by-product or discard of an agricultural or food processing activity. Casein glues are such a material. Polysaccharides may be obtained from many kinds of agricultural plant waste. A typical source material for polysaccharides may be a vegetable oil, e.g., a corn oil.
[0025] The base material and binder may be mixed with water to form a slurry in a bath, or receptacle or tub. When the slurry is evenly mixed, and smooth, it may be extracted from the bath on a screen. The extracted material may then be dried to extract the moisture, and to leave a wafer, or layer, or membrane that, when dried forms a coherent sheet. Although clays and other materials may be used, in some embodiments the card stock paper may be free of such clays. Further, the card stock paper may be calendared, i.e., passed between rollers to yield a smooth finish. In some instances the card stock may be subsequently pressed into a shaped by a form or mold. Such forming may occur while the card stock is partially moist.
[0026] Second layer 34 may be a water-retaining coating, or water barrier coating, or moisture barrier coating, or water impermeable coating, or water-proof coating, however it may be termed, and may be much thinner than the main substrate. That is, the coating layer may be of the order of less than 2 mils thick. Thicker coatings may be applied. However it may be that extra thickness may not be required. The coating may be in the nature of a PLA plastic, namely a thermoplastic aliphatic polyester with a temperature for use above the boiling temperature of water. Such PLA plastics may themselves be by-products or discarded waste of agricultural or food processing activities. That is, a common source of PLA feedstock is corn starch. Corn starch tends to be readily available in North America, and there are commercial manufacturers of PLA. A typical PLA plastic may have a melting temperature in the range of 173-178 C, which is well above the customary temperature range for serving beverages and foodstuffs, such as coffee, tea, or soup.
[0027] The PLA may be applied to the card stock either before or after forming of the card stock into the shape of a containment vessel. It may be applied by spraying, or by mechanical application, or by printing, whether on the card stock in a traditional manner, or by 3-D printing on the surface of the already-formed object. The PLA may be applied to the card stock structure while that structure is still moist. Subsequent drying may yield the laminate structure of FIG. 3 . In addition to PLA, other materials we could use for the plastic are PDLA, biodegradable polylactide aliphatic copolymer (CPLA) and other bioplastics. PLA may tend to be biodegradable, and may degrade in 45 to 90 days, depending on the temperature. It may take less time in an industrial composter, and more time, perhaps as much as 6 months, if put in a backyard composter. PLA may tend not to need sunlight to biodegrade, although sunlight, may improve the speed of the breakdown. PLA may tend to need air to biodegrade more rapidly. That is, it may take 4 to 6 years to decompose in a landfill that is relatively airtight.
[0028] Where the card stock is formed into a liquid containment vessel, the PLA may be applied to one side of the structure. PLA could be applied to both sides of the structure if desired. It may typically be that application to one side—i.e., the inside of a cup or carton or bowl—will establish the desired waterproof qualities. The plastic coating is very thin, and, as such, provides little by way of resistance to heat transfer. The paper or card stock substrate may be a more effective thermal insulator. The paper or card-stock also provides structural stiffness by which the walls of the container or containment structure maintain their form when full, and when warmed by the contents.
[0029] The embodiments illustrated and described above illustrate individual non-limiting examples in which the principles of the present invention are employed. It is possible to make other embodiments that employ the principles of the invention and that fall within the following claims. To the extent that the features of those examples are not mutually exclusive of each other, the features of the various embodiments may be mixed-and-matched, i.e., combined, in such manner as may be appropriate, without having to resort to repetitive description of those features in respect of each possible combination or permutation. The invention is not limited to the specific examples or details which are given by way of illustration herein, but only by the claims, as mandated by law. The claims are to be given the benefit of purposive interpretation to include equivalents under the doctrine of equivalents.
[0030] Although the various embodiments have been illustrated and described herein, the principles of the present invention are not limited to these specific examples which are given by way of illustration, but only by a purposive reading of the claims.
|
A paper, or cardboard, or card stock material is made from an organic material, such as ground-up sunflower seeds using an organic binder, such as a glue, which may have the form of a polysaccharide e.g., a long chain naturally occurring sugar. A water resistant, or water impermeable coating, such as a PLA coating, is applied to one or both sides of the card stock to form a laminate. The card stock may be formed into a shape or structure, such as a carton, or bowl, or cup, either prior to or after coating. The card stock material or the primary layer, the binder, and the plastic coating are all based on materials that are typically considered to be waste by-products of agricultural or food services processing, and they are all materials that may tend to be suitable for composting or biodegradation.
| 2
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to paperboard food packages. Such structures of this type, generally, have lids which can be sealed to the food package without the use of adhesives.
1. Description of the Related Art
One or two serving portions of precooked and/or frozen food are frequently packaged for consumer distribution in paperboard trays. Such trays are folded or pressed from preprinted and die-cut bleached sulphate paperboard blanks or sheets.
Covers for these paperboard trays may take one of several forms including a top flap that is an integral continuation of the same paperboard sheet from which the tray is erected, such a top flap being crease hinged to one sidewall of the tray. Another type of lid is an independent paperboard sheet that is adhesively secured or plastic fuse bonded to a small perimeter flange folded from the upper edge of the tray sidewalls.
As additional factors to the present invention's prior art and development, it should be understood that a typical commercial food tray filling line advances at a rate of 60 to 120 units per minute. Consequently, any step or process in the continuous production line that requires a full stop of the subject unit must be accomplished in one second or less. Other processing steps are performed on a moving unit.
Moreover, once the tray is filled with the food product and the lid is positioned, the tray's inside surfaces are not accessible. Any force applied to a lid flap for sealing against a tray side wall must be less than the crushing capacity of the erected tray. Frequently, only a gentle touch is permissible.
In order to avoid a crushing of the erected tray, the prior art has relied upon both cold set and hot melt adhesives to achieve lid-to-tray seal. Exemplary of such prior art are U.S. Pat. Nos. 5,090,615 to Hopkins et al. and 5,234,159 to Lorence et al. While these two references avoid a crushing of the erected tray, each of these adhesive sealing devices carry respective adverse consequences. For example, cold set adhesives are extremely slow setting and, therefore, incompatible with a production capacity of 120 units per minute. Also, hot melt adhesives have relatively low softening temperatures which are incompatible with typical oven temperatures which are used when the food within the package is heated for consumption. These glue systems also add components to the packaging line which can add expense and time to the packaging of the contents. Finally, these glue systems add additional materials for the food packager to inventory. Therefore, a more advantageous food tray would be one which avoided the use of adhesives.
It is apparent from the above that there is a need in the art for a food tray and lid which can be easily sealed together through simplicity of parts and the uniqueness of structure, and which at least equal the sealing characteristics of the prior food trays, but which at the same time avoid the use of adhesives. It is the purpose of this invention to fulfill this and other needs in the art in a manner more apparent to the skilled artisan once given the following disclosure.
SUMMARY OF THE INVENTION
Generally speaking, this invention fulfills these needs by providing a container/lid assembly, comprising a paperboard container further comprising an outer surface having a bottom surface and a peripheral wall extending substantially upward from a first edge of the bottom surface, and an inner surface located adjacent to the peripheral wall wherein the outer surface is further comprised of a polymeric coating located on predetermined areas of the outer surface, and a lid further comprising a first and second side such that the first side includes a polymeric coating and further includes a first section which substantially overlaps the peripheral wall section of the container and a second section which is located substantially over the predetermined areas of the polymeric coating on the outer surface of the container, wherein the polymeric coatings on the container and the lid form a seal between the container and the lid when the coatings are heated.
In certain preferred embodiments, the polymeric coating on the inner container surface is made up of a thermally stable moisture barrier. Also, the polymeric coating on the lid is constructed of substantially the same thermally stable moisture barrier coating. The polymeric coating may be applied to the bottom surface of the paperboard container. Finally, the coating on the lid may be a continuous coating or a patterned coating.
In another further preferred embodiment, a container/lid assembly can be constructed which adequately protects the food contents and which at the same time avoids the use of adhesives.
The preferred container/lid assembly, according to this invention, offers the following advantages: ease of assembly; an avoidance of adhesives; excellent stability; excellent durability; and good economy. In fact, in many of the preferred embodiments, these factors of ease of assembly, avoidance of adhesives, excellent stability, and excellent durability are optimized to an extent that is considerably higher than heretofore achieved in prior, known container/lid assemblies.
The above and other features of the present invention, which will become more apparent as the description proceeds, are best understood by considering the following detailed description in conjunction with the accompany drawings, wherein like characters represent like parts throughout the several views and in which:
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1a-1c illustrate a container/lid assembly for a multi-compartment container, according to the present invention, wherein FIG. 1a illustrates the lid, FIG. 1b illustrates the multi-compartment container, and FIG. 1c illustrates an assembled container/lid assembly;
FIGS. 2a-2d illustrate a container/lid assembly for a single compartment container, according to the present invention, wherein FIG. 2a illustrates a lid, FIG. 2b illustrates a single compartment container, FIG. 2c illustrates an assembled container/lid assembly with the lid attached to the bottom of the container, and FIG. 2d illustrates another embodiment of a container/lid assembly with the lid attached to the side of the container;
FIGS. 3a-3b illustrate another embodiment of a container/lid assembly for a multi- compartment container, according to the present invention, wherein FIG. 3a illustrates the lid, FIG. 3b illustrates the multi-compartment container, and FIG. 3c illustrates an assembled container/lid assembly; and
FIGS. 4a-4d illustrate another embodiment of a container/lid assembly for a single compartment container, according to the present invention, wherein FIG. 4a illustrates a lid, FIG. 4b illustrates a single compartment container, FIG. 4c illustrates a completed container/lid assembly with the lid attached to the bottom of the container, and FIG. 4d illustrates another embodiment of a container/lid assembly with the lid attached to the side of the container.
DETAILED DESCRIPTION OF THE INVENTION
With reference first to FIGS. 1a to 1c, there is illustrated lid 2 (FIG. 1a), tray 8 (FIG. 1b), and lid/container assembly 20 (FIG. 1c). With respect to FIG. 1a, lid 2 includes in part, score lines 4 and coating 6. Coating 6, preferably, is a continuous polymeric coating. This polymeric coating should exhibit a relatively low softening temperature (below 400° F.) so that it may be heated and tack bonded on a continuous conventional conveying system traveling at typical packaging lines speed with only a gentle compression pressure being permissible to join lid 2 to tray 8. Also, the polymer coating must exhibit temperature stability above 400° F. in order to be considered for ovenable applications. Finally, the upper portion of the lid is conventionally printed with sales graphics or other such information.
With respect to tray 8, tray 8 includes, in part, compartments 10, areas 12 of the polymer coating, and flange 14. It is to be understood that the areas 12 of the polymer coating are coated with substantially the same polymer coating as coating 6 (FIG. 1a). It is also to be understood that the inside of tray 8 is conventionally coated with a continuous coating of a conventional ovenable polymer.
With respect to container/lid assembly 20 (FIG. 1c), assembly 20, includes, in part, lid 2, score lines 4, coating 6, tray 8, tray compartments 10, polymer coating 12, flange 14, and tray bottom 16. As can be seen, patterned polymer areas 12 are placed upon bottom 16 of tray 8 by use of conventional applicating techniques. Also, as can be seep in FIG. 1c, lid 2 is folded along score lines 4 and attached along flange 14 and polymeric areas 12 such that lid 2 is attached to tray 8 after the polymer coatings 6 and 12 are heated by conventional heating techniques.
The coatings that may be applied to lid 2 and tray 8 include, but are not limited to, the MW 10 product of Michelman, Inc., 9080 Shell Road, Cincinnati, Ohio. Another such source is the CARBOSET XPD-1103 product of B. F. Goodrich Company, 9911 Brecksville Road, Brecksville, Ohio.
The Michelman MW 10 product comprises an acrylic copolymer resin and high density polyethylene wax. The Goodrich CARBOSET XPD-1103 product is described as an anionic emulsion of an acrylic ester copolymer in water. CARBOSET XPD-1103 is also characterized as a styrene-acrylic copolymer emulsion containing heat activated curing mechanisms stimulated by a 250°-300° F. curing temperature.
Other coatings which are solvent-based which may work for this application include Adcote 40-3E and 33R2-AH, also produced by Morton.
With respect to FIGS. 2a-2d, FIG. 2a shows lid 50. FIG. 2b shows single compartment tray 56. FIG. 2c shows container/lid assembly 70. Finally, FIG. 2d shows another embodiment of a container/lid assembly 80.
With respect to FIG. 2a, lid 50 includes, in part, score lines 52 and coating 54. Coating 54, preferably, is the same coating placed upon lid 2, as shown in FIG. 1a.
With respect to tray 56, tray 56 includes, in part, flange 58, tray compartment 60, and patterned polymer areas 62. Polymer areas 62, preferably, are constructed of the same material and in the same manner as patterned polymer areas 12 of FIG. 1b.
With respect to FIG. 2c, container/lid assembly 70 includes, in part, lid 50, score lines 52, polymer coating 54, tray 56, flange 58, patterned polymer areas 62, and tray bottom 64. With respect to container/lid assembly 70, lid 50 is scored and folded and attached to the bottom 64 of tray 56 by the heating polymer coating 54 and patterned polymer areas 62.
With respect to container/lid assembly 80, as shown in FIG. 2d, assembly 80 includes, in part, lid 50, score lines 52, polymer coating 54, tray 56, tray compartment area 60, patterned polymer areas 62, and tray bottom 64.
As shown in FIG. 2d, tray 56 does not include flanges. Therefore, the use of an additional score line 52 is eliminated from lid 50. Thus, patterned polymer areas 62 are placed by conventional applicating techniques along the opposite sides of tray 56. However, as with container/lid assembly 70 (FIG. 2c), lid 50 is attached to tray 56 through the heating of polymer coating 54 and patterned polymer areas 62 such that lid 50 is attached to tray 56.
With reference to FIG. 3, FIG. 3a illustrates lid 2. FIG. 3b illustrates multi-compartment tray 8. Finally, FIG. 3c illustrates container/lid assembly 20.
As discussed earlier with respect to FIGS 1a to 1c, lid 2 (FIG. 3a) includes, in part, score lines 4, patterned polymer coating 6, and patterned polymer coatings 7. Coating 6, preferably, is the same coating as that set forth with respect to FIG. 1a. However, patterned areas 7 are located along the outer edges of lid 2 and are preferably, constructed of a different material than coating 6.
The coatings that may be applied to lid 2 in pattern areas 7 include, but are not limited to Adcote 37R972HV, 37T77 and X19-7 produced by Morton International, Inc. of Woodstock, Ill. The basic requirements of the coatings being that the polymer constituent in emulsions is solubilized by conventional acidic modification and then buffered to a pH when the acid exists as a salt. The tack temperature should be about 375° F. and the application rate should range from 0.5 lb/ream to 4.0 lbs/ream, although most applications will find an application rate of 2 to 3 lbs/ream to be preferable. The working viscosity of such emulsions may be reduced by water solvation.
With respect to FIG. 3b, tray 8 includes, in part, tray compartments 10, patterned polymer areas 12, and flange 14. Again, as with respect to FIG. 1b, tray 8 is constructed substantially the same as that described with respect to FIG. 1b. It is to be understood that the polymeric areas 12 are coated with substantially the same polymer coating as coating 7.
With respect to FIG. 3c, container/lid assembly 20 includes in part, lid 2, score lines 4, patterned polymer coating 6, patterned polymer areas 7, tray 8, tray compartments 10, patterned polymer areas 12, tray flange 14, and tray bottom 16. As discussed earlier with respect to FIG. 1c, lid 2 is secured to flange 14 and tray bottom 16 through the heating of patterned polymer coating 6, patterned polymer coatings 7 and patterned polymer coatings 12. Distinct patterned polymer areas 7 are used to attach the flaps of lid 2 to the bottom 16 of tray 8.
With respect to FIG. 4, FIG. 4a illustrates lid 50. FIG. 4b illustrates single compartment tray 56. FIG. 4c illustrates container/lid assembly 70. Finally, FIG. 4d illustrates another embodiment of a container/lid assembly 80.
Lid 50 includes, in part, scores line 52, patterned polymer coating 54 and patterned polymer coatings 55. Coating 54, preferably, is the same material as coating 54 earlier described with respect to FIG. 2a. It should be understood that coatings 54 and 55, preferably, are not the same type of coatings. Coatings 54 and 55 are applied in a patterned technique instead of a continuous coating.
Tray 56, includes, in part, flange 58, tray compartment 60, and patterned polymer areas 62. It is to be understood that tray 56 as shown in FIG. 4b is substantially the same as tray 56 previously described with respect to FIG. 2b. It is to be understood that patterned polymer coating areas 62 are coated with substantially the same polymer coating as coating 55.
With respect to container/lid assembly 70 (FIG. 4c), assembly 70 includes, in part, lid 50, score lines 52, patterned coating 54, patterned coatings 55, tray 56, flange 58, tray compartment 60, patterned polymer areas 62, and tray bottom 64. Lid 50 is attached to tray 56 in substantially the same manner as is described with respect to container/lid assembly 70 of FIG. 2c. However, in this particular instance, instead of the continuous coating, as previously described with respect to FIG. 2c, there is a patterned coating 54 and patterned coatings 55. Patterned coating 54 is used to secure lid 50 to the flange 58. Patterned coatings 55 are used to secure lid 50 to the bottom 64 of tray 56.
Container/lid assembly 80 (FIG. 4d) includes, in part, lid 50, score lines 52, patterned coating 54, patterned coatings 55, tray 56, tray compartment 60, and patterned polymer areas 62. As discussed earlier with respect to FIG. 2d, tray 56 does not have flanges 58 as previously described with respect to FIG. 4c. Consequently, patterned areas 62 must be applied by conventional techniques to the opposite sides of tray 56. In this manner, patterned areas 55 and 62 can come in contact with each other to make a bond when heated to secure lid 50 to tray 56. It is to be understood that patterned areas 55 and 62 will be located on lid 50 and tray 56, respectively, in such a manner that patterned areas 55 and 62 will contact each other prior to a heat treatment of the various assemblies such that these patterned areas will create a bond between the lids and the trays when heated so that the lids will be attached to the trays.
Once given the above disclosure, many other features, modifications or improvements will become more apparent to the skilled artisan. Such features, modifications or improvements are, therefore, considered to be a part of this invention, the scope of which is to be determined by the following claims.
|
This invention relates to paperboard food packages. Such structures of this type, generally, have lids which can be sealed to the food package which utilizes press-applied coatings as a sealing medium.
| 8
|
CROSS REFERENCE
[0001] This is a continuation-in-part of U.S. patent application Ser. No. 11/964,151, filed on Dec. 26, 2007, which is incorporated herewith by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention generally relates to monitoring electrical grounding, and more particularly to a device and system that automatically monitors an operator's grounding mechanisms only when the operator is actually present in front of a work station.
[0004] 2. The Related Art
[0005] How to prevent electro-static discharge (ESD) from damaging valuable equipment or causing critical fabrication process to fail is still an important issue in high-tech industries. It is well known that proper grounding is the essential solution. However, despite the advancement of technology, ensuring such a proper grounding is not as easy as most people imagine.
[0006] A typical manufacturing environment usually contains a number of assembly lines, and each assembly line usually contains a number of work stations, each for a specific assembly task or manufacturing operation. To prevent ESD from damaging the parts, devices, or the semi-products being assembled, the operator at the work station is usually required to wear an anti-static wrist strap, the floor is usually paved with an anti-static floor mat, and the table top of the work station is usually covered with an anti-static table mat. As illustrated in FIG. 1 a, the floor mat 10 , table mat 20 , and the wrist strap 30 are usually electrically connected to a common-point ground 40 of the work station by grounding cables, respectively (for simplicity, the drawing only shows a ground cable connecting the wrist strap 30 and the common-point ground 40 ). The common-point ground 40 is usually a metallic plate fixedly positioned at some place of the work station with a plastic cover for protection. The common-point grounds of an assembly line's work stations are series- or parallel-connected together, which are in turn connected to an equipment ground or an earth ground of the manufacturing facility (again, for simplicity, the equipment and earth grounds are not shown in the drawing). As such, the static electricity carried by or accumulated on an operator sitting or standing in front of the work station is discharged to the earth through the wrist strap, table mat, or the floor mat, via the common-point ground of the work station and then the equipment or earth ground of the manufacturing facility, thereby preventing potential hazards from ESD.
[0007] The aforementioned grounding system is a proven solution and has been widely adopted for years. However, it suffers a number of disadvantages. First, this grounding system works only if the wrist strap, the floor mat, and the table mat are properly connected to the common-point ground. However, the grounding cables therebetween could be rusted or broken, or the grounding cables could be disconnected from the common-point ground due to the movement of the operator. In addition, when the operator has to take a break or to go for lunch, he or she may take down the wrist strap and leave it on the work station. Or, in most of the existing implementations, the grounding cable of the wrist strap has a plug at one end so as to plug into a socket of the common-point ground. Therefore, the operator unplugs the grounding cable (but still wears the wrist strap) before going for a break or lunch. When the operator returns, he or she then put the wrist strap back or plug the grounding cable again. As can be imagined, a lazy operator may avoid wearing the wrist strap; or an absent-minded operator may forget to put back or re-plug the wrist strap after returning to his or her post. The static electricity carried by or accumulated on the operator cannot be discharged to the ground, and may very possible damage the valuable equipment or parts or semi-product or completed product at the work station.
[0008] As such, the present inventor has disclosed a wireless monitoring device for a work station operator to see if the operator has properly worn a wrist strap or similar grounding mechanism (U.S. patent application Ser. No. 11/964,151 filed on Dec. 26, 2007, hereinafter, the previous application). The representative drawing of the previous application is attached as FIG. 1 b. As illustrated, the monitoring device 100 mainly contains a microprocessor circuit 200 as its core. The device 100 is connected to the mains via a power cable or via an external power supply (e.g., a power adaptor such as those used by a notebook computer). The connection to the mains is very important in that, on one hand, the electricity extracted from the mains is processed by a power unit 500 of the device 100 to provide appropriate direct-current (DC) voltages to the microprocessor circuit 200 . On the other hand, the ground 60 of the mains is thereby electrically introduced into the device 100 . The device 100 is also connected to the manufacturing facility's equipment ground or earth ground 50 (hereinafter, jointly referred to as earth ground) via an interface 120 . This can be achieved by connecting a common-point ground 40 of the work station or, as illustrated, by directly connecting the earth ground 50 . Additionally, the device 100 is connected to two conducting wires 31 , 32 of a wrist strap 30 via another interface 110 . As illustrated, an end of the wire 31 is electrically connected to the earth ground 50 inside the device 100 whereas an end of the wire 32 is electrically connected to the mains ground 60 via the microprocessor circuit 200 . The other ends of the wires 31 , 32 are connected to two conducting plates embedded in an insulating casing of the wrist strap 30 , respectively. The conducting plates 33 are usually exposed from the inside of the insulating casing so as to contact an operator's wrist skin 70 . As such, when the operator has properly worn the wrist strap 30 , a discharge circuit, shown by the dashed lines of FIG. 1 b, is established from the mains ground 60 , through the earth, the earth ground 50 , the wire 31 , the skin 70 , the wire 32 , and then to the mains ground 60 via the microprocessor circuit 200 . A major function of the microprocessor circuit 200 is in determining if the discharge circuit has an appropriate resistance. The rest of the details could be found in the previous application and is omitted here.
[0009] There are still some disadvantages for the monitoring device 100 taught by the previous application. First of all, the monitoring device 100 is applicable to grounding mechanism with two conducting wires, yet there are quite some commercially available single-wire grounding mechanisms. The monitoring device 100 is therefore not applicable to these single-wire grounding mechanisms. Secondly, the monitoring device 100 could only monitor the grounding mechanisms an operator is equipped with but cannot provide additional ESD protection to the operator. For example, if the connection between the common point ground 40 and the earth ground 50 is somehow disconnected (e.g., at a place marked by X in FIG. 1 b ), the monitoring device 100 would signal an alarm and the operator has to stop his or her work until the disconnection is fixed. But, as can be seen in FIG. 1 b , the mains ground 60 connected to the monitoring device 100 could provide the required grounding and the operator actually does not need to stop his or her work. In other words, the monitoring device 100 could actually provide the mains ground 60 as an auxiliary grounding for additional ESD protection. Additionally, according to the previous application, every monitoring device 100 would require a power cable or a power adaptor, and an outlet for plugging the power cable or the power adaptor, which would increase the product and installation costs.
SUMMARY OF THE INVENTION
[0010] Accordingly, the present invention provides a device to monitor whether a work station operator has properly worn a wrist strap or similar grounding mechanism, and a system cascading these devices, so as to obviate the aforementioned shortcomings of the prior arts.
[0011] A major characteristic of the device is that a wireless energy (e.g., infrared) transmission and detection mechanism is incorporated to sense if the operator is present in front of the work station. The device monitors the resistance of a loop composed of the operator's wrist strap. If the monitored resistance is not in a proper range, for example, when the wrist strap is not worn or the 1-MΩ resistor in the grounding cable is broken or shorted, the device will automatically issue alarms, only if the wireless energy transmission and detection mechanism has sensed that the operator is indeed present at the work station.
[0012] Compared with the previous application, the present invention further provides a novel electrical connection within the device and a novel cascading means to chain multiple devices together for sharing electricity and ground. The present invention could further achieve the following functions: (1) capable of monitoring both single-wire and two-wire grounding mechanisms; (2) providing backup grounding through the chain so that the static electricity discharging capability is maintained as long as a single device in the chain remains connected to the ground; (3) extending the ground through the chain so that grounding is not required to be previously prepared at every work station; (4) sustaining all devices on the chain by a single external power supply; and (5) providing networking connectivity through the chain's cascading cables so that the network cabling cost and effort is significantly reduced.
[0013] The foregoing and other objects, features, aspects and advantages of the present invention will become better understood from a careful reading of a detailed description provided herein below with appropriate reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 a is a schematic diagram showing a conventional grounding structure commonly found on a work station.
[0015] FIG. 1 b is a representative drawing of U.S. patent application Ser. No. 11/964,151.
[0016] FIG. 2 a is a schematic diagram showing two monitoring devices according to a first embodiment of the present invention are connected into a monitoring system.
[0017] FIG. 2 b is a schematic diagram showing a monitoring device according to a second embodiment of the present invention which monitors an additional series-connected grounding mechanism.
[0018] FIG. 2 c is a schematic diagram showing a monitoring device according to a third embodiment of the present invention which monitors an additional parallel-connected grounding mechanism.
[0019] FIG. 3 a is a functional block diagram showing a monitoring device's microprocessor circuit according to an embodiment of the present invention.
[0020] FIG. 3 b is a schematic diagram showing an active-typed personnel detection unit of a monitoring device of the present invention.
[0021] FIG. 3 c is a schematic diagram showing a passive-typed personnel detection unit of a monitoring device of the present invention.
[0022] FIG. 3 d is a functional block diagram showing a monitoring device's microprocessor circuit according to another embodiment of the present invention.
[0023] FIG. 4 a is a functional block diagram showing a monitoring device's microprocessor circuit according to yet another embodiment of the present invention.
[0024] FIG. 4 b is a schematic diagram showing multiple monitoring devices of FIG. 4 a networked together with a centralized console.
[0025] FIG. 4 c is a schematic diagram showing multiple monitoring devices cascaded to a centralized console.
[0026] FIG. 4 d is a schematic diagram showing multiple monitoring devices cascaded to a centralized console that also provides electricity.
[0027] FIG. 5 a is a schematic diagram showing the monitoring device of FIG. 2 a monitoring a single-wire wrist strap.
[0028] FIG. 5 b is a schematic diagram showing a monitoring device according to a fourth embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0029] The following descriptions are exemplary embodiments only, and are not intended to limit the scope, applicability or configuration of the invention in any way. Rather, the following description provides a convenient illustration for implementing exemplary embodiments of the invention. Various changes to the described embodiments may be made in the function and arrangement of the elements described without departing from the scope of the invention as set forth in the appended claims.
[0030] FIG. 2 a is a schematic diagram showing two monitoring devices are connected into a monitoring system according to a first embodiment of the present invention. As illustrated, the two monitoring devices 100 are series-connected by a cable 700 containing at least two conducting wires 701 and 702 through their respective interfaces 150 . One of the monitoring device 100 (i.e., the upper one in FIG. 2 a ) is further connected to an external power supply 600 by a cable 710 containing at least two conducting wires 711 and 712 through another interface 150 . Similar to the previous application, the monitoring device 100 is a stand-alone device and mainly contains a microprocessor circuit 200 as its core. However, by comparing FIGS. 1 b and 2 a, it should be easy to see the difference between the monitoring devices of the present invention and the previous application.
[0031] Please note that, even though not explicitly shown in FIG. 1 b, the monitoring device of the previous application also has an interface 150 connected to an external power supply 600 , just like the present invention. However, they are omitted in FIG. 1 b for simplicity and, in the present invention, they are explicitly illustrated. Compared to the monitoring device of the previous application, the monitoring device 100 of the present invention has an additional interface 150 for connecting another monitoring device 100 by the cable 700 . In other words, the monitoring device 100 of the present invention has two interfaces 150 and the two interfaces 150 are actually completely identical. There is no requirement which one of them is for connecting the other monitoring device 100 and which one is for connecting the external power supply 600 . The two interfaces 150 are interchangeable. Please note that, as shown in FIG. 2 a, each interface 150 has at least two terminals (not shown): a first terminal and a second terminal. The first terminals of the two interfaces 150 are connected together, and the second terminals of the two interfaces 150 are connected together, both inside the monitoring device 100 . However, the second terminals that are connected to either the wire 702 (in a cable 700 ) or the wire 712 (in a cable 710 ) are further connected to the power unit 500 of the monitoring device 100 . On the other hand, the first terminals that are connected to either the wire 701 (in a cable 700 ) or the wire 711 (in a cable 710 ) are further connected to the microprocessor circuit 200 and the interface 120 of the monitoring device 100 .
[0032] The external power supply 600 on one hand is connected to the mains and, on the other hand, is connected to a monitoring device 100 by a cable 710 . As such, the external power supply 600 draws alternate-current (AC) electricity from the mains and supplies appropriate DC or AC voltage to the directly connected monitoring device 100 via the wire 712 of the cable 710 . The mains ground 60 is also provided to the directly-connected monitoring device 100 by the external power supply 600 via the wire 711 of the cable 710 . As shown in FIG. 2 a, the DC or AC voltage is fed to the power unit 500 which in turn provides appropriate DC voltage to drive the microprocessor circuit 200 . In the mean time, the mains ground 60 is also provided to the microprocessor circuit 200 and the interfaces 110 and 120 . Additionally, the voltage and mains ground 60 from the external power supply 600 is passed to a next monitoring device 100 via the wires 702 and 701 of a cable 700 , respectively. Even though only two monitoring devices 100 are illustrated in FIG. 2 a, more monitoring devices 100 could be cascaded in a chain by using cables 700 to connect the interfaces 150 of any two neighboring monitoring devices 100 . In this manner, the voltage and mains ground 60 from the external power supply 600 could be passed to every monitoring device 100 on the chain and a single external power supply 600 is shared by these monitoring devices 100 . The present invention therefore is more cost-effective compared to the previous application which requires an external power supply 600 for every monitoring device. Please note that the monitoring device 100 is not required to be used always with another monitoring device 100 . A monitoring device 100 could be used individually as long as it is connected to an external power supply 600 by a cable 710 by itself.
[0033] As shown in FIG. 1 b, the previous application forms a closed loop (as denoted by the dashed lines) via the earth to determine if the wrist strap 30 is properly worn by an operator. In contrast, as shown in FIG. 2 a, the present application closes the loop (as denoted by the dashed lines) within the monitoring device 100 itself. As illustrated, the loop consists of the connection between the interfaces 120 and 110 , the wire 31 , the operator's skin 70 , the wire 32 , the microprocessor circuit 200 , and the connection between the microprocessor circuit 200 and the interface 200 . One of the major functions of the microprocessor circuit 200 is to determine whether the loop has an appropriate resistance. In other words, the microprocessor circuit 200 measures the resistance between the wires 31 and 32 to see whether the wrist strap 30 is properly installed by the operator.
[0034] When a monitoring device 100 of the present invention is used individually (for example, considering only the upper monitoring device 100 of FIG. 2 a ), the charges carried or accumulated on the operator could be discharged to (1) the earth ground 50 through to its interface 120 ; and (2) the mains ground 60 through the cable 710 . Therefore, when the monitoring device 100 and the earth ground 50 is for some reason disconnected, the charges carried or accumulated on the operator could still be discharged to the mains ground 60 . In other words, the present invention provides the mains ground 60 as an auxiliary grounding, for an additional level of protection.
[0035] When a monitoring device 100 of the present invention is used in cascade (for example, using the lower monitoring device 100 of FIG. 2 a as example), the charges carried or accumulated on the operator could be discharged to (1) the earth ground 50 through to its interface 120 ; (2) the earth ground 50 connected to another monitoring device 100 series-connected by one or more cables 700 ; and (3) the mains ground 60 through the external power supply 600 connected to another monitoring device 100 series-connected by one or more cables 710 . Therefore, when the monitoring device 100 and the earth ground 50 is for some reason disconnected, the charges carried or accumulated on the operator could still be discharged. In other words, the present invention provides highly redundant grounding, for a significant level of protection. Assuming that there are N monitoring devices 100 cascaded together as described, each monitoring device 100 on the chain in effect has N+1 possible discharge paths. As long as one of the paths is functioning, the discharge capability of every monitoring device 100 on the chain is still preserved. Even when all monitoring devices 100 are disconnected from the earth ground 50 , they could still discharge to the mains ground 60 . This high level of redundancy is made possible by the cables 700 and the cable 710 . If one of the cables 700 or the cable 710 is disconnected, since they are also responsible for the delivery of electricity, this will lead to one or more monitoring devices 100 stop functioning due to the lost of power. This should immediately get the attention of the operators and remedies could be adopted right away.
[0036] From the above description, it should be clear that there are various possible applications of the present invention. For example, only one monitoring device 100 on the chain is connected to the earth ground 50 and this is in effect a way to extend the earth ground 50 via the cascading monitoring devices 100 , instead of requiring the availability of the earth ground 50 at every work station. If each monitoring device 100 has an additional interface, this extended earth ground 50 could actually be shared to other devices through the additional interface. In other words, each monitoring device 100 could actually function as a common-point ground 40 at each work station (therefore, there is no need to install common-point ground 40 at every work station). Another example is not to use the earth ground 50 at all and to simply rely on the mains ground 60 . This would prove to be especially convenient when the earth ground 50 is not available.
[0037] Identical to the previous application, the interface 110 between the grounding cable of the wrist strap 30 and the device 100 could be one that supports dynamically plugging and unplugging. For example, the wrist strap 30 has a plug at an end and the device 100 has a compatible socket. In alternative embodiments, the interface 110 could provide fixed connection only. Similarly, the interface 120 to the earth ground 50 could provide either fixed or dynamic connection.
[0038] The present embodiment only monitors the wrist strap 30 . FIG. 2 b is a schematic diagram showing a monitoring device according to a second embodiment of the present invention which also monitors an additional grounding mechanism (such as a floor mat or a table mat). As illustrated, two wires 21 , 22 of, for example, a table mat 20 are electrically connected to the earth ground 50 and the wrist strap 30 , respectively, via an interface 130 . Again, the interface 130 could provide fixed or dynamic connection. As illustrated, a loop, expressed by the dashed lines, is formed with the wrist strap 30 and the table mat 20 being series-connected, and the microprocessor circuit 200 is therefore able to monitor the table mat 20 and the wrist strap 30 simultaneously. In other words, in addition to the wrist strap 30 , the monitoring device 100 is able to incorporate the monitoring of at least one of any two-wire grounding mechanisms together.
[0039] The microprocessor circuit 200 determines if the loop is normal by measuring the resistance of the loop. However, if there is indeed something wrong with the loop, the present embodiment is not able to tell which grounding mechanism is causing the problem. FIG. 2 c is a schematic diagram showing a grounding monitoring device according to a third embodiment of the present invention. As illustrated, separate loops (shown by the dashed lines) are formed through the wrist strap 30 and the table mat 20 respectively. As such, the microprocessor circuit 200 is able to monitor the wrist strap 30 and the table mat 20 individually and simultaneously. Again, a person with ordinary skill can easily extend the same idea to incorporate the monitoring of the floor mat 10 and therefore the detail is omitted here. Please note that the microprocessor circuit 200 of FIG. 2 b is not identical to the microprocessor circuit 200 of FIG. 2 c, as additional parts are required in the parallel configuration of FIG. 2 c to measure an additional loop. Again, a person of ordinary skill could easily extend the microprocessor circuit of series configuration to cover the microprocessor circuit of parallel configuration. Following the same line of thought, the present invention could be further extended to cover: (1) the monitoring of other grounding mechanisms similar to the wrist strap, the table mat, or the floor mat, as long as they also use two-wire grounding cables; (2) configurations where some grounding mechanisms are parallel-connected and some are series-connected; and (3) configurations with more than one wrist strap, table mat, or floor mat. For simplicity, the present specification will focus on the microprocessor circuit 200 of series configurations (e.g., FIG. 2 b ) and use only the wrist strap 30 as example to explain the details of the device 100 .
[0040] FIG. 3 a is a functional block diagram showing a grounding monitoring device's microprocessor circuit according to an embodiment of the present invention. In the drawing, Vin is a DC voltage produced by the power unit 500 after drawing electricity from the mains to drive the microprocessor circuit 200 .
[0041] As illustrated, the microprocessor circuit 200 contains a comparison and amplification unit 210 which is mainly composed of at least an operation amplifier. The variable resistors R 1 and R 2 are actually an integral part of the comparison and amplification unit 210 but they are separately shown for easier explanation. The provision of the series-connected R 1 and R 2 allows the operation amplifier(s) in the comparison and amplification unit 210 to see if the resistance of the loop introduced by the wire 32 has a value between R 2 and R 1 . In other words, the function of the comparison and amplification unit 210 is to test if the resistance of the loop is bounded by a smaller first resistance (e.g., R 2 ) and a larger second resistance (e.g., R 1 ). If the operator does not put on the wrist strap 30 , or the ground cable of the wrist strap 30 is rusted or broken, the resistance of the loop would be greater than the second (i.e., larger) resistance. On the other hand, if the operator has properly worn the wrist strap 30 and the grounding cable and everything else is normal, the resistance shouldn't be less than the first (i.e., smaller) resistance either. Therefore, if the resistance of the discharge circuit is greater than the second resistance or less than the first resistance, the comparison and amplification unit 210 would trigger a microprocessor unit 220 . In alternative embodiments, it is possible to have only a single variable resistor R 1 (i.e., omitting the variable resistor R 2 ). These embodiments therefore will only detect if the resistance of the discharge circuit is greater than a specific value (i.e., the resistance of the variable resistor R 1 ). There are also embodiments where the first and second resistances are implemented by fixed resistors. The advantage of having variable resistors is that, depending on whether the loop covers only the wrist strap, or has additional grounding mechanism such as table mat series-connected, the first and second resistances can be dynamically adjusted to reflect these variations. The adjustment of the variable resistors R 1 and R 2 can be conducted by manually twisting knobs or by a control panel, both on the device 100 's casing. More details will be given later.
[0042] The microprocessor unit 220 is the core of the device 100 . It could be a microcontroller unit (MCU), a single chip containing a processor, RAM, ROM, clock, and I/O control units. Millions of MCUs are in used in various devices ranging from automobiles to laser printers. The present specification therefore will not go into details.
[0043] After being triggered by the comparison and amplification unit 210 , the microprocessor unit 220 activates an alarm unit 230 to issue alarms so as to remind the operator to wear the wrist strap or to get the attention of supervisors or managers. The alarm unit 230 contains one or more lamps, for example, made of light emitting diodes (LEDs). The alarm unit 230 turns on or flashes these lamps to provide visual alarms. The alarm unit could also contain one or more speakers or buzzers to provide audio alarms. These audio or visual alarms could be implemented individually or together. The alarm unit 230 could further contain electronic or mechanical relays to trigger additional devices. When the abnormality detected by the comparison and amplification unit 210 is resolved, the microprocessor unit 220 is notified to turn off the alarm unit 230 . In alternative embodiments, there are reset buttons on the casing or control panel of the device 100 to shutdown the audio or visual alarms.
[0044] A personnel detection unit 240 is provided to see if there is indeed an operator present in front of the device 100 (i.e., in front of the work station). The personnel detection unit 240 may provide a presence signal when an operator appears or is present and an absence signal when the operator leaves or is absent. The presence and absence signals are delivered to the microprocessor unit 220 as well. As such, the microprocessor unit 220 is able to engage the detection of the loop's resistance and to trigger the alarm unit 230 if required, only when a operator is present in front of the device 100 (e.g., the microprocessor unit 220 has received. a presence signal but not an absence signal yet). When the operator has to leave the work station and take off the wrist strap 30 or disconnect the wrist strap 30 from the interface 110 , as shown in FIGS. 2 a, 2 b, and 2 c, the microprocessor unit 220 will be triggered by the comparison and amplification unit 210 as the latter has seen an abnormal resistance from the loop (the loop is open-circuited). The microprocessor unit 220 , as it has already picked up an absence signal from the personnel detection unit 240 , will not initiate the alarm unit 230 to issue alarms. However, once the personnel detection unit 240 has sensed the presence of the operator, the microprocessor unit 220 automatically begins to activate the alarm unit 230 in accordance with the result of the comparison and amplification unit 210 so that the operator will be reminded to wear or re-plug the wrist strap 30 . In other words, the absence signal from the personnel detection unit 240 functions like an inhibitor to prevent the microprocessor unit 220 from activating the alarm unit 230 whereas the presence signal functions like an enabler to the microprocessor unit 220 . Please note that the personnel detection unit 240 only provides the detection result regarding whether the operator is present or absent. The decision about whether to activate the alarm unit 230 is still carried out by the microprocessor unit 220 . To prevent erroneous judgment and to allow the operator some time to settle, the microprocessor unit 220 will remain inhibited after receiving the presence signal for a period of time (e.g., 5 seconds) and, if there is no absence signal within this period of time, the microprocessor unit 220 will then activate the alarm unit 230 in accordance with the result of the comparison and amplification unit 210 . In contrast, if an absence signal is received at any point of time, the microprocessor unit will stop activating the alarm unit 230 immediately.
[0045] The personnel detection unit 240 can employ either an active means or a passive means in detecting the presence of an operator. FIG. 3 b is a schematic diagram showing an active-typed personnel detection unit of a grounding monitoring device of the present invention. As illustrated, the active-typed personnel detection unit 240 has a wireless energy transmitter, such as the infrared LED 241 in the drawing or radar, which can radiate an electromagnetic or supersonic wave covering a limited range to a front side of the device 100 (i.e., towards the operator). The active-typed personnel detection unit 240 also requires a sensor to detect the energy reflected from the operator, such as the infrared receiver 242 in the drawing. This active-typed detection technique has been widely applied in various fields and there are many different transmitters, sensors, and related circuits disclosed and commercially available. To give a few examples, active-typed detection based on infrared is commonly found on auto-flush toilets, those based on supersonic waves are commonly found on automobile radar backup alarm systems. As illustrated, an output terminal of the microprocessor unit 220 controls an electronic switch 243 to turn on or off the infrared LED 241 . On the other hand, the output of the infrared receiver 242 is delivered to an input terminal of the microprocessor unit 242 .
[0046] The active-typed detection is a rather effective solution to the present invention. However, there are usually chairs also positioned in front of the work stations. The personnel detection unit 240 couldn't distinguish whether it is the operator or the chair (after the operator has left) that is present in front of the work station. The passive-typed detection would provide a more accurate result in this respect. Currently the most common passive-typed detection is based of passive infrared (PIR) sensors, which are able to pick up the movement of a warm object within a specific range. PIR sensors are quite common in security-related applications. However, their adoption has declined in recent years as they cannot distinguish the movement made by a dog or a cat from the movement made by a human being, which are all warm bodies. Interestingly, PIR sensors are quite adequate for the present invention as they have no problem in differentiating the warm human body and the cold chair. As shown in FIG. 3 c, the passive-typed personnel detection unit 240 requires a single PIR sensor 244 , which is even simpler structurally.
[0047] There is another passive-typed detection technique which uses a camera to capture images and performs image analysis to detect object movement. In security surveillance arena, such motion detection technique has already been proven to have a significant accuracy. However, to equip a camera in the personnel detection unit 240 and to make the microprocessor unit 220 powerful enough to carry out image processing would make the device 100 much more complicated and costly.
[0048] FIG. 3 d is a functional block diagram showing a grounding monitoring device's microprocessor circuit according to another embodiment of the present invention. In the present embodiment, the microprocessor circuit 200 contains an additional control interface unit 250 , which provide a human-machine interface to the device 100 . The control interface unit 250 signally connects one or more buttons (not shown) forming a control panel on the casing of the device 100 . The control interface unit 250 in turn connects a number of input terminals of the microprocessor unit 220 for configuring some operation parameters of the microprocessor unit 220 , such as the lead time after receiving a presence signal, turning on and off the detection function of the device 100 , turning on and off the alarms, etc. The control interface unit 250 can further connect a small-scale liquid crystal display (LCD) panel for showing the current status of the device 100 , for examining the parameter values, etc. The control interface unit 250 could also display alarm messages on the LCD panel.
[0049] As a typical manufacturing environment contains multiple assembly lines and each assembly line contains multiple work stations, it could be rather time consuming and laborious to configure and monitor the device 100 at each work station. Therefore, FIG. 4 a shows another embodiment of the microprocessor circuit 200 , which contains an addition network interface unit 260 . The network interface unit 260 connects a network interface 140 of the device 100 and the input and output terminals of the microprocessor unit 220 for two-way data exchange. The network interface 140 provides the physical connection to an external network 300 , which could be a wired local area network conforming to the 802.11x specifications, or a control network conforming to the RS-485, Lonworks, etc. specifications, to name just a few. Depending on the requirement of the network 300 , the network interface 140 should have a compatible physical connection means (such as an RJ-45 socket for hooking onto a local area network). Then, as shown in FIG. 4 b, the devices 100 at different work stations can be remotely monitored by a centralized console 400 through the network 300 . Therefore, when the microprocessor unit 220 is triggered due to an abnormal resistance found on the loop, the microprocessor unit 220 not only activates the alarm unit 230 to issue visual or audio alarms, but also sends a message via the network interface unit 260 and the network 300 to the console 400 . In alternative embodiments, the console 400 could periodically poll and communicate with the microprocessor unit 220 of each device 100 to obtain the status (e.g., whether an abnormal condition in the discharge circuit is detected) thereof. The console 400 could also configure the parameters, turn on and off the detection function, etc. of all devices 100 simultaneously, or of a specific device 100 individually.
[0050] Please note that what is shown in FIG. 4 b is a wired network in a bus architecture. It should be readily understandable that the present invention is applicable to networks of different architectures such those involve network switches and hubs. To extend even further, the network interface unit 260 could contain a wireless transceiver and the network 300 is a wireless local area network conforming to the 802.11a/b/g standard. In other words, the present invention does not pose specific requirement on whether the network 300 is wired, wireless, or adopting a specific protocol.
[0051] In FIG. 4 b, the network interface 140 for connection to the network 300 and the interface 150 for sharing ground and electricity are implemented separately. As shown in FIG. 4 c which depicts another embodiment of the present invention, the network interface 140 could actually be integrated into the interface 150 , and the cable 700 not only carries the ground and electricity, but also provides two-way data exchange. For example, the interface 150 could be an RJ-45 socket having eight terminals and the cable 700 is an eight-wire twisted-pair cable. Among the eight terminals and wires, four could be used for data transmission and two of the remaining four are for ground and electricity. The details should be rather straightforward for a person skilled in network cabling and therefore are omitted here. Please note that, in the above example, since separate wires and terminals are employed, the cable 700 and the cable 710 for connection to the external power supply could actually be implemented using same kind of cable. In the embodiment shown in FIG. 4 d, the external power supply 60 is further omitted and the console 400 now is also responsible for the provision of electricity (i.e., the external power supply 60 and the console 400 are integrated together into a single device). Please note that, in FIGS. 4 b to 4 d, each device 100 is still connected to the earth ground 50 but these connections are not drawn for simplicity.
[0052] As mentioned earlier, each device 100 's two interfaces 150 could be used interchangeably; there is no requirement which one should be connected to a previous device 100 or a successive one along the chain. However, in the embodiment shown in FIG. 4 c, usually one interface 150 is specified for connection to the previous device 100 (e.g., one farther away from the console 400 ) and the other interface 150 is specified for connection to the successive device 100 (e.g., one closer to the console 400 ). The purpose of having such a sequential ordering is that, when the console 400 has learned that one device 100 is detecting abnormal condition, the console 400 is able to locate the specific device 100 through the foregoing sequential ordering of the devices 100 . This would be very convenient for maintaining and managing the system of FIG. 4 c. For those who are familiar with such daisy-chain configuration, the implementation details should be quite straightforward.
[0053] Despite that wrist straps are the most common ground mechanism, and that the proper wearing of the wrist strap has been described so far as the main detection target of the grounding monitoring device, it has to be pointed out that the spirit of the present invention is not limited to the wrist strap only. The present invention could actually be applied to any grounding mechanism that employs two conducting wires to contact two separate spots of the human body to discharge the static electricity. Additionally, the present invention could further be applied to the monitoring of grounding mechanisms using a single conducting wire. This is another major characteristic differentiating the present invention from the previous application.
[0054] As shown in FIG. 5 a, a single-wire wrist strap 30 is usually used along with a grounded and conductive floor 90 . The operator 80 wearing the wrist strap 30 usually also wears a shoe strap 33 to facilitate the static discharge. The device 100 of the present embodiment is basically identical to the monitoring device for two-wire grounding mechanisms. However, an appropriate plug or connector is required so as to connect the single conducting wire 32 of the wrist strap 30 to an appropriate terminal of the interface 110 . FIG. 5 b depicts another embodiment where an interface 160 specifically for connection to a single-wire grounding mechanism is adopted. By comparing FIGS. 5 a and 5 b, the interface 160 also lacks the internal connection to the interface 120 .
[0055] As denoted by the dashed lines of FIGS. 5 a and 5 b, the loop monitored by the device 100 is constituted by the wire 32 , the wrist strap 30 , the body of the operator 80 , the conductive floor 90 , the earth, and the microprocessor circuit 200 . In other words, the device 100 monitors the resistance seen between the wire 32 and the interface 120 . Therefore, unlike the monitoring of a two-wire grounding mechanism where the loop is completed within the device, the monitoring of a single-wire grounding mechanism, the loop actually runs through the earth. Other than the foregoing differences, the devices 100 for two-wire grounding mechanisms and for single-wire grounding mechanisms could be completely identical. Please note that the backup grounding, the way the static electricity discharges, monitoring additional grounding mechanisms by series or parallel connection, networking multiple monitoring devices, wireless detection of the presence of the operator, etc., as detailed earlier could all be applied to the devices 100 of FIGS. 5 a and 5 b as well. Furthermore, a single device 100 could connect and monitor both single-wire and two-wire grounding mechanisms simultaneously. These variations should be easy to extend from the aforementioned embodiments.
[0056] Although the present invention has been described with reference to the preferred embodiments, it will be understood that the invention is not limited to the details described thereof. Various substitutions and modifications have been suggested in the foregoing description, and others will occur to those of ordinary skill in the art. Therefore, all such substitutions and modifications are intended to be embraced within the scope of the invention as defined in the appended claims.
|
The present invention provides a device to monitor whether a work station operator has properly worn a grounding mechanism, and a novel cascading means to chain multiple devices into a chain for sharing electricity and ground. The present invention could achieve the following functions: (1) capable of monitoring both single-wire and two-wire grounding mechanisms; (2) providing backup grounding through the chain so that the static electricity discharging capability is maintained as long as a single device in the chain remains connected to the ground; (3) extending the ground through the chain so that grounding is not required to be previously prepared at every work station; (4) sustaining all devices on the chain by a single external power supply; and (5) providing networking connectivity through the chain's cascading cables so that the network cabling cost and effort is significantly reduced.
| 6
|
BACKGROUND OF THE INVENTION
This invention relates to a filter with a filter element for screening the oil of an internal combustion engine and, more specifically, to a filter in which valve means control the flow of oil between the inlet and outlet of the filter.
Most prior filters of the type with which the invention is concerned have two separate valves. One valve is a flow control valve which causes the oil to enter the filter at one location and discharge from another location after flowing through the filter element and which holds oil in the filter when the engine is shut down. The second valve is a pressure relief valve which, under certain conditions, causes the flow to bypass the filter element altogether and to pass directly from the inlet to the outlet of the filter.
While most commercially available filters utilize separate flow control and pressure relief valves, there are filters in which the valve functions are combined into a unitary structure. Typical of a filter with a multiple function valve is that disclosed in Thornton et al U.S. Pat. 3,567,022. The multiple function valve structure of the Thornton et al patent, however, is relatively complex and is comparatively expensive to manufacture and assemble.
SUMMARY OF THE INVENTION
The general aim of the present invention is to provide a filter having a new and improved multiple function valve which is of relatively low cost as a result of having fewer components than prior multiple function valve structures and as a result of those components lending themselves to extremely quick and easy assembly.
A further object of the invention is to provide a filter with a multiple function valve which seals more effectively than prior valves and reduces the likelihood of oil bypassing the filter element under normal operating conditions.
Still another object is to provide a multiple function valve which remains reliable and trouble-free over the expected life of the filter.
A more detailed object of the invention is to achieve the foregoing through the provision of a novel multiple function valve having three primary components, namely, a flexible one-piece valve member, a valve seat and a spring for urging the valve member into sealing engagement with the valve seat.
These and other objects and advantages of the invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevational view of an oil filter equipped with a unique multiple function valve incorporating the unique features of the present invention, portions of the filter being broken away and shown in section.
FIG. 2 is a fragmentary end view of the filter as seen from the left of FIG. 1.
FIG. 3 is a view similar to FIG. 1 but shows the filter attached to an engine and with the valve permitting normal flow through the filter.
FIG. 4 is an enlarged view of certain parts shown in FIG. 3.
FIG. 5 is a view similar to FIG. 4 but shows the valve positioned to cause oil to bypass the filter element of the filter.
FIG. 6 is an end view of the member which defines the valve seat.
FIG. 7 is a cross-section taken along the line 7--7 of FIG. 6.
FIG. 8 is an end view of the valve member.
FIG. 9 is a cross-section taken along the line 9--9 of FIG. 8.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
For purposes of illustration, the invention has been shown in the drawings as incorporated in an oil filter 10 of the type used on an internal combustion engine. The filter includes a sheet metal housing 11 which is generally in the shape of a deep can, the housing having a cylindrical side wall 12 and an end wall 13 integral with one end of the side wall. Seamed to the opposite end of the side wall 12 is an annular sheet metal retainer 14 for a sealing ring 15.
When the filter 10 is attached to the engine, the ring 14 seals against an adaptor 17 (FIG. 3) having an inlet passage 18 for conducting oil to the filter and an outlet passage 19 for returning oil from the filter to the engine. The outlet passage 19 is defined in part within a threaded fitting 20 which is an integral part of the adaptor 17 and which projects axially toward the filter.
Disposed within the housing 11 is a tubular filter element 21 consisting of two end caps 22 and 23, a perforated inner core 24 and a suitable filter media 25 sandwiched between the caps and captivated against the core. The core 24 defines the inner wall of the filter element 21 while the outer wall of the element is defined by the outer side of the filter media 25. A coil spring 26 is compressed between the end cap 23 and the housing end wall 13 and urges the filter element toward the adaptor 17.
In filters of the same general type as the filter 10, it is conventional to control the flow of oil between the inlet 18 and the outlet 19 of the adaptor 17 in accordance with prevailing engine conditions. When the engine is shut down, oil is prevented from draining from the filter to the inlet 18 in order to retain oil in the filter. Under normal running conditions, oil is forced to flow from the inlet 18 to the outlet 19 by way of the filter element 21 so as to cause the filter element to screen contaminants from the oil. If the engine is started at very low temperatures or if the filter element 21 is heavily plugged, oil bypasses the filter element altogether and flows directly from the inlet 18 to the outlet 19 in order to insure an adequate and continuous supply of oil to the engine.
In accordance with the present invention, an extremely simple and inexpensive multiple function valve 30 is incorporated in the filter 10 to cause the oil to flow through the filter element 21 under normal conditions, to cause the oil to bypass the filter element during abnormal conditions, and to retain oil in the filter when the engine is shut down. The multiple function valve of the invention is particularly characterized in that it is made up of relatively few parts which may be made and assembled at comparatively low cost.
More specifically, the valve 30 coacts with a specially configured end plate 31 which is located within the housing 11 adjacent the retainer ring 14. The plate may be stamped from steel or molded of suitable plastic and is located with its outer peripheral portion positioned adjacent the inner side of the housing wall 12 and in engagement with the inboard face of the retainer 14. The plate is annular and is formed with an internally threaded hub 32 which receives the fitting 20 of the adaptor 17 to enable the filter 10 to be screwed onto the adaptor.
As shown in FIGS. 2 to 4, that portion of the plate 31 immediately adjacent the hub 32 is generally frustoconical in shape and is formed with several (herein, six) angularly spaced inlet openings 33. The inlet openings communicate with the inlet 18 of the adaptor 17 and serve to admit oil into the filter housing 11.
Pursuant to the invention, the valve 30 includes a novel valve seat 35 (FIGS. 4 to 7) preferably made of plastic and having a central sleeve 36 which is telescoped over the hub 32 of the plate 31. A radially outwardly extending flange 37 is molded integrally with the sleeve 36 about midway between the ends of the valve seat 35. Projecting axially from the flange and into the core 24 of the filter element 21 is another sleeve 38 formed integrally with the sleeve 36 and having inside and outside diameters somewhat smaller than those of the sleeve 36.
Further in keeping with the invention, the valve 30 includes a uniquely shaped valve member 40 (FIGS. 4, 5, 8 and 9) which coacts with the plate 31 and the valve seat 35 to control the flow of oil through the filter 10. The valve member 40 is molded of rubber or other resiliently yieldable material and is in the form of a ring which is telescoped over the sleeve 38 to hold the valve member centered in assembled relation with the valve seat 35. The valve member includes an intermediate section 41 disposed in a radial plane and sandwiched between the end cap 22 and the flange 37. An annular bead 42 projects from the outboard face of the valve member intermediate section 41 and hugs the peripheral edge of the flange 37 to help keep the valve member 40 in a centered position relative to the valve seat 35.
The valve member 40 includes a first valve portion or flapper 44 which is defined by an annulus of the inner peripheral portion of the valve member. The inner edge of the flapper 44 encircles the sleeve 38 while a generally V-shaped groove 45 is formed in the valve member at the outer periphery of the flapper. Normally, the flapper lies in the same radial plane as the intermediate section 41 of the valve member (see FIG. 4) but, by virtue of the groove 45, the flapper may swing out of the plane of the intermediate section to the hinged position shown in FIG. 5. Swinging of the flapper to its hinged position is resisted by a coiled compression spring 46 which preferably is conical in shape. The end coil at the small end of the spring seats in a groove 47 (FIG. 9) in the adjacent face of the flapper 44 while the end coil at the large end portion of the spring seats in an annular channel formed in a sheet metal collar 48 (FIG. 4) which is integral with the inner margin of the end cap 22. The inner periphery of the collar is defined by an axially extending lip 49 which tightly engages the sleeve 38 of the valve seat 35. An outwardly projecting annular bead 50 is formed around the inboard end of the sleeve and is engaged by the free edge of the lip 49 so as to keep the valve seat in assembled relation with the collar. Assembly of the valve seat 35 with the collar 48 may be effected simply by slipping the sleeve 38 endwise into the collar to cause the bead 50 to slip past the lip 49 with a snap fit. Once the assembly is achieved, it is virtually impossible to extract the valve seat from the collar.
The valve member 40 is completed by a second valve portion 55 (FIGS. 4, 5, 8 and 9) which is defined by a generally frustoconical skirt formed integrally with the valve member intermediate section 41 and projecting from that section toward the end plate 31. The skirt 55 normally lies along a frustoconical sealing rib 56 (FIGS. 4 and 5) formed on the inboard face of the end plate 31 just outside of the inlet holes 33. By virtue of the resiliency of the rubber, the skirt 55 is biased into sealing engagement with the surface of the rib 56 while a bead 57 on the outer periphery of the skirt is biased into sealing engagement with the inboard face of the plate 31. The skirt may, however, yield and swing from the position shown in phantom in FIG. 4 to the position shown in full, the skirt hinging relative to the intermediate section 41 along a line just outwardly of the bead 42.
When the engine is not running, the valve member 40 of the filter 10 is positioned as shown in FIG. 1. In this position, the spring 46 urges the flapper 44 into face-to-face sealing engagement with the flange 37 of the valve seat 35 and causes the flapper to close off a series of four angularly spaced passages 60 (FIGS. 4 to 7) formed through the flange. In addition, the memory in the rubber of the valve member 40 biases the skirt 55 and the bead 57 of the valve member into sealing engagement with the rib 56 and the plate 31, respectively. As a results, there is no path for oil to flow from the filter housing 11 to the inlet openings 33 and thus oil is retained in the filter 10 for immediate supply to the engine when the engine is next started.
Under normal running conditions, the oil at the inlet openings 33 is pressurized and acts against the skirt 55 and causes the skirt to hinge from the closed position shown in FIG. 1 to an open position shown in FIGS. 2 and 3. This enables oil to flow around the skirt 55 to the outer wall of the filter element 21, through the filter media 25 and the inner core 24 and then back to the engine's crankcase by way of the tubular valve seat 35 and the outlet 19 in the adaptor 17. As long as normal operating conditions prevail, the spring 46 keeps the flapper 44 sealed against the flange 37 and thus the passages 60 are sealed closed.
The flapper 44 opens the passages 60 and serves as a relief valve under certain conditions. For example, in cold weather, the filter media 25 may remain packed with contaminants for a relatively long period of time thus setting up a relatively high differential pressure between the pressure at the inlet openings 33 and the pressure at the interior of the core 24. Also, such a high pressure differential may exist in neglected use of the filter beyond its capacity to retain contaminants. Under such circumstances, the pressure at the inlet openings 33 becomes sufficiently high to overcome the force of the spring 46 and thus is effective to swing the flapper 44 to an open position as shown in FIG. 5. When the flapper is open, oil may flow through the passages 60 and may pass directly to the outlet 19 by way of angularly spaced ports 61 formed through the sleeve 38 of the valve seat 35. Thus, the filter element 21 is bypassed and oil is pumped directly to the engine so as to insure a continuous and adequate supply of oil to the engine even under abnormal operating conditions.
From the foregoing, it will be apparent that the present invention brings to the art an oil filter 10 having a very simple valve 30 which performs multiple functions. The valve consists of essentially three parts (the valve seat 35, the valve member 40 and the spring 46) which may be assembled quickly and easily with the end cap 22 and the plate 31 present in many conventional filters. Such assembly is effected by telescoping the valve member 40 and the spring 46 onto the sleeve 38 of the valve seat 35 in that order and by telescoping the sleeve 36 of the valve seat 35 onto the hub 32 of the plate 31. The subassembly then is moved into the housing 11 to cause the sleeve 38 to snap through and be held by the collar 48. The retainer ring 14 then is seamed to the housing in a conventional manner. Although the retaining ring is seamed, the components of the valve 30 itself may be assembled without need of pre-fabrication or without need of assembly steps such as welding, seaming or crimping requiring external energy sources.
The foregoing advantages are attained without compromising the overall integrity of the filter 10 since the valve 30 has fewer components and thus effectively reduces the chance of inadvertent oil passage through areas other than the filter media 21. Moreover, improved sealability of the components is achieved in that mating, sealing contact surfaces of the valve member 40 and the valve seat 35 are configured to maintain a continuous seal during operation until such time that the dynamic segments 44 or 55 of the valve react to pressure forces. After reaction to pressure forces or during system shut-down periods, the dynamic portions 44 and 55 of the valve member 40 return to their original molded shape and proper seal location. The static portion 41 of the valve member remains in sealed contact with the flange 37 of the valve seat 35 during all functions and operation. Accordingly, the flow control and the pressure relief functions are performed in a manner that is trouble-free and reliable for the expected life of the filter. The valve seat 35, the valve member 40 and the spring 46 are engaged in such a manner as to preclude disassembly prior to, during and after service of the filter.
|
An elastomeric valve member coacts with a valve seat and an apertured plate to control the flow of oil between the inlet and outlet of an oil filter for an internal combustion engine. When the engine is shut down, the valve member seals against both the valve seat and the plate to hold oil in the filter and prevent such oil from returning to the crankcase via the inlet. Under normal running conditions, the valve member unseals with respect to the plate to permit oil to flow between the inlet and outlet by way of the filter element of the filter. If the pressure differential between the inlet and the outlet exceeds a predetermined value, the valve member unseals with respect to the valve seat to enable the oil to bypass the filter element and to flow directly from the inlet to the outlet.
| 1
|
BACKGROUND OF THE INVENTION
The present invention relates to multiplexed telemetering systems and, in particular, to low-power bio-telemetry systems for obtaining EEG and other physiological data.
In recent years, a number of telemetry systems have been developed for obtaining physiological data from conscious, unrestrained individuals or animals. For the most part, the development effort has been directed toward the problem of providing compact, lightweight and low-power equipment which can be mounted, for example, on the individual's head with the individual free to move about unencumbered by trailing wires and other disturbing influences. Examples of such prior systems are described in the following publications: "A Four Channel Integrated Circuit Telemeter for Seizure Monitoring", R. W. Vreeland and C. L. Yeager, Digest of 7th International Conference on Medical and Biological Engineering, 1967, Stockholm, Sweden; "A Compact Six-Channel Integrated Circuit EEG Telemeter", Vreeland, Yeager and Henderson, Jr., Electroencephalography and Clinical Neurophysiology, Elsevier Publishing Company, Amsterdam, 1971, 30:240-245; and "A Multichannel Implantable Telemetry System", Medical Research Engineering, March-April, 1969 by Fryer, Sander and Datnow.
Although these prior systems have been most helpful, there is a continuing need for improvement. In particular, it is highly desirable to provide bio-telemetric systems which can be physically mounted on the subject to be studied and which then are capable of continuously operating for unusually long periods of time without any need for battery changes or other similar maintenance. As will be appreciated, the desire for a lengthy period of undisturbed operation is based upon the benefits which result when the subject of the study is permitted to function throughout the entire period in an undisturbed and unrestrained manner. Obviously, the long periods require the development of systems having unusually low-power consumption. In particular, the power consumption should be such that the need for battery changes can be avoided at least for overnight periods and, preferably, for periods extending for several or more days. Aside from the need for the longer operating periods, other recognized needs include the provision of more available channels for the studies as well as a reduction in the size of the instrumentation and the simplicity of its circuitry. In conventional multi-channel systems one of the factors contributing to power consumption is a separate amplifier for each of the channels with the multiplexing being performed subsequent to the amplification. Such arrangements apparently have been considered necessary to obtain a suitable signal level for the multiplexing. As will be described, a feature of the present system is the use of a single amplifier for all channels. In other words, the present system permits multiplexing at the amplifier input. However, this type of multiplexing imposes another problem in that the gating pulses needed to establish the channels then may be coupled into the channels. This undesired coupling will be recognized as unacceptable when it is considered that, for example, the gating pulses may be in the order of 6 volts while the data sample signals which are to be measured and analyzed by the system may be about 100μv. Such a signal to noise ratio effectively denies the production of any worthwhile data.
The present invention resolves this transient coupling problem by employing special complimentary, metal oxide semiconductor (C/MOS) switches to perform the multiplexing prior to amplification by a single amplifier. As is known, the C/MOS switches utilize and "N" channel FET in parallel with a "P" channel FET and the enabling or gating of these C/MOS switches requires pulses of opposite polarity. Because of the opposite polarity, the portions of the gating pulses that otherwise would be coupled into the channel are effectively cancelled. The invention further employs a particular pulse position modulation for the amplified output as well as other particular features which significantly reduce the power requirements. For example, the system employs a clock-controlled shift register to provide a synchronizing interval or spacing as contrasted with the need for a separate synchronizing pulse.
DETAILED DESCRIPTION OF THE DRAWINGS
The invention is illustrated in the accompanying drawings of which:
FIG. 1 is a schematic block diagram of the present system;
FIGS. 2 and 3 are circuit diagrams of the battery connector arrangement of the system, and
FIG. 4 is a circuit diagram of a suitable transmitter.
DETAILED DESCRIPTION OF THE INVENTION
The present system is particularly adapted for use in depth electrode studies of epileptics. However, because DC amplification is employed, it can be used to telemeter such data as temperature, respiration, blood flow, blood pressure, the electrocardiogram and galvanic skin resistance, as well as the electroencephalogram. Appropriate imput transducers, of course, must be used. Also, in scalp electrode recording, as contrasted with depth electrodes, low level pre-amplifiers should be used and these amplifiers may be of the type shown and described in the Vreeland et al publication entitled "A Compact Six-Channel Integrated Circuit EEG Telemeter".
Physically considered, the system is capable of being packaged in a relatively small, compact arrangement which, for example, may be in the form of two plastic boxes glued together in an open book configuration. Each of the packages, for example, may be about 1.2 cm × 3.5 × 4.5 cm boxes. Such a configuration is designed to fit under the outer head bandages of an epileptic with implanted depth electrodes.
The system is battery powered preferably by a plug-in battery pack which may consist of 10 Burgess CD2 cells potted in epoxy in a 1.7 cm × 3.2 cm × 3.8 cm box. Longer battery life can be achieved by using disposable mercury batteries, such as two Burgess H146X batteries. Such disposable mercury batteries, for example, have been operated continuously for a period of about 13 days and nights. However, a battery pack using the rechargable cells will provide up to 18 hours of continuous operation. To couple the battery power, ten SM3S Winchester connectors (FIG. 2) can be used along with mating SM3P Winchester plugs (FIG. 3). Preferably other connectors are used for the electrodes which may be either needle or disc.
The system is, as already stated, a multi-channel system deriving its input from a number of selectively located electrodes. Each pair of electrode, of course, represents a separate channel having input conductors 1 and 2 as shown in FIG. 1. The illustrated implementation is for a nine channel system, although the number of channels can be increased or decreased as desired. Further, the system is designed for bipolar as well as monopolar recording from all nine channels and, for this reason, differential inputs are provided for each channel. FIG. 1 illustrates only one channel since the remaining eight channels essentially are duplicates. Further, each channel can be coupled to AC or DC. However, when the system is to be used for monitoring low frequency phenomena non-polar input blocking capacitors such as capacitors C 1 and C 2 can be used. Before considering the circuit details it may be helpful to generally review and identify the major components of the system. Accordingly, as shown, differential electrode inputs are applied through conductors 1 and 2 to a pair of switches 3 and 4 which are of the C/MOS type having the N and P characteristics already briefly considered. The arrangement utilizes nine pair of switches 3 and 4 to gate electrode data samples through conductors 6 and 7 to a single broadband amplifier arrangement which includes amplifiers 8 and 9, and a differential amplifier 11. As will be noted in FIG. 1, conductors 6 and 7 are coupled to all of the other switches through conductors x and z. Thus, multiplexing is achieved at the input of the broadband amplifier or, in other words, only one broadband amplifying means is required for this system. The output of differential amplifier 11 is applied through conductor 13 to another C/MOS switch 15 that gates the amplified pulse train derived from the differential amplifier to a driver amplifier 12 by way of conductor 14.
Driver amplifier 12 applies its output through conductor 17 to a comparator 16 which is provided with the customary pair of inputs one of which is the inverting input derived from driver amplifier 12. This input sets a reference level for the comparator. The function of the comparator is to compare the reference level with an input derived from a ramp generator 18 through input conductor 19. When the ramp applied to the comparator through conductor 19 runs up to the level of the reference established by the driver amplifier, the comparator flips to a positive output which removes a holdoff bias applied to ramp generator 18 by an N-channel Motorola NMT 3823 field effect transistor 21 which resets the ramp generator. A capacitor C6 determines the positive output pulse duration of the voltage comparator. This arrangement of the driver amplifier, the comparator and the ramp generator constitutes pulse position modulation of the sequential pulse train derived from the pulse samples. Operationally considered, the reference level of the comparator is set by the instantaneous amplitude of the data being sampled so that variations in the time required for ramp to run up to the fixed reference level will vary only in accordance with the amplitude of the data sample or, more specifically, with the amplitude of each pulse in the data sample pulse train. Consequently, the positive short pulse outputs of the comparator are variably positioned in time in a manner that is directly proportional to the amplitude of the data sample. Thus, if the system is employing a sampling rate of 312 pulse trains per second which, as will be explained, is the intended sampling rate of the system, output pulses of the comparator can be quite short. A particular advantage of this ramp-generated pulse modulation technique is its low duty cycle which materially reduces power consumption.
The pulse train output of comparator 16 is identified in the drawing as pulse input Y coupled to a shift register 22 through a gating arrangement including gates 23, 24 and 26. Gate 24, as shown, is coupled directly to a so-called register `shift` input while gate 26 provides an input for a so-called `reset` register position. A clock arrangement including gates 27 and 28 is operated as a free-running or astable multivibrator to control the sampling rate of the system which, as has been stated, may be in the order of 312 pulse trains per second.
It will be noted that register 22 provides ten output positions numbered o-9 which also are identified as `N` outputs. These `N` outputs each are coupled to the pairs of switches represented in FIG. 1 by switches 3 and 4 and their function is to trigger the switches by providing switch-enabling pulses. If for example, it is considered that the pair of switches 3 and 4 represents channel 1 of the system, the arrangement may be one in which the `O` on the shift register turns on channel 1, while the `1` of the register turns on channel 2, etc. As will be explained, `9` on the register inhibits gate 24 so that no more pulses are transmitted until the shift register is reset.
Considering the shift register circuitry in greater detail, pulse input Y, prior to being applied to the register `shift` position is differentiated and inverted twice in gates 23 and 24 which, respectively, may be CD4001 and CD4000 components. Each pulse in pulse input Y triggers the shift register to shift it one step thereby enabling, as already stated, a different pair of amplifier input switches. The inverted output of gate 23 is applied as an input to gate 26, which also may be a CD4000 three input NAND gate, used to generate the reset pulse. NAND gate 26 generates the reset pulse only if all three of its inputs are "low", this requirement preventing premature resetting of the shift register. The inputs of gate 26 are, as stated, the inverted input from gate 23 as well as a clock input which has been differentiated and inverted in a gate 29. As shown, the output of gate 29 is applied through conductor 31 to gate 26. The third input for NAND gate 26 is a `carry` pulse which, in the present implementation is used to keep its input to gate 26 `high` during the first few shifts of the shift register. At a particular shift, such as the fifth shift the `carry` goes `low`. When the register shifts to position 9, pulse input Y as well as the `carry` input are `low`. Consequently, when the inverted clock pulse derived from gate 29 is applied to the NAND gate, the register resets to 0 to initiate a new train of pulses. This arrangement is advantageous particularly since it permits the use of a synchronizing space or time interval in contrast to a specially generated synchronizing pulse which normally is used but which serves only to further complicate the circuitry and add to the power requirements. The clock, of course, controls the synchronizing space interval and, in doing so, maintains the desired 312 pulse trains per second sampling rate. It also will be noted that register 22 has an `inhibit`position coupled by conductor 32 to an inverter 33 which re-inverts the output of gate 29 of the clock arrangement. This `inhibit` pulse is used as an inhibit toggle after reset.
The modulated pulse train output from gate 24 is used to key a transmitter 34 shown in block form in FIG. 1, this output being applied to the transmitter by a conductor 36. A suitable transmitter circuit is shown in FIG. 4 and subsequently will be considered in some detail. As also will be noted, gate 24, in addition to re-inverting the output of gate 23, is a 3-input NAND gating component having inputs from gate 23 and from the `9` signal from the shift register. Thus, this gate is inhibited during the synchronizing interval of the register by the `9`signal from the register. It should be noted that an inhibit signal `C` simultaneously is derived from the register and that this inhibit `C` is applied to driver amplifier 12 to inhibit this amplifier during the syhchronizing interval.
Other inhibit signals identified in FIG. 1 as inhibit `A` and inhibit `B` are derived, respectively, from the pulse train arriving at gate 23 and from the inverted output of gate 23. In a manner that will be described, inhibits `A` and `B` are used to short circuit the input to broadband amplifier 8, 9 and 11 during the switching intervals and also during the switching intervals to remove switching transients from the output of the broad band amplifier. Inhibit A is applied to a switch 38 coupled between each pair of the input channel switches represented by switches 3 and 4. Inhibit `B` is a negative-going pulse applied to previously-identified switch 15 coupled between the broadband amplifier and driver amplifier 12.
Considered in greater detail, switch 38, which preferably is a C/MOS type of complimentary FET switching arrangement, is coupled between output conductors 41 and 42 of switches 3 and 4 respectively. Switch 15, in turn, is used to couple conductor 13 to driver amplifier 12. The need for switches and 15 and 38 becomes more apparent when it is recognized that the data sample signals which the system is attempting to detect and measure are at a level of about 10 μv while the gating pulse signals used to gate switches 3 and 4 are about 6 volts. Obviously, if any significant portion of the gating pulse is coupled into the channel it would create an impossible detection situation. In this regard, it should be kept in mind that the present system basically employs low level input switching and multiplexing at the amplifier input to achieve the low level switching, it is essential that the gating pulses effectively be removed rather than amplified. Gate 15 removes the remaining transients which, although quite small, nevertheless may be about 50 millivolts or about 500 times the data sample level being measured.
The ability to effectively remove the gating pulses and their transients from the channels is one of the features of the present invention and for the most part, the removal is achieved by the use of the complimentary, MOS/FET switches.
As is known, a complimentary MOS switch is a commercially-available component such as the R.C.A. CD 4016 switch. These switches are available as CD 4016 flat packs and, since each pack contains four switches, only five of the packs are required. The R.C.A. switches are known in the trade as "COS/MOS" switches. A more general designation is C/MOS. Each of the switches in the flat pack has an "N" channel FET in parallel with a "P" channel FET and the required gating pulses are of opposite polarity. Consequently, the portions of the gating pulses that are coupled into the channel effectively cancel. This effective cancellation apparently is not generally recognized but it has been found to be effective for use in circuitry such as that used in the present system. In particular, it should be noted that FET switches have been tried and found to be unsatisfactory. Apparently they permit the gating pulse to be coupled into the channel via the gate-channel capacitance. Thus, the capacity of the present system to remove the gating pulses from the channels is achieved primarily by the cancellation feature of the COS/MOS switches.
A further feature is that the switches are short circuited during switching intervals. As noted, the timing is achieved by the use of inhibit signal `A`. Also, the transient removal achieved by switch 15 is controlled by a negative-going pulse during the switching intervals. This combination of input short circuiting and output gating effectively removes all switching transients. The circuit arrangement for the C/MOS switches is generally illustrated in the drawing. As will be noted, the "N" pulses received as outputs from shift register 22 are applied to the "N" and "P" channels of each switch by conductors 43 and 44. The positive `N` input has its polarity reversed by an inverter 46 before being applied to the `P` channel of the switch.
Briefly summarizing, the present system combines a number of related features in such a manner that the power consumption can be unusually low so as to permit long, unattended periods of operation. The C/MOS switches permit low level switching prior to amplification by effectively cancelling the gating pulses. The single amplifier is a significant power conservation feature as is the modulation technique, the use of the register's synchronizing interval and the use of the clock-controlled register itself. Even so, it will be obvious that the obtaining of the maximum advantages also depends upon the selection of components. Some attention therefore should be directed toward the particular components.
As to the single broadband amplifier, the component used in the illustrated system is one having a frequency response from DC to better than 100 KHZ which is needed because multiplexing is done by switching the amplifier input. National Semiconductor NH0001ACF operational amplifiers may be used in a manner that, for example, provides a gain of about 120 with an input resistance of approximately 200 k ohms and a common mode rejection ratio of at least 60 dB. The common mode rejection is adjusted by selecting resistor 47 identified in FIG. 1. The use of a differential amplifier with good common mode rejection permits bipolar as well as monopolar recording from all nine channels.
As has been noted, the main amplifier consists of two operational amplifiers previously identified as amplifier 8 and 9 operating as followers with gain followed by a differential amplifier 11. Obviously, it is desirable to achieve the amplification with a minimum of power requirements and the components which have been described satisfy this purpose. A National Semiconductor LI 44 also can be used to advantage. Driver amplifier 12 is a non-inverting monopolar amplifier with selectable gain. The gain and DC bias are determined by resistors 48 and 49 which may be mounted on the SM3P Winchester plug shown in FIG. 3. This arrangement permits the system gain to be easily changed to accommodate different types of inputs signals.
The pulse position modulation achieved by comparator 16 and ramp generator 18 has been described in some detail and generally may be provided by conventional components. As has been indicated, its operation is one in which the comparator is saturated with a negative output until flipped to a positive output by the ramp following which positive feedback capacitor 51 holds the comparator for about 17 μs. This 17 microsecond pulse then passes through gates 23 and 24, already identified as NAND gates, to shift the register and key the transmitter. Resetting of the register to maintain the desired sampling rate is achieved by the clock provided by gates 27 and 28 and, as stated, the clock circuitry is in effect in astable multivibrator such as is described by J. A. Dean in RCA Application Note ICAN-12-67. As further shown in FIG. 1, the keyed transmission of the data sample pulse train in its modulated form is transmitted to an PPM receiver 52 which converts the pulse position modulation to pulse width modulation. A suitable receiver is an Astrocommunications Laboratory SR-209 with a 300 KHz bandpass. This receiver utilizes a shift register demodulator to convert the modulation to pulsewidth modulation and its arrangement is described in some detail in the previously referenced publication "A Compact Six-Channel Integrated Circuit EEG Telemeter". The output of the demodulator receiver is recorded and evaluated in any desired manner.
A suitable transmitter for use with the present system is shown in FIG. 4. Transmission is the major power consumer in the system and its power requirements should be minimized by arrangements employing, for example, a series switch to remove all power between pulses. Power is `on` for only very short pulses. Suitable transmitters are commercially available and one such transmitter is a Motorola MM4018 transistor operating as a power oscillator in the 88 MHz to 108 MHz FM broadcast band. The resulting low duty cycle pulse modulation greatly reduces the power consumption. As will be noted, all of the C/MOS circuits are powered by a positive 6.25 volt supply. The power sources may be connected in series to provide 12.5 volts for the transmitter. The same sources provide +6.25 volts and -6.25 volts for the operational amplifiers and, if used, for the scalp electrode preamplifiers.
The system performance for depth electrode recording when tested with a 10 k ohm source is: Crosstalk 30dB down, noise level 5 to 13 microvolts RMS (determined by noise level in the receiving amplifier), maximum input ±1 millivolt, frequency response 0.2HZ to 150HZ, input impedance 200K ohms, common mode rejection 60dB. With scalp electrode pre-amplifiers, the performance is: noise level one microvolt RMS, input impedance one megohm, and common mode rejection 70dB.
In actual operation, the described system powered by throwaway mercury batteries has permitted continuous use for a period of 13 days. Rechargeable batteries easily achieve unattended overnight operation and, of course, this period of continuous operation is dependant upon the type of battery used. Broadly considered, the improved operation achieved by the system is premised upon the low level switching which, in turn, is permitted by the use of the C/MOS switch arrangement. Nevertheless, the other components and their arrangements, such as the gating pulse and transient removal techniques, are important factors which contribute significantly to the ability of the system to detect the low level signals as well as its low power consumption capability.
Obviously many modifications and variations of the present invention are possible in the light of the above teachings. It is therefore to be understood that within the scope of the appended claims the invention may be practiced otherwise than as specifically described.
|
A low-power, transient-free, multi-channelled bio-telemetry system utilizes series of C/MOS switches coupled to the data sampling electrodes. Shift register pulses selectively enable the switches to sequentially shift the data sample inputs through nine, switch-controlled channels. The switches have little battery drain and, due to their N and P complimentary arrangement, their gating pulses are effectively cancelled and removed from the system channels. Multiplexing precedes amplification by applying switch outputs to a single, low-power amplifier. A special pulse position modulator employing a ramp generator circuit provides the pulse trains to a keyed transmitter. Other significant improvements including a unique shift register arrangement with a synchronizing interval permit long periods of continuous operation undisturbed by the need for battery changes. The transmitted data is received by a suitable demodulating receiver to produce a recordable output for evaluation and computer analysis.
| 8
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a device for transferring at least one toner image from a toner carrier belt onto a carrier material, whereby the toner carrier belt carries the toner image to be transferred and has a predetermined belt tension, and whereby the toner carrier belt, in a first operating status, is arranged close to the carrier material in the transfer area in order to transfer the toner image and, in a second operating status, is arranged at a predetermined distance from the carrier material in the transfer area in order to prevent a transfer of the toner image.
2. Description of the Related Art
Published PCT Application No. WO 98/39691 of the same applicant discloses a printer or copier for the performance-adapted monochromous printing and/or colored one-sided or two-sided printing of a recording medium. The device uses a transfer belt onto which toner images of different hues are superimposed onto one another in a first operating status. The overall toner image arising in this way by superimposition is subsequently transferred to the recording medium. In the collecting operating phase, the toner carrier belt is distanced from the carrier material so that a transfer of the sub-toner images is prevented. The transfer belt is arranged close to the recording medium when the collected overall toner image is transferred for transferring the overall toner image. The content of Published Application WO 98/39691, therefore, is incorporated by reference into the present patent application as disclosure content.
In the aforementioned device concept, the transfer belt therefore is removed from the carrier material at the transfer location given a stoppage of the printing operation and is moved again toward the carrier material when the printing continues. This back and forth motion must be smooth given the operating mode for multicolor printing, in particular, since a transfer printing process occurring at the same time between a photoconductor belt and the transfer belt for transferring a toner image is otherwise impaired—the toner image is blurred, for example. Traditional devices with belt tension devices are not without jerky movements in the toner carrier belt, however, so that belt tension changes lead to a lower printing quality.
German Patent A 42 10 077 discloses an image generation device having an electrostatic transfer device for a latent print image. A roller that can be pivoted via a mechanism serves the purpose of optionally causing contact between a transfer belt and a photoconductor drum.
German Patent A 41 39 409 describes a further image generation device having an electrostatic transfer printing device. A transport belt led via at least two rollers guides a print medium along a photoconductor drum. A latent print image thereby is transferred from the photoconductor drum onto the print medium.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a device for transferring at least one toner image from a toner carrier belt onto a carrier material, whereby a high printing quality is obtained even given a back and forth motion of the toner carrier belt in the transfer printing area.
This object is achieved by a device for transferring at least one toner image from a toner carrier belt onto a carrier material, wherein the toner carrier belt carries the toner image to be transferred and has a predetermined belt tension, the toner carrier belt is held by a belt drive guiding the toner carrier belt through a roller device in the transfer printing area in which the toner image is transfer-printed onto the carrier material, the toner carrier belt, in a first state, is arranged close to the carrier material in the transfer printing area in order to transfer the toner image and, in a second state, is arranged at a predetermined distance from the carrier material in the transfer printing area in order to prevent a transfer of a toner image, and wherein the belt tension in the toner carrier belt is essentially the same in the first and second operating state.
Further advantages of the invention are realized by the belt tension also being the same in the transitional phase from the first operating state to the second operating state. In a preferred embodiment, the roller device is moved back and forth at least approximately perpendicular relative to the carrier material given a change of the operating states.
Preferably, the roller device has one single transfer printing roller which is moved back and forth at least approximately perpendicular given a change of the operating states, the belt drive has a stationary roller with a stationary rotational axis at both sides of the transfer printing roller, a movable compensation roller is respectively arranged between the stationary roller and the transfer printing roller, the respective distance between the rotational axes of the transfer printing roller and the compensation roller and the respective distance between the rotational axes of the compensation roller and the stationary roller remains constant in every operating state, and the diameters of the transfer printing roller, the compensation rollers and of the stationary rollers are of the same size. Specifically, the centers of the rotational axes of the transfer printing roller and the compensation rollers, as well as the centers of the rotational axes of the compensation rollers and the stationary rollers are connected to one another by rigid connecting-rod levers. The surface areas of the stationary rollers and of the compensation rollers may have contact with the toner carrier belt in both operating states and in the transitional phases. A movable cleaning roller of equal diameter may be arranged between the transfer printing roller and at least one of the compensation rollers, and the distance between the rotational axes of the transfer printing roller and of the cleaning roller, as well as the distance between the rotational axes of the cleaning roller and of the compensation roller remains constant in every operating state. The centers of the rotational axes of the transfer printing roller and of the cleaning roller, as well as the rotational axes of the cleaning roller and of the compensation roller are connected by rigid coupling elements.
As a preferred development, the rotational axis of the transfer printing roller is connected to a driving device which, in a linear motion, moves the rotational axis back and forth in an approximately perpendicular manner relative to the carrier material. The driving device may contain a switching eccentric. Alternatively, the rotational axis of the cleaning roller is connected to a further driving device moving the cleaning roller back and forth in a linear motion.
The toner carrier belt may be constructed to engage with a cleaning station or be removed from the cleaning station when the cleaning roller is moved back and forth.
The roller device of one embodiment is driven during its back and forth motion by the control surface of a rotating radial cam, at least one compensation roller is moved back and forth during the rotation of the radial cam, and the difference in length of a belt backlash, given the motion of the roller device, is compensated by the motion of the compensation roller. The roller device may contain two transfer printing rollers which are simultaneously moved back and forth by the control surface of a radial cam, each transfer printing roller having one compensation roller allocated to it, which is moved back and forth by the control surface of a radial cam. The transfer printing rollers and the compensation rollers that are respectively allocated to them are driven by the same radial cam. The radial cams are symmetrically rotated in preferred embodiments, or the radial cams can be asymmetrically rotated.
In one embodiment, the roller device can be moved in the direction of a guide bar, two tension rollers are symmetrically arranged relative to the guide bar, whereby the tension rollers are respectively connected by swivel arms to one end of the guide bar and by respectively one connecting rod to a sliding piece, which can be moved back and forth on the guide bar, and the tension rollers are charged with equal forces for pressing against the toner carrier belt.
A spring pressing against the sliding piece can be arranged on the guide bar. The roller device contains two transfer printing rollers that are symmetrically arranged relative to the guide bar. The belt drive may have two stationarily arranged deviation rollers for the toner carrier belt at both sides symmetrically relative to the center line of the guide bar, and the deviation rollers are of equal diameter. The belt drive of the preferred development does not contain additional tension elements apart from the two tension rollers.
In the first and second operating states, the belt tension in the toner carrier belt is inventively kept constant. The length of the toner carrier belt does not change as a result and belt tension spikes are prevented. Given simultaneous transfer printing of a toner image onto the toner carrier belt at a second transfer area, the environmental conditions in this transfer area remain constant and a high printing quality can be obtained as a result of the constant belt tension.
Advantageously, the belt tension in the toner carrier belt also remains the same in the transitional phase from the first operating state to the second operating state and vice versa. This means that the transport motion of the belt can also be maintained during this transitional phase without reducing the quality given simultaneous transfer printing of a toner image onto the toner carrier belt.
A transfer belt is to be preferably provided as a toner carrier belt, whereby a toner image is transferred, in a transfer printing process, from a toner image generation device, such as a photoconductor drum or a photoconductor belt, onto the transfer belt.
BRIEF DESCRIPTION OF THE DRAWINGS
Exemplary embodiments of the invention are subsequently explained on the basis of the drawings. Further advantages and features of the invention are described on the basis of these exemplary embodiments.
FIG. 1 is a side view which schematically shows a connecting-rod lever movement mechanism.
FIG. 2 shows a connecting-rod lever movement mechanism in a simplified perspective representation.
FIGS. 3 a and 3 b are schematic side views which show a movement mechanism with radial cams.
FIGS. 4 a and 4 b are schematic side views which show the radial cams according to FIGS. 3 a and 3 b in a different movement phase.
FIG. 5 is a side view which shows a further exemplary embodiment with tension rollers.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows a first exemplary embodiment of the invention in a simplified schematic representation. A toner carrier belt fashioned as a transfer belt 10 is guided around rollers of a belt drive, which is generally referred to as 12 . FIG. 1 only shows one part of the belt drive 12 and of the transfer belt 10 . The transfer belt 10 is guided around a roller device 13 with one single transfer printing roller 14 , whose rotational axis 16 , with the assistance of a longitudinal guide 18 and a driving device, can execute back and forth motions approximately perpendicular relative to a carrier material 22 , generally single sheets or belt material composed of paper. The driving device 20 contains a switching eccentric 24 , for example, whereby the rotational axis 16 moves back and forth in the direction of the arrow P 1 when the switching eccentric is rotated.
The belt drive 12 contains two stationary rollers 26 and 28 whose rotational axes 30 and 32 are stationarily anchored at the frame of the belt drive 12 . Compensating rollers 34 and 36 , whose rotational axes 38 and 40 are mobile and can be moved in the direction of the arrows P 2 and P 3 , for example, are arranged between the transfer printing roller 16 and the stationary rollers 26 and 28 .
A mobile cleaning roller 42 , whose rotational axis 44 can be moved back and forth in the direction of the arrow P 4 by a further driving device 46 having a switching eccentric, is arranged between the transfer printing roller 14 and the compensating roller 34 . During this back and forth motion, the movable cleaning roller 42 with the transfer belt 10 is engaged or disengaged with respect to a cleaning roller 48 . This cleaning roller 48 serves the purpose of removing residuary toner material which is still present after the transfer printing on the transfer belt 10 .
The rotational axis 32 of the stationary roller 28 and the rotational axis 40 of the movable roller 36 are connected to one another by a rigid coupling element 50 , which can execute swivelling motions on the rotational axes 32 and 40 . This rigid coupling element 50 serves the purpose of keeping the distance between the rotational axes 32 and 40 in all operating phases constant. A rigid, pivotable coupling element 52 is also arranged between the rotational axis 40 of the movable roller 36 and the rotational axis 16 of the transfer printing roller 14 . A further rigid coupling element 54 is provided between the rotational axis 16 of the transfer printing roller 14 and the rotational axis 44 of the cleaning roller 42 . The rotational axis 44 of the cleaning roller 42 and the rotational axis 38 of the movable roller 34 are connected via a rigid coupling element 56 . Finally, the rotational axis 38 of the movable roller 34 is also connected to the rotational axis 30 of the stationary roller 26 via a rigid, pivotable coupling element 58 . The coupling elements 50 , 52 , 54 , 56 and 68 can be of different length. A critical feature of the invention is that the diameter of the rollers 26 , 28 , 34 , 36 , 42 and 14 is the same. The rotational axes 16 , 30 , 32 , 38 , 40 and 44 are arranged parallel to one another and reside perpendicular relative to the paper plane in FIG. 1 .
The transfer belt 10 is generally composed of a plastic material. A slight change in length of the transfer belt 10 , e.g. within the mm range, can arise as result of changes in humidity or temperature, for example. For compensating this change in length, a separate tension roller (not shown) can be provided. The roller 28 can also assume the function of a tension roller and can have an excursion of approximately 1 mm. The roller 28 , however, can still be considered stationary, since this excursion at the transfer printing location or, respectively, at the transfer printing locations, does not cause a change in location of the toner picture elements to be transferred with respect to the carrier material 22 or a photoconductor belt.
The functions of the arrangement are subsequently explained according to FIG. 1 . In the illustrated state of FIG. 1, the transfer belt 10 is kept in immediate proximity of the carrier material 22 given its forward motion in the direction of the arrow P 0 or, respectively, is in contact with this carrier material 22 . In this operating state, toner images, which are present on the transfer belt 10 in a relatively loose form and have not yet been fixed, can be transfer-printed onto the carrier material 22 . Given activation of the driving device 20 , a second operating state is adjusted, wherein the transfer printing roller 14 is upwardly moved in the direction of the arrow P 1 . The motion is transferred, by the coupling elements 50 , 52 , 54 , 56 and 58 , onto the movable rollers 34 , 36 and 42 when the transfer printing roller 14 is lifted. The stationary rollers 26 and 28 do not move. As it has already been mentioned, the coupling elements 50 , 52 , 54 , 56 and 58 are pivotably borne on the rotational axes 32 , 40 , 16 , 44 , 38 and 30 . The movable rollers 36 , 42 and 34 are predominately moved in the direction of the arrows P 2 and P 3 , since the cleaning roller is stopped and does not execute a movement in the direction of the arrow P 4 . Since the connecting-rod levers 50 , 52 , 54 , 56 and 58 extend exactly parallel to the corresponding sections of the transfer belt 10 , the diameters of the allocated rollers 28 , 36 , 14 , 42 , 34 and 26 are identical, a change in length in the transfer belt 10 does not arise, regardless of how large the stroke is by which the transfer printing roller 14 is lifted by the driving device 20 . This means that the belt tension in the transfer belt 10 is independent of this stroke and therefore remains constant. A spike or an additional force does not occur when the transfer printing roller 14 moves. Therefore, the belt tension also remains constant in the transitional phase between both operating states of the transfer printing roller 14 .
Independently of the motion of the transfer printing roller 14 , the driving device 46 can move the cleaning roller 42 back and forth in the direction of the arrow P 4 . The connecting-rod levers 58 , 56 and 54 then perform compensating motions assuring that the transfer belt does not become loose, so that the belt tension therefore also remains the same within the transfer belt 10 .
A number of advantages are achieved by the arrangement of FIG. 1 . Each time the transfer printing roller 14 moves, the arrangement of the connecting-rod levers 50 , 52 , 54 , 56 and 58 assures an exact allocation of the compensating rollers 36 and 34 to the transfer printing roller 14 . Mechanically complicated parts are not necessary; the effective mechanism of the arrangement is clear. The connecting-rod levers 50 , 52 , 54 , 56 and 58 assume the driving and guiding of the compensating rollers 36 and 34 . Only the transfer printing roller 14 and the cleaning roller 42 must be moved by a separate drive. The connecting-rod lever movement mechanism makes it possible to include a further swivelling motion of neutral length at a different location of the transfer belt 10 , as is shown in the example of the movable cleaning roller 42 which is separately driven by a drive 46 .
FIG. 2 shows a perspective representation of the movement mechanism of FIG. 1, whereby the same parts are referred to by the same reference character. In the arrangement of FIG. 2, the connecting-rod levers 54 and 56 are combined to one single connecting-rod lever 55 . It can be seen in FIG. 2 that connecting-rod levers are arranged on both sides of the rollers. The arrangement in FIG. 2 has corresponding connecting-rod levers 50 ′, 52 ′, 55 ′ and 58 ′ that are arranged in the back.
FIGS. 3 a and 3 b show another exemplary embodiment, wherein control cams are used. Parts that correspond to previous exemplary embodiments are referred to by the same reference characters. The transfer belt 10 is moved in the direction of the arrow P 0 by the belt drive 12 . At a first transfer printing location 60 , the toner image on a photoconductor belt 62 is transferred onto the transfer belt 10 . The transfer belt 10 is deviated at a deviation roller 64 and is guided past a first compensating roller 66 , which can be moved in the indicated arrow directions. The transfer belt 10 subsequently arrives at a second transfer printing area 68 , in which the toner image situated on the transfer belt 10 or the collected overall color toner image is transferred onto the carrier material 22 . The roller device 13 , which can be moved back and forth in perpendicular direction relative to the carrier material 22 , is arranged in the transfer printing area 68 . The roller device 13 has two transfer printing rollers 70 and 72 , which can be moved in the direction of the shown arrows. Subsequently, the transfer belt 10 is guided past a second compensating roller 74 , which can be moved in the direction of the shown arrows. The belt drive 12 contains a second transfer printing roller 76 at which the transfer belt 10 is deviated.
The deviation rollers 70 and 72 and the compensation rollers 66 and 74 are driven by control cams 78 and 80 , as can be seen in greater detail in FIG. 3 b on the basis of the control cam 78 . The control cam 78 has an elliptic control surface 82 and can be rotated around a rotational axis 84 . In the shown state, the deviation roller 70 is maximally downwardly excused, whereas the compensation roller 66 is maximally excused to the left. Given a clockwise rotation of the control cam 78 , the compensating roller 66 , in FIGS. 3 a and 3 b, is excused to the right due to the elliptic control surface 82 , whereas the deviation roller 70 moves upward given a corresponding pretension. If the compensating roller 66 was stationary, the transfer belt 10 wrapping around the two rollers 66 and 70 would become loose by a difference of length when the transfer printing roller 70 moves upward. The control surface 82 of the control cam 78 is arched such that the difference of length resulting from the upward motion of the transfer printing roller 70 is precisely compensated by the motion of the compensating roller 66 to the right. The resulting control surface 82 must not necessarily be elliptical but can also assume a different cam shape.
FIGS. 4 a and 4 b show the relationships when the radial cams 78 and 80 have rotated by 90° in a clockwise direction. The transfer printing roller 70 and the compensation roller 66 moved from the position which is shown in broken lines in FIG. 4 b to the position shown with solid lines. It can be seen in FIG. 4 a that the transfer belt 10 is lifted from the carrier material 22 in the shown state. In this state, a transmission of toner images onto the carrier material 22 is prevented; the transfer belt 10 and the carrier material 22 can have different speeds, whereby this is advantageous for starting the printing operation and for stopping the printing operation, since a relative motion can occur in these operating statuses. The control surface 82 of the radial cam 78 is preferably arched such that a length compensation for the transfer belt 10 ensues such that the difference in length of the transfer belt 10 , in the entire motion phase of the deviation rollers 70 and 72 and of the compensation rollers 66 and 74 , is compensated as a result of the back and forth motion of the deviation rollers 70 and 72 . In this case, belt tension modifications do not arise in the transfer belt 10 , so that a transfer printing can continue at the transfer printing location 60 without blur effects.
In the exemplary embodiment according to the FIGS. 3 a, 3 b, 4 a and 4 b, the two radial cams 78 and 80 are symmetrically rotated, whereby a symmetric motion process also results and the two deviation rollers 70 and 72 are swivelled in a parallel fashion. This exemplary embodiment according to the FIGS. 3 a to 4 b can be multiply varied. The radial cams 78 and 80 can be asymmetrically rotated, so that different asymmetrical swivel courses are obtained. For operating the roller pair deviation roller 70 and appertaining compensation roller 66 or, respectively, the roller pair deviation roller 72 and compensation roller 74 , a common radial cam 78 or, respectively, 80 or separate radial cams can be arranged on common or separate axes.
FIG. 5 shows a further exemplary embodiment of the invention, wherein spring-loaded tension rollers are used. The belt drive 12 transporting the transfer belt 10 has stationary deviation rollers 90 , 92 and 94 , two tension rollers 96 and 98 and a roller device 13 , which is composed of two transfer printing rollers 100 and 102 and which can be moved back and forth. The tension rollers 96 and 98 , by swivel arms 104 , 106 , are pivotably attached to a rigid rotational axis 108 at the end of a guide bar 110 . The rotational axes 112 and 114 of the tension rollers 96 and 98 , via connecting rods, are pivotally borne on a pivot 120 , which is attached to a sliding piece 122 . The sliding piece 122 can be moved along the guide bar 110 . The roller device 13 with the two deviation rollers 100 and 102 can also be moved along the guide bar 110 . The guide bar is stationarily fastened with respect to the belt drive 12 at the upper end in a rigid manner. A pressure spring 124 generates a pretension onto the sliding piece 122 . If the roller device 13 is now upwardly moved along the center line 126 , a belt backlash would occur in the transfer belt 10 given stationary belt rollers 96 , 98 . The pressure spring 124 downwardly pushes the sliding piece 122 along the guide bar 110 , whereby the connecting rods 116 and 118 symmetrically move the tension rollers 96 and 98 to the outside along an orbit, which is defined by the swivel arms 104 and 106 . It is thus prevented that a belt backlash arises. The transfer belt 10 is equally tensioned on both sides of the roller device 13 as a result of the symmetrical arrangement of the tension rollers 96 and 98 , the connection by the connecting rods 116 , 118 and the central spring 124 . Assuming that the transfer belt does not stretch itself, the actual belt length cannot change. It results therefrom that the individual picture elements on the transfer belt 10 move along the center line 126 and therefore perpendicular to the carrier material 22 at the transfer printing location 68 . It is thus ensured that the toner image is not blurred. Given swivelling-to and swivelling-from the roller device 14 onto the carrier material 22 , the printing image cannot become blurred. In order to obtain a symmetrical behavior, the two deviation rollers 92 and 94 are to be symmetrically arranged relative to the center line 126 . Due to the spring excursion, the belt tension can be slightly different in the printing transfer belt 10 in both operating modes; however, it is assured that the length of the transfer belt remains constant in both operating states with swivelled-to and swivelled-from roller device 13 .
Although other modifications and changes may be suggested by those skilled in the art, it is the intention of the inventors to embody within the patent warranted hereon all changes and modifications as reasonably and properly come within the scope of their contribution to the art.
|
A printer or copier has a toner transfer belt which is moved into an out of engagement with a transfer printing area. The toner transfer belt is carried on an arrangement of rollers that maintain a constant tension on the toner transfer belt. Rigid linking levers extend between the rollers of the roller arrangement so that belt tension is maintained by movement of compensation rollers, outward while moving a transfer roller upward, for example.
| 6
|
FIELD OF THE INVENTION
The invention relates to rug hooking devices and relates particularly to such devices in which the base material upon which the hooking operation is being performed may be positively held but incrementally fed as desired by the operator and further in which there is provided hold-down means for positive holding against fixed means a portion of said base adjacent that upon which the hooking operation is being performed.
BACKGROUND OF THE INVENTION
The so-called "hooking" of rugs is an old art and many devices have been proposed over the years for facilitating same. In a more recent development of this art, there has appeared a procedure wherein a sheet of flexible base material is provided with suitable openings therethrough, as by being woven with a large mesh, wherein the base material is fed to the operator under a controllable restraint and wherein the hooking operation is performed by introduction of the desired rug materials into and through such openings in said base. This development of the art has also given rise to a large number of devices by which the base material may be held and fed to the operator as desired with the finished portion of the rug then moving to some portion which is clear of the working zone. These devices in greater or less complexity have in the past provided means for holding the base material and incrementally feeding it into a working zone as required by the operator and they have done so with greater or less degrees of convenience to the operator. However, in the operation of rug hooking, it is further desirable to provide means for holding said base substantially immovably in a zone close to the working zone and none of the prior devices of which I am aware provide this function. The need for same has been recognized in the past inasmuch as certain instructions for rug hooking have suggested placing weights, as books, on top of the base adjacent the working zone but none insofar as I am aware have provided means for such holding within the structure of the rack itself.
Accordingly, the objects and purposes of the invention include:
1. To provide a rug hooking rack for supporting and incrementally feeding a base material to a working zone which rack will be simple to make, effective in use and easily converted from a collapsed to operating condition and vice versa.
2. To provide a rug hooking rack, as aforesaid, which includes also clamp structure by which the operator may if and when he so desires hold such base material firmly against fixed means at a point adjacent the working zone whereby to improve the firmness with which a hooking operation may be performed with respect to a particular segment of such base material.
3. To provide a rug hooking device, as aforesaid, which may be expressed in either a relatively simple and portable table model and/or in a somewhat more permanent free-standing model.
4. To provide rug hooking devices, as aforesaid, which will be extremely simple in manufacturing but will be durable and capable of long and satisfactory use.
5. To provide rug hooking devices, as aforesaid, which will hold such base material firmly when the operator so desires but which may by a simple manipulation be enabled to advance such base material incrementally as desired by the operator.
6. To provide rug hooking devices, as aforesaid, which will operate easily and freely when so desired by the operator but which when in clamped condition will hold a base material firmly against any strains normally placed thereon by the rug hooking operation.
Other objects and purposes of the invention will be apparent to persons acquainted with apparatus of this general type upon reading the following specification and inspection of the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is a side view of a floor model of a rug hooking device incorporating the invention.
FIG. 2 is a view of the device of FIG. 1 from the side thereof faced by the operator when same is in use.
FIG. 3 is a view of the device of FIG. 1 from the side thereof facing away from the operator when same is in use.
FIG. 4 is a fragment of FIG. 1 illustrating a modification.
FIG. 5 is an oblique view of an embodiment of the invention adapted for use on a table.
FIG. 6 is an oblique view of the device of FIG. 5 as seen from the side faced by the operator when same is in use.
FIG. 7 is a section taken on the line VII--VII of FIG. 6.
FIG. 8 is a section taken on the line VIII--VIII of FIG. 5.
FIG. 9 is a section taken on the line IX--IX of FIG. 5.
FIGS. 10 and 11 correspond to FIGS. 6 and 9 but illustrate a modification.
DETAILED DESCRIPTION
Referring first to FIGS. 1, 2 and 3, there is provided frame structure comprising legs 1 and 2 connected together at their respective upper ends by any convenient longitudinal element, here a shelf and light shade S, and strengthened by a brace 3. Similar structure is provided at the other end of the machine and comprises legs 6 and 7 and a brace 8. A further longitudinal element 11 connects the two brace members.
Table structure is provided comprising a brace member 13 removably fixed as by bolts to the leg members 1 and 2. A similar brace member 14 is similarly fixed to the leg members 6 and 7. A table 16 connects the table support members 13 and 14. A roll 17 is pivotally mounted on the table support members 13 and 14 and is fixed for incremental advancement by any convenient means, such as an opening 18 in the support member 13 registerable with a selected one of a series of selectable openings 20 in the end of the roll 17 into which a pin 19 can be inserted.
The base material for the rug hooking operation is wrapped around the roll 17, extended across the top of the table 16 and back out of the operator's way, preferably by being led above the longitudinal member 11.
A light 21 and shade S may be provided if and as desired. The light shade S may also include shelf structure 22 which will further function as a connecting member between the end structures.
Forward clamp structure 23 is in this embodiment provided by a clamp member 24 pivoted at its one end at 26 to the leg 2 and its other end 27 to the leg 6. The spacing of said pivot point 26 (and its counterpart at the other end of clamp member 24) from the surface of the table 16 is such that the clamp will interfere with and bear against said table when same is rotated in a counterclockwise direction as viewed in FIG. 1 but same can be released from such contact with said table upon rotation in a clockwise direction as viewed in FIG. 1. A resilient device, such as the spring 28, is fixed between the clamp 24 and a suitable anchor point, such as the anchor point 29 on leg 1, and continuously urges said clamp for rotation in a counterclockwise direction. A handle 31 may be provided if desired to facilitate manual pivoting of said clamp in a clockwise direction.
With the base material above mentioned extending from the roll 17 under the clamp 23 and across the table 16 as above described, the hooking operation is carried out adjacent the end of said table, normally in the zone Z. In such case, the pin 19 will be inserted into the opening 18 and a selected opening 20 in registry therewith on said roll to prevent rotation of the roll 17 and the clamp 23, being urged by the resilient means 28 against said base, will hold said base material down firmly against the table as desired to facilitate the hooking operation. When it is desired to advance such base material, the pin 19 is merely withdrawn sufficiently to free the roll 17 and the base material is pulled toward the operator the desired distance. When the base material is so pulled toward the operator, the clamp provides no interference and no manipulation thereof is desired. However, if for reasons of inspection or otherwise it is desired to release the clamp entirely, it is a simple matter to grasp the knob 31 to pivot the clamp as far as desired and when the reason therefor has been satisfied, the clamp may be released and it will resume its normal function as above described.
It will be apparent that by appropriate proportioning of the apparatus the clamp 23 may be placed adjacent the rearward edge of the table 16 as shown or it may be placed as far toward the forward edge of said table as desired. It is further possible by providing a further member 32 (FIG. 4) extending between legs 1 and 2, and similar construction at the other end of the frame unit, to mount the clamp adjustably as desired by the operator for any given hooking device. This provides a wide range of flexibility in the use of said clamp according to the desires of the operator.
MODIFICATION OF FIGS. 5 TO 9
In this form of the apparatus, there is provided a base frame 41 comprising side members 42 and 43 and fixed end members 44 and 46. End member 44 is preferably fixed to extend downwardly from said side members in order to hook against the edge of a table as shown while end member 46 is provided across the top of said side members, and fixed thereto such as by screws 45, to provide a table functionally similar to the table 16 of FIGS. 1-3 adjacent the working zone Z. Said side members are provided with rows 47 and 48 of spaced openings for purposes appearing hereinafter. Openings 76 and 77 (FIGS. 7 and 9) are provided in end member 46 and are respectively in registry with a pair of the openings 78 and 79 in the side members 42 and 43. In this embodiment the rows of holes 78 and 79 are respectively offset from the rows of holes 47 and 48 (see FIG. 9).
An incremental clamp 49, corresponding functionally to the roll 17 in FIGS. 1-3 here comprises a pair of clamp members 50 and 51 which are held clampingly together in any desired manner, such as by bolts 52 and 53 and wing nuts 54 and 56. Pins 57 and 58 (FIG. 8) project from the lower clamp member 51 and are respectively receivable within the openings of the rows 47 and 48. Thus, a sheet of base material may be placed between said members 50 and 51, the wing nuts screwed down to fix same firmly therebetween and the pins 57 and 58 placed in the pair of openings furthest from the end of table member 46. As work progresses, the clamp member 49 is advanced one pair of openings at a time, or more if the operator so desires, along the rows 47 and 48 until the clamp 49 reaches a position close to the table member 46 at which said clamp may be relocated and the process repeated.
There is also provided a further clamp 63, corresponding functionally to the hold-down clamp 23 of FIGS. 1-3. This comprises a pair of members 64 and 66 which may be gripped together by any convenient manually operable means such as the bolt and wing nut assemblies 67 and 68 (FIGS. 6 and 9). In addition, further bolts 69 and 71 (FIG. 9) extend from the lower clamp member 66 through selected ones of the openings 76 and 77, together with the ones immediately therebelow of openings 78 and 79, and are fixed in place by wing nuts of which one appears at 74. Preferably, the bolts 69 and 71 of said clamp 63 will pass through the ones of the openings 76 and 77 (and 78 and 79) as to enable the clamp 63 to be as close as possible to the work zone Z. Thus, as the work is advanced by moving the clamp 49 forward as above described, it will be released and relocated in the hold-down clamp 63 by releasing the wing nuts associated with bolts 67 and 68, moving the work forward the distance desired and then retightening said wing nuts.
It will be seen that this form of the invention is very simple to make, can be rendered operational merely by placing same on a table as shown and may be lifted off from such table at any time desired when the work is interrupted and stored without the necessity of releasing the work from either of the clamps there provided. It is thus very simple and hence inexpensive to make but is extremely versatile and fully effective in use.
It will be apparent that functionally the lower clamp member 66 is in part a working surface spaced from the table member 46. Thus, if desired, and as illustrated in FIGS. 10 and 11, said lower clamp member may be eliminated and the upper clamp member 64 may operate directly on and with respect to the working surface of said table member 46. In such case, the table 46 is extended endwise to provide extensions 46A and 46B (FIGS. 10 and 11) and the bolts 67 and 68 extend into selected ones of a series of holes 86 and 87 therein.
A further possibility recognizes that one of the clamp members 64 and 66 may be a continuation of the working surface of the table 46, especially if said clamp member is placed in the position indicated by broken lines 63A in FIG. 7. Thus, one may provide clamp member 64 with the pins 81 and 82 which are sized and spaced to fit into a pair of the openings 47 and 48. With this, if desired, the clamp 63 may be inverted as shown at 63A and the pins 81 and 82 inserted into a pair of openings 47 and 48 whereby the lower member becomes flush with the table 46.
Although a particular preferred embodiment of the invention has been disclosed in detail for illustrative purposes, it will be recognized that variations or modifications of the disclosed apparatus, including the rearrangement of parts, lie within the scope of the present invention.
|
A rug hooking rack, in both a floor model and a readily supportable table model, is provided for positively holding, but incrementally feeding as desired, the base material upon which the hooking operation is being performed. Means are also provided for holding said base material firmly against a working surface at a point closely adjacent the zone in which work is being performed, whereby to facilitate such work both as to ease of performance and, in many instances, the quality of the finished work.
| 3
|
This is a division of application Ser. No. 870,636, filed Jan. 19, 1978, now U.S. Pat. No. 4,221,064, which is a continuation of application Ser. No. 675,966, filed Apr. 12, 1976 and now abandoned.
BACKGROUND OF THE INVENTION
This invention is concerned with a device for displaying indicia in the form of symbols, colors, pictures, words and other visual representations. The device can also be used for displaying storing and dispensing articles.
In the past, many devices have been described for displaying predetermined indicia such as letters or numbers or combinations thereof. Exemplary of these devices are yearly and perpetual calendars which generally comprise a fixed or movable cover having a plurality of apertures spaced apart from one another beneath which a card bearing predetermined date numbers and month or weekday titles is mounted and can be movable or stationary with respect to the cover. By moving the card or cover, the correct dates of any given year, (year, month, day of the week, day of the month) are displayed through the apertures. Such devices are described for example in U.S. Pat. Nos. 1,429,096; 2,499,329; 2,768,459; 1,373,744; 2,668,382; 2,009,630; and 3,800,454.
These prior art devices are generally characterized in that the card is movable, slidably or otherwise, with respect to the cover or the cover with respect to the card in either one or two directions, as for example solely horizontally or solely vertically, and that the user of the device must himself move the card or the cover in the proper direction and the proper distance to expose the predetermined display on the card through the apertures. This is generally accomplished by pulling a tab connected to the card or by inserting an instrument into a slot on the card and shifting the card or moving the cover over the card, or by operating a simple gear mechanism which engages the card or cover. Moreover, in the case of devices such as perpetual calendars the overall design of the card and cover is relatively complicated. The apertures must generally be divided into year apertures, month apertures, week apertures and day apertures in order to display all the information arranged on the card.
The present invention however provides a device for displaying indicia in the form of symbols, colors, words, pictures and other visual representations including articles to be dispensed from the device, which device is simple in design and requires that the user merely rotate the device in a substantially vertical plane to display and to change the indicia. No sliding, pulling, gear movement or any other means for moving any element of the device is required.
SUMMARY OF THE INVENTION
The device of this invention generally comprises:
(a) at least one cover member having at least one visual display means on at least one surface thereof; and
(b) at least one display member slidably movable by gravity with respect to one of said cover members within a predetermined area underlying said one cover member, said display member having at least one prepositioned indicium on at least one surface thereof, said indicium registering with at least one of said display means when said device is positioned in a substantially vertical plane, and whereby said display member slidably changes position with respect to said cover member under the force of gravity in response to rotation of said device in a substantially vertical plane to change the registry of said indicium with respect to said visual display means.
In the preferred embodiments of this invention, the display device can be adapted for use as a perpetual or yearly calendar.
The perpetual calendar embodiment of this invention comprises two substantially planar fixed cover members in the shape of a square having a plurality of apertures arranged in a seven by seven square matrix on each of their surfaces. Disposed between the cover members within a square area under the seven by seven square matrix of apertures on each cover member is a planar insert or display member in the shape of a square having sides shorter in length than the sides of the square area. Associated with one of the cover members and located on the inner surface thereof is a slide groove or runner which runs along the perimeter of the square area and also acts as a spacer between the cover members. By virtue of the insert's having relatively smaller dimensions than the square area and the free space between cover members provided by the spacer, the insert is slidably movable by gravity with respect to the cover members and can shift position when the device is rotated in a substantially vertical plane, the slide groove or runner serving as guiding and limiting means for the movement. The insert contains on each of its sides date integers and letters corresponding to the seven days of the week arranged in a single square matrix having dimensions of 14×14 (rows and columns). The orientation of the integers and letters with respect to each other vary (i.e., inverted, facing left, facing right and in line with each other). However, within each 14×14 square matrix arrangement on one side of the insert are 4 distinct sets of 7 weekday letters and 31 date integers arranged in 4-7×7 matrices, and on the opposite side 3 distinct sets of 7 weekday letters and 31 date integers arranged in 3-7×7 matrices. The distance (center to center) between each consecutive row and column of each distinct set is equal to the distance (center to center) between apertures on the cover member such that each distinct set will be capable of registering with and being displayed through the 7×7 matrix of apertures of one cover member when the device is placed in any of four predetermined positions in a substantially vertical plane. A distinct set can be viewed on the insert in its correct orientation by reading alternate columns and rows of the 14 ×14 matrix when the insert is held in a substantially vertical plane with one edge of the insert in an upper horizontal line. By rotating the insert 90° in each of three steps the other 3 distinct 7×7 sets of date integers and weekday letters can be viewed on one side of the insert. On the opposite side of the insert are 3-distinct sets of 7×7 matrices corresponding to three positions of rotation of the insert. The weekday letters, S, M, T, W, T, F, S, are arranged along the outer perimeter of each edge of each side of the insert and therefore occupies the first row of each distinct matrix set. The 31 date integers occupy the remaining rows and columns of each distinct set. However the first date integer 1 in each distinct set is under a different column headed by a weekday letter in each set. Since the first day of any given month can only begin on one of seven different days of the week, there are seven distinct sets of 31 date integers and 7 weekday letters arranged for any month of any year on both sides of the insert. One side of the insert contains 4 distinct sets of 31 date integers and 7 week letters and the other side contains 3 distinct sets of 31 date integers and weekday letters. The space required for one set of date integers and weekday letters are eliminated on one of the sides of the insert. Since the calendar contains 31 date integers in each set, any date integers between the actual numbers of days of the month to be displayed and 31 are disregarded by the user.
In using the device, it is first necessary to determine the day of the week on which any date of the month to be displayed falls, as for example the day of the week on which a given month begins. The device is then held in a substantially vertical plane with one edge of the cover member in an uppermost horizontal line. A row of week day letters on the insert will appear in registery with the top row of apertures of the 7×7 square matrix on the cover member. The next row on the cover member will show a row of date integers beginning with one and not exceeding 7 in a row. The number 1 in that row will appear below a column headed by one of the seven weekday letters. If date 1 of the month, for example, does not appear below the weekday letter corresponding to the correct day of the week on which the month begins, the device is rotated clockwise in a substantially vertical plane, viewing both sides, through an angle equal to 90°. Because the insert is dimensionally smaller than the area between the cover members rotation of the device clockwise 90° will cause the insert to slide by gravity a distance equal to the distance (center to center) between consecutive rows or columns of the 14×14 matrix toward the lower most edge of the cover member. The top row of the seven apertures of the cover member appearing after rotation will again display the weekday letters of the month but date integer 1 will appear under a different weekday letter column than in the previous positioning of the device. The user continues the process of rotating and positioning the device in a substantially vertical plane viewing both sides of the device until the correct date integer appears below the correct weekday letter column, and the calendar is then set for that month. From there on after a change in the month the user rotates the device as described above clockwise in steps of 90° until the new month is correctly displayed with the first day of the month corresponding to the correct week day letter.
In another embodiment of this invention, a yearly calendar is provided which has the same structural elements as the perpetual calendar, viz a pair of square cover members having a 7×7 matrix of apertures thereon and a square insert slidably movable within a predetermined square area between the cover members and having a 14×14 square matrix arrangement of indicia on each side of the insert. Operation of the yearly calendar is similar to the perpetual calendar; that is, by rotating the device in a substantially vertical plane to provide movement of the slidable insert by gravity toward the lower edge of the cover member to effect a display. The yearly calendar differs in the arrangement of indicia on the insert however, in that there is 1 distinct set of weekday letters and date integers and 3 distinct sets of date integers alone on each side of the insert, each set arranged in a 7×7 matrix. Each side of the insert covers a 6 month period. The date integers in a distinct set begin under a column corresponding to the correct day of the week of the month and the number of date integers which occupy the rows and columns correspond to the correct days of the month of the year the calendar is to measure. In addition an abbreviation of the month name i.e. Jan is displayed above the first date numeral of each month. However, since there are 49 positions for date integers in a 7×7 matrix, (42 in each when the 7 weekday letters are subtracted), a part of the succeeding month can also be displayed in each set with the first day of the succeeding month being under the correct weekday letter column. The succeeding distinct sets of 7×7 matrices will then carry over remainders of the date integers of the previous month and will be displayed through the cover apertures as the device is rotated in each of four steps, each step equal to a rotation of the device 90° clockwise in a substantially vertical plane. Since the total arrangement of indicia in each side is the form of a 14×14 square matrix, the total number of positions in each arrangement on each side is 196. Since there are 181 days from January 1 to June 30, (182 in a leap year) plus 7 weekday letters in one distinct set totalling 188 or 189, the first side of the insert covers the first six months of the year and the second side of the insert covers the second six months of the year (July 1 to December 31). A row of weekly letters appears in only one distinct matrix set on each side of the insert corresponding to the first month of each side, January and July. Since these weekday letters are in their traditional calendar positions, S M T W T F S they are not displayed again on subsequent rotations of the device.
The yearly calendar is not limited to displaying a given month by clockwise rotation. By designing the indicia on the insert accordingly it can also effect displays by counter-clockwise movements.
The present invention is not limited to the specific applications of a perpetual or yearly calendar. The indicia on the insert can be varied in kind and arrangement to cover a multitude of useful applications. For example the insert can contain on one or both of its surfaces a predetermined arrangement of photographs, caricatures, geometrical shapes, graphics, designs, colors, letters, numerals, abstract designs or other visual representations so that when the device is rotated a changing, visual display appears through the apertures by each rotation. For example, the device can be used to employ a sequence of numerals or letters useful for educational purposes such as a conversion table or a multiplication table, or a sequence of colors and shades thereof for artistic, aesthetic, or advertising purposes or for providing educational displays such as reading matter or an illustrated story. The indicia as used herein can also be the absence of a distant visual representation as for example a blank space. The device can also be used for storing and dispensing articles such as lipsticks and cigarettes, cosmetics and the like by making the display member or insert three dimensional and arranging the insert with compartments for housing these articles. As the device is rotated these articles will register with the apertures and can be removed therethrough. Rotation again can serve to change the registry of the articles with the apertures to remove the articles from view. Moreover the device need not be rotated by hand. A mechanical, electrical or other automatic means of rotation can also be used. The important feature of this invention is that the insert be slidably movable by gravity with respect to one or more cover members on rotating the device in a substantially vertical plane the insert moving within a predetermined area underlying one of the cover members. The cover members may be opaque or transparent and may also contain graphics, information etc. or other indicia on each surface thereof.
There is no limitation as to the size and shape of the cover member(s) or slidable insert with respect to each other. In this regard the cover member and insert can be in the shape of any figure such as a convex regular polygons i.e. triangle, pentagon, hexagon and convex circular figures such as a circle, "doughnut" or oval or concave and irregular figures. As used herein the term convex figure means a closed figure bounded by straight or curved lines wherein any line connecting any two points within the figure also lies totally within the figure. In a concave figure, at least a segment of the line lies outside the figure. It is not critical in this invention that there be two cover members. One cover member can be employed with the insert slidably disposed beneath it, as for example engaging a slide groove located on the cover which groove surrounds the predetermined area. The means for displaying the indicia are also not limited to apertures or holes in the cover member. Instead of discrete apertures the display means can be made of a prismatic translucent material such as glass which allows viewing of the indicia when the device is held at a certain angle to a light source. The cover member may be transparent if desired and the insert opaque or vice versa. It is also not necessary that a plurality of apertures be used or that they be arranged in a matrix. At least one aperture or other display means can be used to display the indicia which aperture can be varied in size and number.
The insert or display member also need not be a single unit. Multiple inserts can also be employed which can also be slidably movable with respect to each other. The predetermined area on which the insert slides can take the form of one of the cover members, i.e. a square area under a square cover member or can be different in form such as circular, triangular or any other regular or irregular closed figure. The area need not be limited to planar areas, but can also be curved or dimensional.
The guide means is also not limited to a groove or runner. Any other means for limiting the movement of the insert or display member can be employed such as screws or pegs positioned at predetermined positions on the cover member or a raised ridge around the predetermined area can also be employed.
Although the preferred display device of this invention comprises at least one fixed cover member as previously described overlying a display member slidably movable with respect to the cover member, the device can also be designed so that the cover member is slidably movable within a predetermined area overlying a fixed display member. The cover member moves into predetermined positions by slidably engaging guide means associated with said display member surrounding said predetermined area to change the registry of indicia with the display means on the cover member.
In order to more fully describe the present invention, reference will be made to the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a front view of one cover member of the perpetual calendar embodiment of this invention.
FIG. 2 shows one side of a slidable insert for the perpetual calendar having a first predetermined arrangement of date integers and weekday letters in a 14×14 square matrix on the surface thereof.
FIG. 3 shows the opposite side of the slidable insert of FIG. 2 having a second predetermined arrangement of date integers and weekday letters in a 14×14 square matrix on the surface thereof.
FIG. 4 shows a side view of the perpetual calendar.
FIGS. 5A and 5B show a stepwise operation of the perpetual calendar and the corresponding date and week displays for each stepwise rotation.
FIG. 6 shows one side of a slidable insert for a yearly calendar.
FIG. 7 shows the opposite side of the slidable insert of FIG. 6.
FIGS. 8 and 9 show the cover member and slidable insert of two embodiments of a display device according to the invention having a circular shape.
FIG. 10 shows a triangular embodiment of the present invention.
FIGS. 11A, B and C show a dimensional embodiment of the present invention useful for storing and dispensing articles.
FIGS. 12A, B and C illustrate a multiple-insert display device according to the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In FIGS. 1 and 4 a square cover member 10 is shown having a 7×7 square matrix of apertures 11 centered on the cover member. The cover member 10 can be made of paper, cardboard, plastic, metal, wood or many other solid materials. A second cover member 13 is fixed to cover member 10 directly under cover member 10 (see FIG. 4) having its 7×7 square matrix of apertures in registry with the apertures of cover member 10 and is therefore not seen in FIG. 1. The cover members are spaced apart by a spacer 14 which is associated with one of the cover members. The spacer 14 is essentially a thin strip of solid material which defines a narrow void area between the cover members having sides A, B, C and D. FIG. 2 shows one side of a slidable insert 12 and FIG. 3 shows the opposite side of insert 12. The insert 12 fits within the void area between the cover members 10 and 13 and occupies an area in FIG. 1 having sides BCEF as indicated by the inner dotted lines. The insert is therefore slidably movable with respect to the cover members within the void area. The insert can be made of paper, cardboard, plastic, metal, or the like. Thus in its combined form the device comprises a sandwich of two cover members with the insert 12 slidably movable between them.
Each surface of insert 12 as shown in FIGS. 2 and 3 contains an arrangement of weekday letters 15 and date integers 16 in a 14×14 square matrix. Although the orientations of date integers and weekday letters in the 14×14 matrix vary, i.e., upside down facing left to right, there are 4 distinct sets of 7 weekday letters and 31 date integers in the total arrangement on one side of the insert (FIG. 2) and 3 distinct sets of 7 weekday letters and 31 date integers on the other side of the insert (FIG. 3). These sets are arranged in 7×7 matrices and can be logically viewed as rows and columns in four distinct orientations on the insert, each of these orientations corresponding to four positional rotations of 90° in a vertical plane in which each edge or side of the insert occupies an upper horizontal position with respect to the vertical plane. In FIG. 2, side a occupies the upper horizontal position and thus a matrix of 7 rows and 7 columns can be viewed from left to right and downward from alternate rows and columns of the 14×14 matrix in which the first row is a series of weekday letters and the succeeding rows and columns are occupied by 31 date integers.
For example in FIG. 2 a set of 7 weekday letters, S, M, T, W, T, F, S appears from left to right in the first row in alternate columns of the 14×14 matrix. In the next six alternate rows a sequence of 31 date integers appear under the 7 columns defined by the weekday letters. In FIG. 2 the date integer 1 lies below the first column headed by S (Sunday). By rotating the insert in a vertical plane clockwise 90° to place side b in an upper horizontal line another distinct set of 7 weekday letters and 31 date numerals can be read in alternate rows and columns of the 14×14 matrix in which date integer 1 is below M (Monday). In the orientation in which side c is the uppermost horizontal line, data numeral 1 is below T (Tuesday) and in the orientation in which side d is in the uppermost horizontal position numeral 1 is below W (Wednesday). Thus on one side of the insert 4 distinct sets of weekday letters and date integers are arranged, in which the first day of a month begins on 4 different days of the week, S, M, T, W. On the opposite side of insert 12 as shown in FIG. 3 there are three distinct sets of 7 weekday letters and 31 date integers corresponding to the orientation of the insert in which sides e, f, g of the insert are each separately disposed along an upper horizontal line, and in which the date integers 1 lie under T (Thursday, side e uppermost), (Friday, side f uppermost) and S (Saturday, side g uppermost) respectively.
Since there are only 7 days in a week there are only 7 months which can exist having its first day beginning on a different day of the week. Therefore since there are 8 sides to both surfaces of the insert, only 7 sides are needed to project a distinct set. Therefore orientation h, of FIG. 3 does not contain a distinct set of weekday letters and integers.
FIGS. 5A and 5B show the operation of the perpetual calendar embodiment viewing one side of insert 12 through cover member 10. The cover member 10 is shown as being transparent to illustrate the relative positions of the date integers and weekday letters on the insert 12 beneath it. The sides of the spacer 14 are indicated by i, j, k and l.
In FIG. 5A, the insert fits into the angle defined by sides i and l of the spacer 14. A 31 day month beginning on a Sunday appears through the apertures. The remaining date integers and weekday letters are masked by the spaces between the apertures and the spaces between the apertures and the edges of the spacer 14. As the calendar is rotated 90° clockwise so that side i becomes the horizontal uppermost side, the insert 12 slides downward along side l by gravity so that in FIG. 5B it fits into an angle formed by sides l and k. The distance the insert moves is equal to the distance between adjacent rows or columns of the 14×14 matrix (Center to Center). This distance is also equal to the difference in demension between a side of the void area and a side of the insert. This causes a new 31 day month display to appear through the apertures 11 wherein the first day of the month begins on Monday (M). Similarly, by rotating the device clockwise again 90° so that side l is in the uppermost horizontal position, the insert slides downward along side k to fit into the angle formed by sides k and j (not shown). A new month display is exposed in which the first day of the month begins on Tuesday (T). One more rotation of the device clockwise 90° to place side k in the uppermost horizontal position will expose another display in which the first day of the month begins on a Wednesday (W).
The reverse side of the device using side 14 of the insert can be similarly rotated in three 90° steps to display three 31 day months with the first day beginning on a Thursday (T), Friday (F) and Saturday (S), respectively.
The user of the device need only know a day of the week on which a given date of the month falls and the number of days of the month. The user rotates the device on either side to find a monthly display corresponding to the month to be displayed, and the device is set for that month. Any days between the actual number of days in a month and 31 are disregarded. When the month changes the process is again repeated using either side of the device.
FIG. 6 shows one side of a yearly calendar slideable insert 17 and FIG. 7 shows the opposite side of the insert 17. The insert has the same dimensions as in the perpetual calendar insert and is slidably movable with respect to the cover members. Within the area defined by the spacer 14 the arrangement of indicia on the insert as shown in FIGS. 6 and 7 is also a 14×14 square matrix system having within it on each side, 3 distinct sets of date integers and 1 distinct set of weekday letters and date integers arranged in 7×7 matrices. However each display corresponding to a position of the device in a vertical plane with an edge uppermost and horizontal is not limited to a single 31 day month. In FIG. 6 the first set corresponding to side m in the upper horizontal position contains a row of weekday letters (S, M, T, W, T, F, S) in alternate columns of the 14×14 matrix with the first day of January beginning on a Saturday (S). Thereafter the date integers in January occupy additional rows ending with 31 under Monday (M) in row 7 of the 7×7 matrix. Thereafter the first date integer for February properly begins in the same row under T (Tuesday) and ends under S (Saturday) as February 5, to completely fill the 7×7 matrix corresponding to the set. (49 units in the matrix-7 weekday numerals=42 units remaining in the matrix minus 6 weekday letter columns not used in January=36, minus 31 days in January=5, minus 5 days in February=0). The first day of each month has the month title abbreviated over the date integer i.e. JAN. The next display corresponding to a slidable movement of the insert 90° clockwise with side n uppermost and horizontal contains a new 7×7 matrix of date integers continuing from the previous months display (February). Since the traditional calender positions of days of the week are already known, repetition of them in succeeding displays is not necessary. The date integer 6 appears at the top left hand aperture and indicates that Feb. 6 is a Sunday (S). The remaining date integers for February are arranged in the rows and columns of the distinct 7×7 matrix up to 28 integers, the number of days in February. Thereafter the first date of March, begins in the next column following 28 with MAR printed above it. The remaining rows and columns contain date integers corresponding to the dates in March until the 7×7 matrix having 49 members is occupied. The remaining dates not appearing in March are carried over to the next rotation of the device and so on until June 30 is reached in orientation p. The device is then turned over on its opposite side and insert 12 is used for displaying July as shown in FIG. 6. The arrangement on the side shown by FIG. 6 covers the period from July 1 to December 31 and also has 3 distinct 7×7 date integer matrices and 1 distinct weekday letter and date integer matrix for the month of July (orientation q, r, s and t). Thus each side of the insert covers a 6 month period.
FIG. 8 shows an embodiment of the present invention in which the cover member 18 is "doughnut" shaped having a center hole 20 and the slidable insert 19 is circular. The insert 19 beneath the cover member is in the form of a circle having a smaller diameter than the cover member but larger than a straight line equal to the extension of the diameter of the inner circle or "doughnut hole" 20 to the circumference of the outer circle of the cover member. The indicia on the insert are a sequence of numbers 21. A spacer 22 defining a circular area beneath the cover member is provided. As the device is rotated the insert will slide along the circular edge of the spacer 22 by gravity and to provide a change in the registry of the indicia 21 with the aperture 20.
In FIG. 9 the cover member 21 is in the form of a circle having a plurality of circular apertures 24 around its circumference. The slidable insert 25 (dotted lines) is also in the form of a circle having a smaller diameter than the cover member 21 and has a series of indicia, i.e. letters of the alphabet on its periphery. The letters are so arranged that they will register with a lower aperture on the lower portion of the cover member as the device is rotated and will change continuously as the device is rotated again. Such a device can be used for educational purposes.
FIG. 10 shows a triangular embodiment of the present invention having a triangular cover member 26, a triangular insert 27 slidably movable by gravity within the area defined by the spacer 28. The triangular indicia 29 on the display member which can be triangular colors for example are arranged so that they will change registry with the triangular apertures 30 when the device is rotated in each of three positions in a substantially vertical plane.
FIGS. 11A, B and C illustrate an embodiment of the present invention for storing and dispensing articles. In FIG. 11A a cubical insert 31 is shown, which insert is divided into four hollow compartments 32 for housing articles such as cigarettes, lipstick or confection. FIG. 11B shows a hollow box-like structure comprising square cover member 33 having a square aperture 34, sides 35 and second cover member 36 which may optionally also contain an aperture. The insert 31 fits between the cover members as shown by FIG. 11C with a compartment 32 of the insert in registry with the aperture 34. As the device is rotated the insert moves by gravity and another compartment registers with the aperture.
FIGS. 12A, B, and C illustrate a multiple insert embodiment of this invention.
FIG. 12A shows a square insert 37 having on its surface groups of prepositioned indicia 38. In the center of the insert is a square hole 39. FIG. 12B shows a second insert 40 in the shape of a triangle and having on its surface prepositioned indicia 41. FIG. 12C shows inserts 37 and 40 in position beneath cover member 42. The dotted lines show the area in which both inserts move and is defined by a spacer 43. The cover member has four outer apertures 44 and one inner aperture 45. Insert 37 underlies the cover member 42 and insert 40 underlies insert 37. Another cover member lying under insert 40 is not shown in the Figure. Insert 37 has side dimensions less than the side dimensions of the area and is slidably movable by gravity in response to rotation of said device in a substantially vertical plane the registry of indicia 38 changing with outer apertures 44 on the cover member. A portion of the square hole 39 on the insert 37 is always in registry with inner aperture 45 of insert 37. The triangular insert 40 has side dimensions approximately equal to the side dimensions of the area defined by the spacer 43. The indicia 41 on insert 40 registers with inner aperture 45 of cover member 42 via hole 39 of insert 37 and changes registry on rotation of the device in a substantially vertical plane. Such a device is useful for educational purposes.
|
A device for displaying indicia is provided comprising:
(a) at least one cover member having at least one visual display means on at least one surface thereof; and
(b) at least one display member slidably movable by gravity with respect to at least one of said cover members within a predetermined area underlying said cover member, said display member having at least one prepositioned indicium on at least one surface thereof, said indicium registering with at least one of said visual display means, whereby said display member slidably changes position with respect to said cover member under the force of gravity in response to rotation of said device in a substantially vertical plane to change the registry of said indicium with respect to said visual display means.
In preferred embodiments of this invention a perpetual and yearly calendar is provided.
| 6
|
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of International Application No. PCT/DE2005/000723, filed on Apr. 20, 2005, entitled “Method and Device for Programming CBRAM Memory Cells,” which claims priority under 35 U.S.C. §119 to Application No. DE 10 2004 019 860.8 filed on Apr. 23, 2004, entitled “Method and Device for Programming CBRAM Memory Cells,” the entire contents of which are hereby incorporated by reference.
BACKGROUND
[0002] “Conductive bridging” memory cells (CBRAM) constitute a new and promising technology for semiconductor-based memory components. In the future, products based on CB technology are possible as a replacement both for flash memories and for DRAM memories. R. Symanczyk et al. describe in “Electrical characterization of solid state ionic memory elements” in Non-Volatile Memory Technology Symposium (NVMTS'03), San Diego, 2003, the electrical properties of memory elements based on so-called solid electrolytes, these elements also being called programmable metallization cells, or PMC when abbreviated, on account of their operating principle. In memory cells of this type, a vitreous or porous layer, for example made of chalcogenide glass such as GeSe, GeS or made of AgSe, CuS, WOx, etc., is situated between a metal electrode serving as ion donor, for example made of Cu, Ag, Au, Zn, and a counterelectrode made of inert material, for example W, Ti, Ta, TiN, doped Si or Pt. When a voltage or current pulse is applied between the electrodes, metal ions are driven into the chalcogenide glass by a redox reaction and form metal-enriched clusters, with the result that, given a sufficient metal concentration, a conductive bridge is formed between the two electrodes, which forms a low-resistance or “on” state of the memory cell. An electrical current or voltage pulse having opposite polarity inverts the redox reaction, so that the metal ions are drawn from the chalcogenide glass and the metal-enriched clusters are reduced. In this way, the metallically conductive bridge is terminated, and a high-resistance or “off” state of the memory cell then forms.
[0003] The accompanying FIGS. 1A and 1B schematically illustrate the above mentioned possible states of such a CBRAM memory cell 1 , namely the high-resistance or off state in FIG. 1A and the low-resistance or on state in FIG. 1B , it being possible for the high-resistance state to be assigned for example to the logic state “0” and the low-resistance state to the logic “1” state. FIGS. 2A and 2B schematically illustrate a write operation for writing a logic “1” by application of a current or voltage pulse to the CBRAM memory cell 1 , while FIGS. 2C and 2D schematically illustrate an erase operation in which a CBRAM memory cell 1 in the low-resistance or on state is put into the high-resistance or off state ( FIG. 2D ) by application of a current or voltage pulse having opposite polarity.
[0004] The suitability of such memory cells for high-density and fast nonvolatile memories has been recognized and investigated in the specialist report mentioned above.
[0005] For reliable operation over relatively long times, special programming and erasure strategies are necessary in order to guarantee the cycle stability. The accompanying FIG. 3 graphically shows the result of a typical cycle test such as occurs with an inadequately calibrated erase operation: the number of cycles with which the CBRAM cell was cycled is plotted on the abscissa axis and the electrical resistance of the CBRAM cell is plotted on the ordinate axis. Since the on state was written to a greater degree than erased, the resistance of the off state thus generated degrades with an increasing number of cycles. It is thus clear that in the extreme case, direct repeated writing of a logic “1” state corresponding to the on state in CBRAM memory cells causes serious write imprint and the cell would be very rapidly destroyed.
SUMMARY
[0006] Described herein is a method and a device for programming CBRAM memory cells in which repeated writing of a logic “1” corresponding to the low-resistance cell state to a CBRAM memory cell can be avoided and premature destruction of the cell by write imprint can thus be prevented.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The programming method according to the invention and the devices according to the invention for programming CBRAM memory cells are explained in more detail below with reference to the drawings, wherein like reference numerals in the various figures are utilized to designate like components:
[0008] FIGS. 1A and 1B schematically and symbolically show the high-resistance off state and low-resistance on state of a CBRAM memory cell;
[0009] FIGS. 2A-2D schematically show the different states of a CBRAM memory cell during the writing of a logic “1” and during the erase process;
[0010] FIG. 3 graphically shows results of a cycle test of CBRAM memory cells;
[0011] FIG. 4 shows a schematic flow diagram of an exemplary embodiment of a programming method according to the invention;
[0012] FIG. 5 shows a schematic pulse diagram of the pulses fed to the cell in each case for erasing (“0”) and for writing a logic (“1”);
[0013] FIG. 6 shows a programming device designed for carrying out the programming method corresponding to the first aspect of the invention, as shown by the flow diagram in FIG. 4 ;
[0014] FIGS. 7A, 7B and 7 C respectively show a schematic circuit diagram, a truth table and pulse shapes fed to the cell for the programming device corresponding to the third aspect of the invention;
[0015] FIG. 7D shows a flow diagram illustrating the mode of functioning of the programming device illustrated in FIG. 7A ;
[0016] FIGS. 8A, 8B , 8 C respectively show a schematic circuit diagram, a truth table and pulse shapes of a programming device corresponding to the fourth aspect of the invention; and
[0017] FIG. 8D shows a schematic flow diagram illustrating the mode of functioning of the programming device as illustrated in FIG. 8A .
DETAILED DESCRIPTION
[0018] A first method for programming CBRAM memory cells involves putting the memory cells into a low-resistance or on state corresponding to a first logic state by application of a write pulse having a specific polarity and into a high-resistance or off state corresponding to a second logic state by application of an erase pulse having opposite polarity, an erase pulse being applied to each memory cell to be programmed before a write pulse with which the memory cell is intended to be put into the first logic state.
[0019] A first device for carrying out the above method includes a command generator which receives a write request signal and an enable signal from a memory control unit and outputs command signals corresponding to the signals in the write cycle, with which command signals a respective switch can be opened or closed, the switch inputs respectively having applied to them a write pulse, an erase pulse and a center level and applying these input signals of the memory cell depending on their “open” and “closed” state.
[0020] A second device for programming CBRAM memory cells, in which the memory cells can be put into a low-resistance or on state corresponding to a first logic state by application of a write pulse having a specific polarity and into a high-resistance or off state corresponding to a second logic state by application of an erase pulse having opposite polarity, includes an evaluation logic that compares a cell content read out from a memory cell that is respectively to be written to with a datum to be stored and always feeds an erase pulse to the memory cell in the write cycle if the datum to be stored is equal to the second logic state and feeds a write pulse for writing a datum corresponding to the first logic state if the comparison by the evaluation logic reveals that the logic value of the cell content read out differs from the datum to be stored. In this device, the evaluation logic preferably has a NAND element in order to carry out a logic NAND combination of the cell content read out with the datum that is respectively to be stored.
[0021] A third device for programming CBRAM memory cells, which can be put into a low-resistance or on state corresponding to a first logic state by application of a write pulse having a specific polarity and into a high-resistance or off state corresponding to a second logic state by application of an erase pulse having opposite polarity, includes an evaluation logic that compares a cell content read out from a memory cell that is respectively to be written to with a datum to be stored and feeds a write pulse to the memory cell in the write cycle only when the comparison reveals that the logic value of the cell content read out differs from a datum to be stored, if a datum corresponding to the first logic value is to be stored, and feeds an erase pulse if a datum corresponding to the second logic value is to be stored. In this device, the evaluation logic preferably has an exclusive-OR element in order to carry out a logic “exclusive-OR” combination of the cell content read out with the datum that is respectively to be stored.
[0022] The programming method corresponding to the first device ensures that memory cells are always erased before being written to anew. In the programming method corresponding to the first device, the write processes are composed of one operation in 50% of all cases and of two operations in 50% of all cases. By contrast, one read operation always and one write operation in 50% of all cases are necessary in the second and third programming devices. As a result, in the second and third devices, the number of write operations, in particular, is reduced, the write operations bringing about a significantly greater loading of the memory cell than read processes on account of the significantly higher voltages and currents. In the second and third programming devices, the evaluation logic achieves the effect that the cell content is altered in the event of overwriting only if this is actually necessary on account of a changing bit state. As a result, from standpoints of speed, the programming method corresponding to the first device matches the mode of functioning of the second and third devices since (assuming read and write cycles of equal length) on average 1.5 operations per write access are required.
[0023] In comparison with directly overwriting of cells, the programming method according to the invention requires more time, but in return enables a long cycle stability of the memory cells. In addition, the second and third programming devices have the potential for a reduced energy requirement, depending on the written data or data to be written.
[0024] Exemplary embodiments will now be described in connection with FIGS. 4-8D . In the method for programming CBRAM memory cells which is illustrated in the form of a schematic flow diagram in FIG. 4 and corresponds to the first embodiment, the instantaneous state of the CBRAM memory cells is always erased before they are written to anew and the memory cell is put into the off state (cf. FIGS. 2C and 2D described in the introduction). This is possible without problems since CBRAM cells exhibit no erase imprint (cf. the document mentioned in the introduction). In this case, the command sequence provides that after the write request (S 1 ) and the identification or interrogation of whether a “1” or “0” is being written (S 2 ), firstly an erase pulse is always output to the selected cell (S 3 and S 4 ) and the subsequent write pulse (S 5 ) follows only in the case where a “1” is intended to be written. This eliminates the risk of the write imprint for the “1” datum.
[0025] FIG. 5 shows, on the left, an example of an erase pulse “0” fed to a memory cell, whereas, on the right, FIG. 5 shows a pulse diagram for the case where a “1” is written to the memory cell. As shown, the erase pulse V erase and the write pulse V write have opposite polarities and proceed from a center or zero level. Furthermore, the right-hand part of FIG. 5 shows that each write pulse with which a “1” is programmed into the memory cell is preceded by an erase pulse V erase .
[0026] The circuit arrangement illustrated schematically in FIG. 6 is a device for carrying out the programming method illustrated in the flow diagram of FIG. 4 . This device includes an interface to a memory control unit SE, which outputs a write request I/O, an enable signal E, the potential V write for the write pulse, the potential V 0 for the center level and the potential V erase for the erase pulse. The programming device illustrated in FIG. 6 contains a command generator CG, which outputs command signals C 1 , C 2 and C 3 depending on the signals fed to it by the memory control unit SE, FET transistors Sch 1 , Sch 2 and Sch 3 serving as switches respectively being opened and closed via the command signals. The outputs of these three switches are combined and, depending on the command signals C 1 , C 2 , C 3 of the command generator CG, pass the erase pulse with the potential V erase , the write pulse with the potential V write and the center level to the cell. Consequently, the programming device illustrated in FIG. 6 has the effect that the command generator CG, upon reception of a write request signal I/O and an enable signal E from the memory control unit SE, in the write cycle, outputs the command signals C 1 , C 2 and C 3 which correspond to the input signals and which a respective one of the switches Sch 1 , Sch 2 and Sch 3 is opened or closed. The switches Sch 1 , Sch 2 and Sch 3 respectively have applied to them a level V write corresponding to the write pulse, the center level V 0 and the level V erase corresponding to the erase pulse and, on the basis of these levels or potentials, pass the write pulse and erase pulse and the center level to the cell as required by the method described above and illustrated in the flow diagram of FIG. 4 .
[0027] FIG. 7A shows a schematic circuit diagram of a programming device for programming CBRAM memory cells which corresponds to another embodiment of the invention. An evaluation logic has a NAND element 2 , to which are applied on the input side a write request signal W received externally or from a memory control unit (not shown) and a read signal R generated by a sense amplifier (SA). The NAND element 2 performs a logic NAND combination of these two input signals R and W according to the truth table shown in the three left-hand columns in FIG. 7B . This signal logically combined by the NAND element 2 is present at a first input of a first AND element 3 , the second input of which is fed an enable signal E either externally or from a memory control unit. The signal generated at the output of the first AND element 3 is then additionally logically combined with the write request W from the input I/O via a second AND element 4 , which generates an output signal “OUT” as contained in the right-hand column of the truth table shown in FIG. 7B . Consequently, the output signal “OUT” is generated by the programming device shown in FIG. 7A only when the cell state read from the cell and detected by the sense amplifier 1 according to the signal R differs from the state of the write request W.
[0028] The pulse diagrams of FIG. 7C respectively show (left-hand-side) the write pulse generated for programming a logic “1” at the output “OUT” of the circuit shown in FIG. 7A , which write pulse is generated only if the input signals R and W of the NAND element 2 have different states, and (right-hand side) an erase pulse applied in all other cases of the cell. The write pulse “1” and erase pulse “0” are voltage pulses and have opposite polarities, proceeding from a zero or center level that is not specifically designated in FIG. 7C .
[0029] FIG. 7D shows, in the form of a schematic flow diagram, the mode of functioning of the programming device illustrated in FIG. 7A . After the write command has been sent to the memory (S 10 ), a read pulse is applied to the memory cell, and the cell content is read out and evaluated for example by the sense amplifier 1 shown in FIG. 7A (S 11 ). With S 12 , the write request signal (W) is evaluated, i.e., compared, with the evaluated cell content signal (R) by the NAND element 2 .
[0030] If both input signals R and W present at the NAND element 2 are identical, it is the case that, if the datum to be written corresponds to a logic “1”, i.e., interrogation (S 13 ), nothing further is instigated, i.e., no write pulse is output (S 15 ). If the datum to be written corresponds to a logic “0”, an erase pulse is applied (S 16 ).
[0031] By contrast, if the two input signals R and W at the NAND element 2 are different, interrogation (S 14 ) assesses whether writing of the datum corresponds to a logic “0” or “1”. An erase pulse is applied in the first case (S 16 ) and a write pulse is applied in the second case (S 17 ).
[0032] In the circuit arrangement which is shown schematically in FIG. 8A and represents a programming device corresponding to another exemplary embodiment of the invention, the NAND element 2 in the evaluation logic ( FIG. 7A ) has been replaced by an exclusive-OR element 12 , while the other components, input signals and signal connections correspond to the circuit arrangement shown in FIG. 7A .
[0033] The different mode of functioning—illustrated schematically in the form of a flow diagram in FIG. 8D —of the programming device illustrated in FIG. 8A is explained on the basis of the truth table shown in FIG. 8B and the pulse diagram shown in FIG. 8C , which does not differ from that in FIG. 7C . Specifically, the function of the exclusive-OR element 12 contained in the evaluation circuit prevents the memory cell from being overwritten if a datum to be written corresponds to the present state of the cell. Firstly, S 10 -S 12 of FIG. 8D are identical to S 10 -S 12 of FIG. 7D . If the comparison in S 12 reveals that a write datum is identical to the present content of the cell, nothing further is instigated, to be precise irrespective of whether a datum to be written corresponds to a logic “1” or “0”. By contrast, if the comparison (S 12 ), carried out by the exclusive-OR element 12 , reveals that the datum to be written differs from the present state of the memory cell, it is the case that, depending on the logic state of the write datum determined in S 14 , a write pulse for writing a logic “1” is applied (S 17 ) or in the other case an erase pulse for erasing the cell content of the memory cell is applied (S 16 ).
[0034] The programming device of the invention as explained with reference to FIGS. 7A-7D has the advantage over the programming device according to the invention as explained above with reference to FIGS. 8A-8D that the high-resistance “0” state is always updated or “refreshed” by the device of FIG. 7A .
[0035] In the case of the programming devices described above it was assumed by way of example that the write pulse and erase pulse are voltage pulses each having an identical duration and approximately identical amplitude. Since this presumption is only by way of example, however, the programming device claimed by the independent claims is also intended to encompass, for write and erase pulses, current pulses and pulses each having a different duration and amplitude.
[0036] While the invention has been described in detail with reference to specific embodiments thereof, it will be apparent to one of ordinary skill in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. Accordingly, it is intended that the present invention covers the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.
LIST OF REFERENCE SIGNS
[0000]
CBRAM memory cell
“0”, “1” Logic states
I/O Write request
E Enable signal
V write Level of the write pulse
V erase Level of the erase pulse
V 0 Center level
C 1 , C 2 , C 3 Command signals
Sch 1 , Sch 2 , Sch 3 Switches
R Read state of the memory cell
W Signal of the write request
“OUT” Output signal to the cell
SA Sense amplifier
S 1 -S 5 Command steps of a first exemplary embodiment
S 10 -S 17 Command steps of a second exemplary embodiment
|
Methods and devices for programming conductive bridging RAM (CBRAM) memory cells improve the cycle stability by ensuring that the memory cells are erased before being written to anew. Optionally, in the event of overwriting the memory cells, memory cells may be written to only when the writing operation would alter the cell content (i.e., the state of bit stored in the memory cell is being changed from a logical 0 to a logical 1 or vice versa).
| 6
|
BACKGROUND OF THE INVENTION
This invention was made with government support under contract number DE-AC06-76RLO 1830, awarded by the U.S. Department of Energy. The government has certain rights in the invention.
A substantial number of ground contaminated areas exist, especially as the result of industrial disposal, which either threaten populated areas or which cannot be used for conventional purposes Soil heating techniques have been proposed for treating contaminated soils containing volatile or semi-volatile organics, such as dioxins, PCB's, and light hydrocarbons. Known methods of heating the soil are relatively cumbersome and expensive, or are incapable of heating the soil itself to the desired depth for removing large quantities of contaminants. For example, radio frequency heating can be expensive and furthermore is capable of treating only a superficial region of the soil.
In Brouns et al U.S. Pat. No. 4,376,598, in situ vitrification of soil is described wherein sufficient electrical energy is applied via electrodes in the ground for converting the soil itself to a conductive, i.e., liquid, state which is then allowed to harden into a vitrified mass. Although, as a result of the intense heat generated in the vitrification process, volatile materials can be driven off or pyrolyzed, the electrical power requirements in heating the soil are reduced in accordance with the present invention for the purpose of volatilizing or pyrolyzing organic materials.
In accordance with the present invention, soils are heated electrically to temperatures substantially lower than those employed for vitrifying the soil. A ground region is heated to a temperature between 100° C. and 1200° C. to volatilize and/or pyrolyze undesired material. For the most part a steady source of resistive heating power, as employed for in situ vitrification, is neither required nor desirable for controlled temperature heating of soil. Although such AC or DC resistive heating can be employed to reduce soil moisture, this type of heating is not acceptable when the soil begins to dry. For dry soil, or when the moist soil tends to dry out in process, the soil becomes a poor electrical conductor such that resistive heating becomes ineffective.
If sufficient DC or AC voltage is applied between electrodes to produce continuous arcing, large or artificially cooled electrodes may be required, and once a gas plasma forms, higher currents are drawn from the power supply to maintain a reasonable power level. That is, as long as current is flowing, the voltage between electrodes then remains substantially lower than employed to initiate the current in the first place because gases in the electrical path become ionized to a more conductive state.
SUMMARY OF THE INVENTION
In accordance with the present invention, a region of ground containing hazardous, volatilizable material is heated to a temperature between 100° and 1200° C. by applying a voltage between a pair of electrodes spanning the region and causing a current flow therebetween for volatilizing the hazardous material. In accordance with a preferred embodiment of the present invention, the voltage between electrodes is applied in a range of 100-2,000 kilovolts DC for heating the region by intermittent DC arcing. A high voltage impulse generator is preferably employed which causes direct current discharges between electrodes, separated by short time periods to permit any ionized gases to recombine. This system enables the delivery of effective power to the ground at reasonable power levels for heating the ground to the required temperature and volatilizing the undesired material.
In accordance with another aspect of the present invention, a plurality of electrodes are inserted into the ground, and the power supply is switched between various pairs of electrodes. According to yet another aspect of the present invention, an electrically conductive heavy oil is inserted in the ground region between electrodes and the soil region is heated by AC or DC resistance heating through the conductive heavy oil. According to a further aspect of the invention, a negative pressure is maintained with respect to the treated region of ground by means of a hood over the ground surface being treated or hollow electrodes through which the volatilized material is withdrawn by an induced draft or vacuum source.
It is therefore an object of the present invention to provide an improved method and apparatus for detoxifying sites containing hazardous volatilizable material.
It is another object of the present invention to provide an improved method and apparatus for detoxifying sites containing hazardous, volatilizable material on a reasonably economic basis.
The subject matter of the present invention is particularly pointed out and distinctly claimed in the concluding portion of this specification. However, both the organization and method of operation, together with further advantages and objects thereof, may best be understood by reference to the following description taken in connection with accompanying drawings wherein like reference characters refer to like elements.
DRAWINGS
FIG. 1 is a top view of an in situ heating hood apparatus,
FIG. 2 is a side view of the FIG. 1 apparatus,
FIG. 3 is a cross-sectional view of an electrode as employed with the FIG. 1 apparatus,
FIG. 4 is a side view of in situ heating apparatus, including plural hollow electrodes and a common header,
FIG. 5 is a cross-sectional view, partially broken away, of a FIG. 4 electrode,
FIG. 6 is an electrical circuit diagram of power supply apparatus employed with the present invention including switching means for plural electrodes, and
FIG. 7 is a schematic illustration of gas treatment means as may be employed with the present invention.
DETAILED DESCRIPTION
Referring to the drawings, and particularly to FIGS. 1 and 2 illustrating soil heating apparatus according to the present invention, a plurality of substantially vertically disposed electrodes 10-5 are slideably supported via insulating feed-throughs 26 from the roof of portable hood 28. Hood 28 is movable with respect to the ground and may be placed over a region containing hazardous material which is to be removed. The hood is also equipped with off-gas outlets 30 connected with the top interior of the hood which suitably lead to a gas treating, recovery, and/or destruction system.
The electrodes 10-25 are either driven into the ground or the ground is pre-drilled for their reception at locations within the underground area containing hazardous materials. The electrodes are suitably formed of one-half to one inch diameter carbon steel or aluminum rod and are inserted into the soil on approximately two foot centers in spaced array as illustrated. The electrodes are connected to a power system that suitably builds an increasing charge amongst the electrodes until discharge occurs. At the point of electrical discharge, heat is generated in the soil for raising its temperature.
The electrodes are connected to a power supply in the manner illustrated in FIG. 6 such that, for example, even numbered electrodes are connected or connectable to the positive side of the source and the odd numbered electrodes are connected or connectable to the negative side. The electrodes are evenly spaced, for example, in a 4×4 array as shown, so that each positive electrode is equally spaced from at least a pair of negative electrodes. Switching means 32 is employed for cyclically energizing positive electrodes 10, 12, 14, 16, 18, 20, 22 and 24 from the positive power supply terminal while the negative electrodes remain connected to the negative power supply terminal. Therefore, at least pairs of electrodes are sequentially actuated for initiating conduction in the ground between such pairs. Alternative switching means are clearly possible, i.e., a switching means similar to means 32 may be interposed between the negative power supply terminals and the respective odd numbered electrodes.
The power supply utilized in FIG. 6 is an impulse generator represented by direct current source 30 and a capacitor bank 34 connected across the terminals of DC source 30. The supply is capable of delivering a high DC voltage in the range of 100-2,000 kilovolts. When the capacitor bank charges to a predetermined level, a discharge takes place in the ground between a pair of electrodes, e.g. between electrode 12 and one or more of electrodes 11, 14, and 15 for the switch position shown. After substantial discharge of capacitor bank 34, the capacitor bank recharges from source 30 until the next discharge takes place between the same electrodes, or other electrodes if the position of switch 32 has been changed. High voltage impulse generators are commercially available and will not be described further.
Generally, the position of switch 32 is maintained for directing sequential discharges between a pair or pairs of electrodes until such electrodes reach a predetermined temperature level after which switch 32 is moved to the next position. Thus, switch 32 is suitably actuated by a timing mechanism (not shown) so that a given positive electrode will support, for example, ten discharges before the next positive electrode in sequence is selected. Typically a period of one second occurs between discharges which allows for gas recombination. The discharge voltage for the circuit of FIG. 6 is primarily dependent upon the spacing of the electrodes, as well as to some degree the type of soil therebetween.
Although applicable to all soil types, the system according to the present invention is most economically employed in regions of dry, sandy soil. As capacitor bank 34 charges, a voltage will be reached for which a discharge will be initiated between selected electrodes. Clearly the circuit can be modified, if desired, to insert additional switching means between capacitor bank 34 and the electrode array such that discharge between electrodes is initiated at a selected voltage level, preferably between 100 kv and 2,000 kv.
For the FIG. 6 circuit as illustrated, if moisture is present in the soil to any great extent, a steady current will first pass through water in the soil, driving off water vapor by resistance heating. As the soil begins to develop non-conductive dry spots, the voltage across the capacitor bank increases further and repetitive arcing through the soil begins. The charge-discharge cycle then continues to impart energy to the soil, heating the soil and driving off the volatiles. Once the soil adjacent the electrodes is dried, the arcing will usually provide higher voltage and higher power input to the soil than the resistive heating.
Referring to FIG. 3, a typical electrode 10 is illustrated in longitudinal cross-section. The electrode is cylindrical, having an inner axial electrode portion 36 suitably formed of carbon steel or aluminum and provided with an enlarged cylindrical tip 38 at its lower extremity. The inner axial portion 36 is covered by an insulating sleeve 40 formed of a high voltage insulating material such as pre-formed mica. Disposed over insulting sleeve 40 is a further metal sleeve 42, suitably carbon steel or aluminum, having the same outside diameter as electrode tip 38 but separated from tip 38 by radial flange 44 of insulating sleeve 40, the last mentioned flange also having the same outside diameter as tip 38. The metal sleeve 42 may be partially or fully withdrawn after the electrode assembly 10 is driven or inserted into the ground to eliminate the possibility of electrical arcing between the electrode tip 38 and metal sleeve 42.
Central portion 36 extends a distance outwardly above sleeves 40 and 42 for receiving electrical connection 46 which may lead to switching means 32 in FIG. 6. Electrical connection 46, as well as the protruding part of electrode portion 36, are suitably covered by high voltage shrink plastic insulation (not shown) rated at 100 kv or greater. An example is shrink-fit Okanite material. The voltage required to arc through dry soil is found to be greater than that required for arcing through air and it is therefore necessary to provide electrical insulation above the soil to prevent unwanted arcing. Alternatively, or in addition, pairs of arcing electrodes may be disposed in angular relation to one another rather than vertically as depicted in FIG. 2. For instance, the lower tips of electrodes 13 and 14 may be angled closer to one another with the upper portions farther apart, possibly eliminating the need for insulating sleeve 40.
Insulating the upper part of the electrode provides a means for concentrating electrical arcing at a given level in the ground to which the electrode is driven. At the same time, sleeve 42 and flange 44 have the same outer diameter as tip 38 to facilitate driving or insertion of the electrode into the ground. Assuming it is desired to initiate electrical discharge at a fairly low ground level, followed by raising the level of discharge so as to sweep through a given ground region, the electrodes of the type illustrated in FIG. 3 may be gradually or intermittently raised after performing desired heating at different levels. The power supply of FIG. 6 may be periodically deactivated and the capacitor bank discharged, after which the electrodes are raised manually from the top of hood 28 by sliding the same upwardly through insulators 26. After adjusting the levels of various electrodes to a higher level, arcing operation can be resumed. Alternatively, each electrode is suitably supplied with means for raising the same. Referring to FIG. 3, a hydraulic cylinder 48 which is mounted to the frame of hood 28 (by means not shown) is provided with an actuating rod 50 pivotally engaging a bracket 52 secured to the outer metal sleeve 42 locked to an electrode. The hydraulic cylinder 48 is periodically or continuously actuated to gradually move the electrode upwardly.
Another type of electrode is illustrated in FIGS. 4 and 5. This type of electrode as illustrated in longitudinal cross-section in FIG. 5 is similar in construction to the FIG. 3 electrode, and primed reference numerals are employed to refer to corresponding elements. However, this electrode is provided with an axial passage 54 extending the whole length thereof for communicating with a 13', 14', 21' and 22' in FIG. 4 are successively negative and positive electrodes and are connected to power supply means by separate conductors (not shown). However, a negative pressure can be applied to header 56 from conduit 60 for drawing hazardous material from the ground as it is volatilized by electric heating. The conduit 60 extends to a plant for generating the negative pressure and treating, recovering, or destroying the gaseous material removed from the ground. Alternatively, selected ones of the hollow electrodes may be connected to a source of stripping air, while other hollow electrodes may serve as means for removing stripping air from the soil being treated.
It will be appreciated the array of hollow electrodes illustrated in side view in FIG. 4 is desirably extended to a 4×4 array as illustrated in FIGS. 1 and 6, with similar connections being made thereto. Such array may or may not be provided with a covering hood 28, inasmuch as gaseous substance may be withdrawn by means of conduit 60 rather than conduits 30. However, the electrodes of FIGS. 1 and 2 may also be made hollow, i.e., to have the cross-section of FIG. 5, being provided with venting means 62 in FIG. 2 underneath hood 28 whereby the gaseous effluent is withdrawn from below the surface of the ground via the electrodes and into hood 28 so as to be withdrawn through conduits 30 in combination with gasses emitted directly upwardly through the ground surface.
Intermittent DC potential applied according to the present invention passes a series of electrical discharges between electrodes inserted in the contaminated soil such that energy dissipated by the discharges heats the soil and volatilizes or destroys organic wastes in the soil. In general, the soil temperature should be raised to at least 150° C. above the boiling point of an organic contaminant to achieve greater than 99% removal efficiency. This means that for removal of light organics, a temperature of about 200° C. should be achieved, and for heavy organics the soil should be heated to about 500° C. or greater. Therefore, a range between 200° C. and 600° C. is preferred in order to attain good efficiency on the one hand without requiring excessive power on the other. However, it is clear some removal can take place below and above this range. The total duration of time required by the discharge regime to heat the soil to the requisite temperature sufficiently for decontamination will depend upon the individual soil content as well as on the material buried therein. Soil temperature is readily measured by conventional means and the process may be continued until the soil region is substantially out-gassed with respect to the contaminant.
Higher soil temperatures which assure destruction of hazardous chemicals are an option. Accordingly, the ground may be heated to a temperature for substantially destroying the contaminant chemicals by pyrolysis, followed by combustion of the pyrolysis products when these products reach the surface. In this case, a higher ground temperature than 600° C. is preferred, although many materials will begin to pyrolyze at 300° C. Thus, a range of 300° C. to 1200° C. is suitable for some degree of destruction of the offending materials in the ground. For achieving combustion when the pyrolysis products reach the surface, the hood 28, as illustrated in FIGS. 1 and 2, may be employed, and an additional inlet (not shown) for combustion gas is suitably provided, with the combustion products being removed via conduits 30. As another alternative, the ground may be heated to the preferred temperature range, i.e., between 200° C. and 600° C., with destruction or other treatment taking place at an above ground location to which the offending substances are conveyed via conduits 30 and FIGS. 1 and 2 or conduit 60 in FIG. 4.
In a test for the removal of 2-chlorophenol test chemical, a removal efficiency of 95 wt. % was achieved in a run time of 4.2 hours, with an average power expenditure of 115 watts. The maximum soil temperature was 304° C. in sandy soil. Successful tests have also been conducted for test deposits of trichloroethene and hexachlorobenzene.
The effluent is suitably conveyed by conduits 30 in FIGS. 1 and 2, or 60 in FIG. 4 to a gas treatment, recovery, or destruction system. By way of example, a treating or cleaning system is depicted in FIG. 7 where the off gas is received at 64 either from the hood of FIGS. 1 and 2 or the header of FIG. 4. In the case of off gas received at very high temperatures, for example in the instance of combustion within hood 28, a cooler 66 is employed and comprises a finned air-to-glycol heat exchanger. This cooler can be by-passed by opening valve 70 and closing valve 68.
From the gas cooler, the off gas is suitably split and directed into one of two wet scrubber systems that operate in parallel. One such system, indicated at 72, is shown in block fashion and the other parallel system will be described. Valve 74 leads to quench tower 76 feeding tandem nozzle scrubber 78 which in turn leads to vane separator 80. The tandem nozzle scrubber may comprise a tandem nozzle hydrosonic scrubber manufactured by Hydro-Sonic Systems, Dallas, Tex. The quencher reduces the gas temperature to about 66° C., and supplies some scrubbing action to remove a portion of entrained particles. The primary functions of the tandem nozzle scrubber are to remove any remaining particles and condense remaining semi-volatile components as well as to provide additional cooling of the off gas. The vane separator that follows is designed to remove all droplets greater than or equal to 12 μm.
A glycol scrub solution that is injected into the quencher and tandem nozzle scrubber from tank 82 is cooled through heat exchanger 84 before being returned to the process. After the scrub solution is returned to tank 82, it is circulated via pump 86 back to quencher 76 and scrubber 78.
Following the scrubber system, the gas is cooled in condenser 88. The condenser and mist eliminator or vane separator 90 remove droplets greater than or equal to 12 μm. Final decontamination of off-gas particulates is achieved in a two stage filter/adsorber assembly following heating of the gas at 92. The first stage is composed of two parallel HEPA (high-efficiency particulate air) filters and charcoal adsorbers 94 feeding a single HEPA filter and charcoal adsorber 96.
The gaseous effluents are drawn through the off-gas system components by an induced draft system, the driving force being provided by a blower 98. This blower, which has substantial capacity, is employed to provide negative pressure within hood 28 or within header 56 and the hollow electrodes for aiding in removing gaseous products from the ground. After passing through the blower system, the off-gasses are exhausted to a stack which is indicated at 100.
The system of FIG. 7 is somewhat conventional and it is understood it could be replaced by other gas treatment systems. It may be used alternatively in conjunction with a destruction system comprising controlled air incinerators coupled between the ground site being detoxified and the off-gas system of FIG. 7, particularly in the case where combustion within the hood 28 is not being carried out. Alternatively, ground chemicals may be recovered in a cryogenically cooled condenser or air exchange condenser prior to delivery to the off-gas system of FIG. 7. Various combinations of gas treating systems of this type can be employed.
As an alternative embodiment, a continuous conduction system may be employed with the electrode configuration depicted in FIGS. 1 and 2, wherein an electrically conductive heavy oil is sprayed, inserted or injected into the ground for supporting conduction between the electrodes before power is applied. A higher current, lower voltage source of power is required in such case because of the higher current levels. The voltage utilized is suitably between 1,000 and 4,000 volts, for supporting a current in the ground between electrodes of between 1600 amps and 450 amps. The electrically conductive fluid is suitably sprayed on or inserted into the soil to be treated, so that it is absorbed evenly into the soil, and the electrodes are then inserted into the soil. The electrical conductivity of the fluid will allow sufficient current to pass among the electrodes to dissipate substantial heat in the soil. This method is suitable for heating volumes of soil to relatively low temperatures, e.g. less than 200° C. The first described embodiment, i.e., utilizing high potential arc discharge, is preferred for several reasons. High temperatures can be more easily reached without the introduction of conductive materials and, moreover, the high potential arcing is less dependent upon soil types, i.e., less dependent upon the absorption of the conducting medium in the soil and the appropriate distribution of the conducting medium through the soil.
As a further alternative embodiment, high potential intermittent arcing may be followed by more continuous arcing with a suitable power supply. Source 30 may in such case take the form of an impulse source and a somewhat lower voltage parallel source capable of delivering greater and substantially continuous arcing current.
While several embodiments of the present invention have been shown and described, it will be apparent to those skilled in the art that many changes and modifications may be made without departing from the invention in its broader aspects. The appended claims are therefore intended to cover all such changes and modifications as fall within the true spirit and scope of the invention.
|
A method and apparatus for decontaminating ground areas where toxic chemicals are buried comprises disposition of a plurality of spaced electrodes in the ground to be treated and application of a voltage across the electrodes for bringing about current flow through the ground. Power delivered to the ground volatilizes the chemicals which are collected and directed to a gas treatment system. The preferred form of the invention employs high voltage arc discharge between the electrodes for heating a ground region to relatively high temperatures at relatively low power levels.
| 4
|
This is a non-provisional application claiming priority to U.S. Provisional Application Ser. No. 60/601,410 filed Aug. 13, 2004.
BACKGROUND OF THE INVENTION
1. Field of The Invention
Applicant's invention relates to a system and method for covering existing moldings around doorways and along walls and baseboard moldings in existing homes, and, more particularly, to a system and method for installing said system for attaching doorway overlay molding and baseboard encapsulate to existing doorway and baseboard molding. This system substantially improves the appearance of baseboard molding and molding around the doorways and walls by covering the existing molding with a more decorative molding. This system and method is user friendly such that an amateur or “do-it-yourself” person working alone can install these new molding designs with less costs and less frustration, and still create an expensive look. The examples presented are primarily for doors and are shown for purposes of illustration and not limitation. It is understood that this system and method could apply to other openings and architectural features such as baseboards, railings, stairs, windows, skylights, attic openings, etc.
2. Background Information
In many homes, builders and general contractors generally use inexpensive type of trim around the doors and other openings, and along the floor. This molding is used to conceal imperfections that occur during the construction of the home around doorways and bases of walls, specifically where the wall meets the doorway or the floor. Because these walls and doorways have various corners, such as corners of doorways or corners where two walls meet, in order to install molding completely around a doorframe or where two walls meet and form an internal or external corner, it is necessary to cut the molding at various angles using a miter box so that the corners of the molding fit smoothly together around the corners. Furthermore, when the molding is installed, the molding is usually set back from the opening edge to form a reveal. This reveal is used to overcome the problems with trying to match flush edges. Wood moves and changes shape through the course of time. Because of this characteristic, it is impossible to get edges to stay flush when aligning molding to a doorway or wall. Stepping molding back to form reveals causes shadow lines and creates different planes that make it harder for the eye to pick up discrepancies. Creating this reveal when replacing molding so that the reveal is consistent and aesthetically pleasing is a complicated task. This molding is complicated and is usually installed by professionals.
Once the average consumer purchases a home, he/she may be inclined to change the standard trim used by the builder in favor of molding that is much more attractive and aesthetically pleasing. However, this creates a dilemma: Having spent a substantial amount of money in order to obtain the home, is the desire to upgrade the old molding around the doors and along the floor strong enough to justify spending even more money to have professionals come in and completely remove all the trim along the floor and around the doors and then install new trim? Additional expenses inevitably incur during this removal and installation process because of the difficulty of removing items that were intended by the builder to be permanent fixtures. Inherent in the removal process of the mold trim are damages in the forms of nicks, scrapes, dents, scratches, and even holes to the wall surface adjacent to the trim being removed. Furthermore, replacing molding does not merely consist of removing the old molding and attaching new molding. In addition to removing the old molding, one must clean the surfaces where the old molding left paint and caulk, measure and cut the new molding, sand and paint the new molding, align the new molding to insure that the corners align and the molding is square, and only then may the molding be attached to the wall or doorway surface. Even then the molding should be set back from the doorway or wall to form the reveal. This is an arduous process requiring a great deal of time and many tools, such as a hammer, a pry bar, nails, a hand saw, a miter box, a tape measure, and sanding and painting supplies, just to name a few. Furthermore, if great care is not taken, the consumer may well have to hire other professionals, such as painters or sheet-rockers, incurring an additional unanticipated expense in order to obtain the final upgraded “look” the consumer initially had in mind. The result is a costly renovation project.
The same concerns occur with the owner of an older home. In the course of time, the molding will become nicked, scraped, dented or scratched. This molding system allows the old molding to be covered with an upgraded more decorative molding with a minimum effort.
Obviously, most consumers are not in a position financially to undergo such a costly renovation shortly after purchasing their home or renovating an older home. Indeed, many consumers wait years before they may even consider such an expensive project. There are still others who, because of the cost and expense involved, remain complacent with their old molding.
There exists in the art the general concept of molding that would cover preexisting molding. Several patents relate to this field. These include: U.S. Pat. No. 871,028 to Brian; U.S. Pat. No. 2,887,739 to Bensman; U.S. Pat. No. 3,899,859 to Smith; U.S. Pat. No. 5,199,237 to Juntunen; U.S. Pat. No. 5,809,718 to Wicks; U.S. Pat. No. 6,021,619 to Mansson; U.S. Pat. No. 6,189,276 to Pinto, et al.; and U.S. Pat. No. 6,516,576 to Balmer. Of these patents, only Pinto, et al., come close to the present invention. However, as home owner's interest in “do-it-yourself” projects increase coupled with increasing costs of skilled labor, there still does not exist a system for the average consumer, working alone, to easily install and maintain aesthetically pleasing and attractive molding in their homes with a minimum of tools.
One problem “do-it-yourselfers” face include the need for precise measurement of corner pieces on the top corners of the doorframes and the left and right bottom portions of the doorframe as well as places where two walls meet in a corner to minimize any gaps or overlaps. Another is the skill involved in cutting these components using a specialized tool such as a miterbox. Yet another problem is the realistic notion that a “do-it-yourselfer” would most likely not have any assistance from other people during the project.
Although the Pinto patent teaches the general concept of having a new baseboard molding that is more decorative to cover inexpensive baseboard molding, this patent does not disclose or solve the problems encountered by the “do-it-yourself” homeowner previously discussed such that it minimizes or entirely eliminates the use of skilled craftsmen, complicated tools and machinery (such as a miterbox), and minimal assistance required. Additionally, none of the other patents mentioned overcome the disadvantages and problems associated with “do-it-self” door and base molding renovation projects. Nor do any present an integrated system to solve the problem created when one type of molding transitions into another, such as occurs at the bottom of a door when baseboard molding meets doorway molding, or where two walls meet to form an external or internal corner.
The present invention substantially improves and solves the problems discussed above because it can be completed by a single “do-it-yourself” homeowner without the use of professional craftsmen or complicated tools and machinery. The final result is a dramatically improved appearance of existing door, baseboard, and baseshoe molding over the currently installed molding. The use of this system and method thus now enable the average consumer and “do-it-yourself” homeowner to fully renovate all the door and baseboard moldings at less cost, less hassle, less frustration, and less time than would have previously been possible, and with a high degree of confidence in the results.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a molding that is applied over existing molding without the removal of the existing molding.
It is further an object of the present invention to provide a molding system that eliminates the need of a miter box to make angled cuts.
It is another object of the present invention to at least partially cover existing moldings.
It is another object of the present invention to cover existing molding of varying widths and thicknesses.
It is still further an object of the present invention to have a molding design that can be easily installed by the “do-it-yourselfer” market with very little effort, so there will be no need for the use of a miterbox to cut angles when installing this system.
It is another object of the present invention to use existing doorway molding as a base point for establishing a reveal.
It is yet another object of the present invention for such molding to be much more decorative in nature.
The miterless molding design system has three primary components: (a) overlay molding that follow along the doorways; (b) baseboard encapsulate that follow along the floors; and (c) corner blocks that seamlessly connect molding where the walls meet at an interior or exterior angle, or a corner is encountered around the doorway. The corner blocks eliminate any need for a miterbox to cut angles when installing the system. All the individual user has to do is cut the proper lengths of molding required. Recesses are cut into the backside of the corner blocks which allow the corner blocks to receive the old molding. With the corner blocks in place around the doorway, the overlay molding and baseboard encapsulate can attach to existing molding and be butted against the corner blocks, thus eliminating any need for angle cutting.
For dealing with moldings going around corners where two walls meet at an internal or external approximate right angle, a right angle block is used. A recess is cut into the right angle block in order to receive the existing baseboard at the internal corner. For dealing with moldings and walls forming corners where two walls meet at an external right angle, a right angle corner block with an additional recess is used to receive the exposed corner of the wall above the existing molding where the two walls meet.
By using the corner blocks and right angle blocks, right angles can be cut in every piece of molding for installation. If there are any openings at the corner blocks or right angle blocks, those openings between the molding and corner blocks would be calked. The design illustrated on the figures below are merely for illustrative purposes and not for limitation purposes.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front elevation view of an embodiment of the present invention.
FIG. 2 is a cross-sectional view of FIG. 1 along section lines 2 - 2 .
FIG. 3 is a cross-sectional view of FIG. 1 along section lines 3 - 3 .
FIG. 4 is a front elevation view of another embodiment of the present invention.
FIG. 5 is a perspective view of an upper corner block of the preferred embodiment of the present invention.
FIG. 6R is a perspective view of a right lower corner block of the preferred embodiment of the present invention.
FIG. 6L is a perspective view of a left lower corner block of the preferred embodiment of the present invention.
FIG. 7A is a perspective view of a right angle block for internal right angles of the preferred embodiment of the present invention.
FIG. 7B is a perspective view of a right angle corner block for external right angles of the preferred embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
An embodiment of the present invention is illustrated in FIG. 1 . FIG. 1 is a front elevation view of a doorway 10 in a wall surface 12 that has a doorway overlay 14 therearound and a baseboard encapsulate 16 extending therefrom. The baseboard encapsulate 16 is abutted against the wall surface 12 and meets with a floor 20 .
A cross-sectional view of FIG. 1 along section lines 2 - 2 is depicted in FIG. 2 . The doorway overlay 14 attaches and thus covers the existing doorway molding 18 . A side edge 26 of the doorway overlay 14 aligns distantly from the doorway 10 . The recessed abutting inside portion 24 of the doorway overlay 14 is disposed over a length 130 of the existing doorway molding 18 and attaches along vertical and upper horizontal peripheral edges of the doorway 10 by a pair of vertical members (not shown). A corner formed by a wide end 126 and the length 130 of the existing doorway molding 18 is bedded into and recessed inside a corner 30 of the doorway overlay 14 . A small dead space 132 is created and enclosed by the wide end 126 of the existing doorway molding 18 , an angled inside portion 22 of the doorway overlay 14 , and the wall surface 12 . A small end 128 is aligned proximately to the doorway 10 . The new doorway overlay 14 includes an outer decorative surface 28 shown merely for illustrative purposes and not for limitation purposes.
Although the wide end 126 is described as embedded into the corner 30 of the doorway overlay 14 , it is understood that a typical spacer (not shown) could be inserted between the corner 30 and the wide end 126 to accommodate doorway moldings of different widths. In this configuration, the small end 128 of the doorway overlay 14 continues to be set back from the existing doorway molding 18 , exposing a small portion of the existing doorway 18 , forming a reveal.
A cross sectional view of FIG. 1 along section lines 3 - 3 , as seen in FIG. 3 , illustrates the existing baseboard 32 covered by the baseboard encapsulate 16 . An upper angled wall abutting portion 34 of the baseboard encapsulate 16 is fitted over a top surface 156 of the existing baseboard 32 . A recessed inside corner 36 gives room for thicker than normal existing baseboards. A recessed angled lower portion 38 of the baseboard encapsulate 16 allows the baseboard encapsulate 16 to accommodate existing baseboard 32 . A bottom surface 40 of the baseboard encapsulate 16 is flat and is disposed adjacent the floor 20 . A dead space 42 is created and defined by the recessed angled lower portion 38 of the baseboard encapsulate 16 , the floor 20 , the existing baseboard 32 , and the recessed inside corner 36 of the baseboard encapsulate 16 .
The baseboard encapsulate 16 and the doorway overlay 14 cover the existing baseboard 32 and the existing doorway molding 18 , respectively, and adhere the to wall surface 12 through a securing means such as a nail (not shown). In particular, it is preferable to use headless nails to minimize the nail's appearance on the baseboard encapsulate 16 . Headless nails may also be tapped into the molding for further concealment. Additionally, wood putty or other similar substance may be used to cover the nail entirely.
An alternative embodiment of the present invention is illustrated in FIG. 4 . In this figure, the baseboard encapsulate 16 is separated from the doorway overlay 14 by a lower left corner block 48 and a lower right corner block 50 . At the lower left hand side of the doorway 10 , the baseboard encapsulate 16 abuts a side edge 134 of the lower left corner block 48 . A bottom surface 136 is disposed adjacent the floor 20 . A top surface 76 joins the doorway overlay 14 . The doorway overlay 14 then continues upward in a longitudinal direction until it abuts a bottom surface 142 of the upper left corner block 46 . A side edge 144 of the upper left corner block 46 abuts the doorway overlay 14 which then extends in a latitudinal direction until it abuts the right upper corner block 150 at a side edge 146 . The doorway overlay 14 is then joined at a bottom surface 148 of the right upper corner block 150 and extends downward in a longitudinal direction to align with a lower right corner block 50 along a top surface 64 . A side edge 70 of the lower right corner block 50 then joins the baseboard encapsulate 16 . A bottom surface 138 of the lower right corner block 50 is disposed adjacent the floor 20 .
The upper corner blocks 46 and 150 are used in the upper left and right corners of the doorframe. Their use eliminates the need to make angle cuts other than perpendicular cuts in order for the doorway overlay 14 to join together at the corners. A more detailed description of the upper left corner block 46 and the upper right corner block 150 follows.
FIG. 5 shows A backside 52 of the upper corner block 46 . Although the numbering for the corner blocks for FIG. 4 differentiated an upper left corner block 46 from the upper right corner block 150 , the corner blocks are identically designed so as to be able to be used with either the left or right upper corner; the only difference being its orientation. The use of different numbers for the upper left and right corner blocks in FIG. 4 was merely for convenience. Therefore both the upper left and upper right corner blocks are from here forward described as the upper corner block 46 . The backside 52 of the upper corner 46 rests against the wall surface 12 . A recess 54 is cut into the back side 52 of the upper corner block 46 . The cut is made at an angle 140 . This angle 140 then can be fixed snuggly over the inward angle (not shown) of the existing doorway molding 18 . A recessed edge 60 and a recessed edge 62 wrap snuggly around the corners of the existing doorway molding 18 . The bottom surface 142 and a side edge 58 then become the receiving surfaces for the doorway overlay 14 . The doorway overlay 14 then extends downward in a longitudinal direction until it aligns with either the lower left corner block 48 or the lower right corner block 50 . The lower left corner block 48 and the lower right corner block 50 are similarly designed, but accommodate the doorway overlay 14 and the baseboard encapsulate 16 as detailed below.
Referring now to FIG. 6L , a wall abutting surface 82 of the lower left corner block 48 rests against the wall surface 12 . A second recess 86 cut therein allows the existing baseboard 32 to be received therein. The baseboard encapsulate 16 then fits over the existing baseboard 32 and abuts the lower left corner block 48 along the side edge 134 . A side edge 84 faces the doorway 10 . A first recess 78 cut therein receives the existing doorway molding 18 . The existing doorway molding 18 is further secured by an inside corner 80 . The first recess 78 is cut at an angle 152 in order to accommodate the angles typically associated with existing doorway molding. The doorway overlay 14 connects with the lower left corner block 48 along the top surface 76 , while the bottom surface 136 is disposed adjacent the floor 20 .
Referring to the lower right corner block 50 , as depicted in FIG. 6R , a wall abutting surface 68 rests against the wall surface 12 . A second recess 72 cut therein receives the existing baseboard 32 therein. A first recess 66 cut therein receives the existing doorway molding 18 therein. The first recess 66 is cut at an angle 154 in order to accommodate the angles typically associated with existing doorway molding. The existing doorway molding 18 resting inside the first recess 66 is further secured by an inside corner 88 . The baseboard encapsulate 16 covering the existing baseboard 32 couples to the lower right corner block 50 along a side edge 70 . A side edge 74 faces toward the doorway 10 . The doorway overlay 14 aligns with the lower right corner block 50 at the top surface 64 , while the bottom surface 138 is disposed adjacent the floor 20 .
The concept of blocks placed over corners may also be used where two wall surfaces meet, creating an internal or external corner. FIG. 7A illustrates a right angle block 90 . The right angle block 90 is used when two wall surfaces meet perpendicularly at substantially internal right angles to each other. The right angle block 90 is positioned such that a recess, formed by a surface 100 and a surface 102 cut therein receives the existing baseboard 32 . The baseboard encapsulate 16 is placed over the existing baseboard 32 and abuts the right angle block 90 at a side edge 96 and a side edge 98 . A bottom surface 104 of the right angle block 90 is adapted to be positioned adjacent the floor 20 . An outside decorative surface 94 is also included on the right angle block 90 , while a top surface 92 remains unobstructed.
A similar design is used when two walls meet at substantially perpendicularly external right angles to each other, forming an external corner. FIG. 7B illustrates a right angle block 106 with a recess, formed by a surface 120 and a surface 122 cut therein, to receive the existing doorway molding 18 . Additionally, a second recess defines a first surface 112 and a second surface 114 , and is adapted to receive a portion of the wall corner disposed above the existing baseboard 32 . The baseboard encapsulate 16 abuts the right angle block 106 along a side edge 116 and a side edge 118 . A bottom surface 124 is adapted to be positioned adjacent the floor 20 , while a top surface 108 remains free from obstruction. The right angle block 106 also includes an outside decorative surface 110 (similar to the outside decorative surface 94 for the inside lower corner block 90 ). Thus, after installation, the right angle block 90 covers the existing baseboard 32 and abuts the baseboard encapsulate 16 at internal corners. Similarly, after installation, the right angle block 106 covers the existing baseboard 32 and abuts the baseboard encapsulate 16 at external corners.
|
A molding system and method for installation that covers existing molding. The molding system covers existing trim for doorways and floors with a more decorative molding. The invention includes a molding overlay. An upper corner block covers the intersections of the existing doorway molding, and a lower corner block covers a section of the existing doorway molding with the existing baseboard, eliminating the need to cut mitered angles in the overlay molding. Recesses in the backside of the corner blocks allow the corner blocks to receive the old molding. The molding overlay abuts the corner blocks, thereby avoiding the requirements for making any cuts other than perpendicular cuts.
| 4
|
REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of the filing date under 35 U.S.C. § 119(e) of U.S. Provisional Patent Application No. 60/785,422 filed Mar. 24, 2006.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to the coloring of human hair, and more particularly, to an improved method and device for quickly and effectively coloring human hair.
2. Background Art
Hair color variegation is a popular service performed by the professional beauty industry. The process involves the segregation of one or more sections of human hair followed by the treatment of the segregated hair with a hair coloring method or chemical. The technical skill required to separate particular sections of a person's hair from the remainder has kept this procedure mostly in the purview of hair salons.
A previously popular method for highlighting hair is described in U.S. Pat. No. 5,562,111. The method disclosed therein involves a cap tightly fitted over a scalp of combed-back hair. Strands of hair are then pulled through holes in the cap with a crochet hook and the exposed hair is colored to create the effect of variegation. Although this method can be somewhat successful at both keeping the chemical hair coloring from bleeding onto hair not intended for treatment and creating a generally variegated look, the necessity of drawing hairs through individual holes in the cap makes it difficult for the technician to consistently draw out a section of hair from the desired area without unintentionally entraining undesired sections of hair from areas surrounding the hole. The end result is unpredictable and, sometimes, very undesirable. Moreover, the available variegation pattern is dictated by the location and distribution of the holes in the cap. Additional disadvantages to this method include the inability to effectively color hair roots, the inability to consistently prevent the bleeding of color to adjacent sections of unselected hair, and the pain experienced by the recipient due to the repeated pulling of his or her hair through small holes. U.S. Pat. No. 4,165,754 is another example of a hair highlighting method employing a cap over the scalp. That method has the identical drawbacks of the '111 patent.
Alternatively, there are various combing methods used to apply hair color in a variegated manner. A general method involves dipping a comb into a liquid hair color and pulling the comb through the hair to be treated. Only relatively large sections of hair can be treated in this manner and it is difficult for the operator to avoid color bleeding onto hair not intended for treatment. U.S. Pat. No. 3,349,781 describes a method wherein a hair stylist parts hair into sections and uses a brush with a series of spaced tufts to brush streaks onto random strands. The tufts of the brush are dipped into a hair color composition and retain the composition until the brush is drawn across the strands to be colored, thus depositing the artificial colorant thereon. This method utilizes protective sheets placed under and over the streak-treated partings before and after treatment to avoid color bleeding to adjacent hair. However, using this brush method makes it difficult to choose which strands of hair will be treated. Hence, there is minimal control over the placement of the hair treatment. Therefore, larger sections of hair are treated, resulting in a more unnatural hair coloring effect.
U.S. Pat. No. 5,337,765 describes a modular brush for applying hair color compositions with a brush body and detachable bristle modules so that the brush can be configured to achieve a user-defined variegated pattern. However, this apparatus presents the same limitations as described above for the '781 patent.
A more commonly used technique by those skilled in the art involves selecting hair through weaving with a conventional tail comb and then placing the selected sections onto aluminum foil (or some other barrier material) and then painting the selected sections with a hair color composition. A dispensing device for metallic foil that may be used in this process is disclosed in U.S. Pat. No. 6,237,608. The foil method allows for smaller, more independent, more consistently variegated sections to be treated, resulting in a more naturally variegated final appearance. When using this method, the potential for color bleeding onto surrounding hair is reduced. The foil method is also more effective for applying color composition to the segregated sections of hair as close to the scalp as possible. However, even with these advantages over other hair coloring procedures, the foil method is very time consuming and expensive. For an average client, at least 30 to 50 minutes is required to complete this method of hair coloration.
Hair color variegation techniques that involve color treated sections that have been woven away and placed inside a barrier material for processing produce natural and attractive variegated appearance. It follows then that advancement in the field of hair color variegation involves weaving, color treatment and barrier material. Reference will now be made to technology that attempts to advance on one or more of these three general systematic elements.
U.S. Pat. Application No. 2005/0028835 discloses “A Device For Dispensing a Barrier Material to a Lock of Hair.” This device can be generally understood (although some of the embodiments vary greatly) as being comprised of two tape dispensers that are hinged at the roll end. The tape dispenser end (distal to the roll end) opens and closes in such a way as to cause the faces of the two tapes to touch. A section of hair can be chosen and encapsulated between the two tapes. The face of one or both of the tapes is treated with one or both of the chemical hair color components. The embodiments also include means within the device to apply hair color just before the hair is encapsulated within the tape. This method, although saving time and product, still lacks the ability to automatically, quickly and accurately weave away a plurality of selected hair sections for variegation purposes.
U.S. Pat. No. 5,152,306 discloses a hair-weaving comb that has regular teeth and inwardly barbed teeth attached alternately across the spine of the comb. In practice, a thin section of hair is parted away from the scalp. The teeth of the comb are then pushed into the parting and drawn back out. The barbed teeth pick up sections of hair while the straight teeth do not. An operator grabs the hooked hair, pulls the comb away and lets the non-hooked hair fall. This device allows for a faster and more consistent weave than the manual hair weaving method. However, it does not offer any device or method to apply color or barrier material. In addition, the device does not effectively pick up sections of hair in a predictable manner, nor does it pick up hair against a curved scalp surface.
U.S. Pat. No. 5,024,243 discloses a comb/color applicator combination. The device discloses a comb with a hollow spine that screws onto a container filled with chemical color composition. When the container is squeezed, the chemical composition fills the hollow spine of the comb and exits the spine through small holes positioned in between the teeth of the comb. Although this device will yield a variegated hair color appearance, there is a substantial risk of color bleeding because the variegated hair is not woven away from the rest, and the device fails to provide the technician with a high degree of control or accuracy.
U.S. Pat. No. 5,303,722 describes a hair lightening method involving the use of an optical photosensitizer and a compound capable of providing a hydrogen radical (ethanol is preferred) in a solution. The solution is applied to the hair and then left to saturate for 5 to 60 minutes. Low intensity ultraviolet light (typically provided by a comb or hood) is then applied to the hair causing a hydrogen to be exchanged between the two components in the solution, thereby creating hydrogen peroxide inside the hair shaft. The peroxide is excited by the light causing some of the hair pigment (melanin) to be destroyed. As a result, the hair subjected to the process is lightened. Using this same photochemical reaction, the '722 patent describes a method whereby the entire head of hair is saturated with the photosensitive solution followed by the segregation of small sections of hair by manual weaving. The non-segregated hair is masked with an opaque material so that only the segregated hair is exposed to the low intensity ultraviolet light. The result is a “highlight” effect among the segregated hair strands. The techniques described in the '722 patent involve considerable time and manual labor.
U.S. Pat. No. 4,325,393 discloses a hooking mechanism for hair coloration. The implement has a plurality of equidistantly spaced, accurate hook members movable between open and closed positions with respect to the bottom surface of the body of the implement by an operating slide member at its top. After thus hooking and engaging spaced groups of hair strands for treatment, the implement is lifted from the scalp to isolate the strand groups for bleach or dye treatment. This implement does not offer the operator nearly the degree of control that is inherent in the instant invention. Although the bottom surface of the device is curved, it does not flexibly conform to the curve of the head. This prohibits the device from uniformly selecting portions of hair.
More importantly, a major drawback results from the fact that the '393 patent discloses a hooking arrangement that moves from an open to closed position by partially rotating on an axis that is approximately 1½ of its own hook diameter lengths above the actual hook. Thus, the hooks “swing” through an opening at the bottom surface of the body from a point just inside the body. The hooks swing from a not entirely open position to a not entirely closed position. The “swinging hook” will not entrain hair as effectively or as precisely as a hook that rotates out of a body spinning from its radial center, as do the hooks in the preferred embodiment of the present invention. Furthermore, the '393 patent offers no means by which the hooked hair can have a variable tension applied to it when the hooks are in the closed position. Hair may be hooked away from the scalp, but it cannot be held against tension; the hair will simply slide through hooks when the operator pulls the device away from the head. Finally, the '393 patent does not include any means by which it can apply color compositions or processing accelerators (e.g., heat, light), nor any means to assure a safe and controlled contact with the scalp by the swinging hooks.
U.S. Patent Application No. 2006/0042643 discloses a hair highlighting tool. However, the disclosed invention does not address the multiple problems overcome with the instant invention. In fact, it may exacerbate some of the problems regarding the regulation and control of hair coloration.
All of the above-cited prior art addresses certain needs. However, none solves the time, consistency and control problems that are encountered when performing the manual hair color variegation technique presently most popular in the purview of the hair salon. In addition, none have successfully combined mechanical elements into a single device to give it the ability to do all that is mentioned in the present disclosure. Accordingly, there is a need for a hair coloration device that safely, accurately, predictably, and quickly applies colorant to uniformly selected and entrained portions of hair.
SUMMARY OF THE INVENTION
The present invention is a hair coloration device that quickly, accurately, predictably, and safely applies hair color to selected strands of hair. The device is held by a handle and activated by a trigger using the index finger. The main body, or chassis, of the device extends forward perpendicularly from the top of the handle, ending distal to the top of the handle in an array of “floating heads,” preferably, more than three, and more preferably, five or more floating heads. Each of the floating heads includes a hooking mechanism, that, when in contact with the scalp, has the ability to safely hook, or entrain, a single small stalk or section of hair away from the scalp and apply a variable tension to it. The hooking mechanism generally consists of a hook and a hooking platform. When the aligned array of floating heads are applied parallel to and approximately ⅛ of an inch below a straight parting of hair, certain embodiments of the invention allow each floating head to individually flex into accurate contact with the varying curvature of the scalp. In other embodiments, the floating heads are aligned along a contoured base designed to conform with the curvature of the scalp. Once the hooking platforms of the floating heads have made contact with the scalp, the trigger is pulled and each floating head hooks and entrains a strand of hair, and grasps it between the hooking platform and the hook.
As each hook rotates on its axis through its course from its resting position on the tops of the hooking platforms to the point where the hooks have lifted stalks of hair away from the scalp, the hooks only make light, controlled contact with the scalp. Once the hooks have entrained strands of hair, the more pressure that is applied to the trigger, the tighter the hair is grasped between the hook and hooking platform.
A preferred embodiment of the present invention includes an array of liquid hair color applicators that are removable and interchangeably membered to the top front portion of each floating head. A preferred embodiment of the liquid hair color applicator comprises a reservoir, a platform and a fluid dispensing means, such as a strip of felt or other suitably porous material capable of capillary action, or a roller ball or rotating cylinder. The fluid dispensing means shall be generally referred to herein as the “wick.” One end of the wick extends into the reservoir while the other runs along the bottom of the hooking platform. Accordingly, when the stalks of hair are grasped between the hooks and hooking platforms, the stalks are pressed against the wick, thereby applying liquid to the hair. The liquid may be a chemical colorant, hair mascara, henna, or other types of temporary, semi-permanent or permanent hair color compositions. As a result, when the floating heads are urged against a parting of hair and the trigger is pulled, hooking and therefore entraining a plurality of stalks of hair away from the scalp, an operator may maintain a certain pressure on the trigger and proceed to pull the device away from the scalp thereby coating the stands of hair with liquid hair color from a point very close to the scalp to the ends of the strands, or any point between. When the trigger is released, the hooks will release by rotating in a radial fashion away from the bottoms of the platforms completely releasing the hair color coated stalks of hair.
Each liquid hair color applicator can be designed to include a reservoir with two or more chambers and/or two or more wicks, so that two products or chemicals can be combined at the point of contact with the entrained hair to cause or catalyze a desired chemical reaction to the hair. The chemical reaction may occur as the two chemicals are mixed outside the liquid hair color applicator on the entrained hair. Alternatively, the chemicals could be mixed in the applicator. For instance, hydrogen peroxide could be contained in one chamber and an ammonia based dye precursor mixture could be contained in another. The two chambers can be separated by an thin membrane (e.g., a thin layer of plastic) that can be easily broken bending or squeezing the liquid hair color applicator. By breaking the thin membrane, the chemicals in both chambers mix and create a new compound. The mixing can also be accomplished with a removable barrier between the chambers that can easily be removed after the reagents have been poured into the separate chambers.
In other embodiments, one chamber is placed in front of another chamber inside the reservoir. In such embodiments, each chamber could have its own wick. As the hair color applicator is dragged along the surface of the hair, the reagent in the front chamber is applied to the hair first. After that, the reagent in the back chamber is applied to the hair on top of the reagent that was in the front chamber. In effect, this allows the reagents in both chambers to mix after being applied to the entrained strands of hair. These embodiments allow the chemical reaction necessary to artificially color the entrained hair to take place after the reagents have been applied to the hair.
In yet another embodiment of the invention, a source of light can be added to the device and directed to the point where the hair color applicator contacts the entrained hair. The light source can be produced with optical fibers or lasers, or other such means known in the art. The light source should produce the required wavelength(s) to catalyze or activate the desired chemical reaction at the point where the hair color applicator applies a photosensitive hair color composition to the entrained hair. As the entrained hair is pulled through the hooks, the hair color applicator applies a photosensitive hair color composition to the hair. The photosensitive chemical then comes into contact with the light source causing a chemical reaction to occur that colors the hair.
In other embodiments, the hooking mechanism can be manufactured to heat up (e.g., by sending an electric current through a hooking mechanism capable of electric conduction) and apply heat to the entrained strands of hair
The advantages and features of novelty characterizing the present invention are pointed out with particularity in the appended in Appendix A, including specific examples of how the device may be utilized to save hair stylists substantial amounts of time in coloring hair. To gain an improved understanding of the advantages and features of novelty, however, reference may be made to the following descriptive matter and accompanying drawings that describe and illustrate various embodiments and concepts related to the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the hair color variegation device according to the present invention showing the trigger-operated grip, a series of five (5) independently mounted floating heads, and the connection of the trigger mechanism to the rotating hooks located at the ends of the floating heads in various embodiments.
FIG. 2 is a perspective view of floating heads in an alternative embodiment of the hair color variegation device showing the manner in which the series of floating heads may be affixed to the platform in order to conform to the contour of the head.
FIG. 3A is a perspective view of a floating head of the hair color variegation device showing the hooking platform, the means for rotating the hook and the means by which a detachable hair color applicator applies hair color composition to the strands of hair selected by the rotating hook in varied embodiments.
FIG. 3B is a perspective view of the rotating hook mechanism and the hooking platform that have been isolated from a floating head of the hair color variegation device.
FIG. 4 is a series of lateral views of a floating head of the hair color variegation device positioned in close proximity to a person's cranial hair.
FIG. 5 is a series of anterior views of five floating heads of the hair color variegation device positioned in close proximity to a person's cranial hair.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is a trigger-operated, hand-held device that is used to selectively entrain and color human hair. The invention solves separate and distinct needs of professional hair stylists and individuals desiring the artificial coloring of their hair.
Each of the figures illustrates embodiments of the hair coloring device 1 . As shown in FIG. 1 , the device 1 includes a handle 2 , having a first end 3 , configured to be gripped by a user, and a second end 4 adapted to connect to a chassis 5 . The handle 2 is preferably four and one-half (4½) inches (10.5 cm) in length, but may be made in various lengths. The handle 2 can be glued, frictionally fitted, or bonded to the chassis 5 , as shown in FIG. 1 . The chassis 5 is preferably five (5) inches (12.5 cm) in length, but may be made in various lengths. The handle 2 and chassis 5 of the device 1 may be made from a variety of materials (e.g., plastic, wood) depending on design considerations.
As shown in FIG. 1 , a trigger mechanism 6 is attached to the base of the chassis 5 in front of the handle 2 . The trigger mechanism 6 is a simple lever that allows a user of the device 1 to pull the trigger 7 of the trigger mechanism 6 towards the handle 2 . As will be explained in more detail, pulling the trigger 7 causes the rotating hook mechanism 11 to rotate, which causes the rotating hook mechanism 11 to entrain a strand of hair when the device 1 is positioned against a section of cranial hair.
Referring to FIG. 1 , atop the chassis 5 are attached a floating head 8 . The floating head 8 is preferably three and one-half (3½) inches (8 cm) in length, but may be made in various lengths. The floating head 8 may be made from a variety of durable materials (e.g., plastic, metal) depending on design considerations. In the preferred embodiment of the invention, there are at least five (5) floating heads 8 attached to the chassis 5 . As shown in greater detail in FIG. 2 and FIG. 3A , the floating head 8 consists of: (1) a rotating hook mechanism 11 ; (2) a means 12 for causing the rotating hook mechanism 11 to rotate; (3) a channel mount 13 ; (4) a stabilizing mechanism 23 ; (5) a hooking platform 30 ; and (6) a hair color applicator 22 . Additional details regarding the mechanical design of a specific embodiment of the instant invention are contained in Appendix A.
Referring to FIG. 3A and FIG. 3B , the rotating hook mechanism 11 includes a hook 14 attached to the front of a thin, flexible rod 15 . The hook 14 is preferably crescent shaped and affixed to the front of the thin, flexible rod 15 in such a way as to allow the hook 14 to rotate 180° from an “open” position to a “pinching” position. The hook 14 is preferably made of metal, but can be made of any durable material. In various embodiments of the invention, the thin flexible rod 15 comprises a tightly wound coil spring 16 approximately one (1) inch long by approximately one-eighth (⅛) of an inch in diameter with a round metal (or other suitable material) rod attached to both ends.
The means 12 for causing the rotating hook mechanism 11 to rotate is located at the end of the thin, flexible rod 15 opposite the hook 14 . In one embodiment of the invention, the means 12 consists of a hollow tube 17 encasing the end of the thin, flexible rod 15 . A spiral channel 18 is cut along the length of the hollow tube 17 , and a peg 19 is affixed to the thin, flexible rod 15 in such a way as to protrude through the spiral channel 18 . As shown in FIG. 1 and FIG. 2 , the hollow tube 17 is attached to a bracket 20 . The bracket 20 slides freely along the top of the chassis 5 . The bracket 20 is attached to the trigger mechanism 6 (such as by a simple pulley 21 and cable 29 as shown in FIG. 1 ) in such a way as to cause it to slide away from the floating head 8 when the trigger 7 is pulled. Additional details regarding the mechanical hooking mechanism design of a specific embodiment of the instant invention is contained in Appendix A, including one possible locking mechanism. Alternative mechanical designs well known to one skilled in the art may be utilized to activate the floating head 8 , including motor-driven means. When the bracket 20 slides away from the floating head 8 , the thin, flexible rod 15 is pulled out through the hollow tube 17 . When the thin, flexible rod 15 is pulled out through the hollow tube 17 , the peg 19 follows the path of the spiral channel 18 causing the thin, flexible rod 15 to rotate, which thereby causes the hook 14 to rotate. While an embodiment of the rotating hook mechanism 11 allows the thin, flexible rod 15 to easily rotate when the trigger 7 is pulled, any other means of rotating the thin, flexible rod 15 may be used. Such means will be well understood by one skilled in the art.
As shown in FIG. 2 and FIG. 3A , the stabilizing mechanism 23 connects the floating head 8 to the chassis 5 in a position distal to the handle 2 . Preferably, the stabilizing mechanism 23 allows the floating head 8 to be attached to the platform 5 in such a way that allows the floating head 8 to pivot on an axis. For example, the stabilizing mechanism 23 can comprise a simple hinge 9 . As an alternative, the stabilizing mechanism 23 can comprise a telescoping rod 24 connecting the floating head 8 to the chassis 5 . Various embodiments of the stabilizing mechanism 23 are shown in FIG. 2 and FIG. 3A . The stabilizing mechanism 23 may be made from a variety of durable materials (e.g., plastic, metal) depending on design considerations.
Referring to FIG. 2 and FIG. 3A , The channel mount 13 is affixed to the top of the floating head 8 . The channel mount 13 is constructed of a durable material (e.g., plastic, metal) and positioned above the hook 14 of the rotating hook mechanism 11 . The channel mount 13 is shaped in such a way as to firmly and securely hold a hair color applicator 22 in place, yet allow a hair color applicator 22 to be easily removed therefrom. In some embodiments, the channel mount 13 is open on the top, front, and bottom as depicted in FIG. 2 . Additional details regarding the mechanical design or one possible embodiment of the instant interchangeable cartridge mechanism is set forth in Appendix A.
As shown in FIG. 3A and FIG. 3B , various embodiments of the hooking platform 30 comprise a concave channel of a durable material (e.g., plastic, metal) shaped and dimensioned to attach to the base of the floating head 8 with the base 25 of the hooking platform 30 lying just below the center of the circular face of the hook 14 , and the sides 26 , 32 of the hooking platform 30 curling upward toward the channel mount 13 . The hook 14 is positioned in such a way relative to the hooking platform 30 so that when the hook 14 is rotated, such as by the means 12 depicted, the hook rotates underneath the base 25 of the hooking platform. When the interior radius 31 of the hook 14 rotates from its beginning position at one side 26 of the hooking platform 30 around to the other side 32 of the hooking platform 30 , the interior radius 31 of the hook 14 applies downward pressure to the hooking platform 30 as the hook continues to rotate. The downward pressure causes the base 25 of the hooking platform 30 to eventually press against the hook 14 . This allows the hook 14 and hooking platform 30 to “pinch” or entrain the strands of hair that have been placed in between the hook 14 and hooking platform 30 by the rotation of the hook 14 , thereby allowing the user of the device 1 to pull the selected strands against tension. The invention allows for the predictable and uniform entrainment of strands of hair.
As shown in FIG. 3A , and 4 , an optional hair color applicator 22 is attached to the floating head 8 at the channel mount 13 . In various embodiments of the invention, the hair color applicator 22 includes a reservoir 29 for storing hair color composition and a wick 10 for applying the hair color composition to the stands of hair selected by the device 1 . The reservoir 29 can store any hair color composition that is typically used in the field to color human hair (e.g., hydrogen peroxide, ammonia based dye precursor mixture, bleach). The type of hair color composition stored in the reservoir 29 will depend on the desired hair color. The top of the wick 10 is in constant contact with the reservoir 29 . The base of the wick 10 is positioned outside of the hair color applicator 22 and at the point where the hook 14 and the hooking platform 30 “pinch” the selected strands of hair. In some embodiments of the invention, the wick 10 is made of a semi-porous substance that allows the hair color composition to drain from the reservoir 29 and then be applied to the hair when placed in contact with the surface or the hair. For example, the wick 10 can be made of felt and operate similar to a standard felt-tipped pen. The rate of hair color composition flow through the wick 10 can be controlled in a number of ways typically understood in the art, including the addition of a hole to the top of the hair color applicator 22 allowing the air pressure in the reservoir 29 to normalize and thereby increasing the flow rate of the hair color composition through the wick 10 .
In other embodiments of the hair color applicator 22 , the wick 10 is a sealing mechanism at the base of the reservoir 29 . For example, a roller ball mechanism can be used as the wick 10 to seal the base of the reservoir 29 . The roller ball mechanism can consist of a metal or plastic sphere positioned inside the reservoir 29 and having a circumference slightly larger than the circumference of he opening at the base of the reservoir 29 , with the bottom of the sphere protruding outside the reservoir 29 . The entrained strands of hair are brought in contact with the bottom of sphere. The majority of the sphere's surface is in contact with the liquid contained in the reservoir 29 when the device 1 is not in use. As the entrained strands are pulled through the device 1 , the sphere rotates and brings the liquid contained inside the reservoir 29 into contact with the entrained strands. After applying the liquid to the entrained strands, the sphere continues to rotate and repeats the process as the entrained strands are pulled along. The roller ball mechanism may be spring activated.
In other embodiments of the hair color applicator, the sealing mechanism can comprise a simple seal that seals the opening at the base of the reservoir 29 from the inside of the reservoir 29 when the device 1 is not is use. For example a piece of plastic large enough to cover the opening at the base of the reservoir 29 that is hinged on one side of the opening can serve as sealing mechanism. When the hook 14 and the hooking platform 30 “pinch” the selected stands of hair, the seal is pushed away from the opening at the base of the reservoir 29 and the hair color composition flows onto the selected strands of hair. When the “pinching” of the hook 14 and the hooking platform 30 is released, the sealing mechanism seats back onto the opening at the base of the reservoir 29 and the flow of hair color composition is stopped through the formation of a seal.
In one embodiment of the hair color applicator 22 shown in FIG. 4 , the wick 10 is a cylinder positioned adjacent to the hook 14 when the hook 14 is in the “pinching” position. The cylinder is attached to the hair color applicator 22 in such a way as to allow it to spin. As the device 1 is pulled along the selected strand 37 of hair 35 , the cylinder comes into physical contact with the strand 37 causing the cylinder to spin. As the cylinder spins, it captures hair colorant in the reservoir 29 and then, as it continues to spin, applies the colorant to the selected strand 37 . The cylinder can be made of any durable material (e.g., plastic) and can have a semi-porous affixed to its length to better absorb the hair colorant. Spiral grooves can also be added to the surface of the cylinder's length to ensure the hook 14 does not remove the hair colorant from the cylinder when the cylinder presses against the hook 14 .
FIG. 4 demonstrates how the hook 14 can select a strand 37 of hair 35 , and thereby apply artificial color to the selected strand 37 . The left slide of FIG. 4 shows the hook 14 in the “open” position. While the hook 14 is in the “open” position, the bottom of the floating head 8 is positioned against a person's cranial hair 35 , preferably at the beginning of a parting 36 of the cranial hair 35 . The thin, flexible rod 15 is then rotated, as shown in the right slide of FIG. 4 , which causes the hook 14 to rotate around and underneath a strand 37 of hair 35 . The right slide of FIG. 4 shows the hook 14 in the “pinching” position. By selecting the strand 37 and then lifting it, the hook 14 brings the strand 37 in contact with the wick 10 . The floating head 8 is then pulled away from the part 36 . The length of the strand 37 is thereby pulled through the floating head 8 and against the wick 10 . Hair color composition is drained from the reservoir 29 of the hair color applicator 22 and onto the selected strand 37 .
In the preferred embodiment of the device 1 , each floating head 8 is independently attached to the chassis 5 . In the embodiment shown in FIG. 1 , each floating head 8 has an independent stabilizing mechanism 23 that attaches to the chassis 5 . In the alternative embodiment shown in FIG. 2 , each floating head 8 is affixed to a flexible base 33 . Stabilizing mechanisms 23 are attached to the lateral ends of the flexible base 33 . The stabilizing mechanisms 23 then attach the flexible base 33 to the chassis 5 . The flexible base 33 can be made of any flexible material (e.g., rubber, plastic) or any solid material with regular hinges positioned throughout to allow each individual floating head 8 to pivot on at least one (1) axis.
FIG. 5 demonstrates the use of the preferred embodiment of the device 1 . In slide 1 of FIG. 5 , the floating heads 8 are positioned above a part 36 of cranial hair 35 . In slide 2 of FIG. 5 , the floating heads 8 are pressed against the hair 35 , causing the device 1 to “flex” the floating heads 8 into positions that contour to the surface of the hair 36 . The hook 14 is then rotated into the “pinching” position, as shown in slide 3 and slide 4 of FIG. 5 . As shown in slide 5 of FIG. 5 , the floating heads 8 are pulled away from the part 36 of hair 35 allowing the selected strands 37 of hair 35 to be pulled against tension.
The present invention has been described with respect to certain preferred embodiments and conditions that are not meant to, and should not be, construed to limit the scope of the invention. Those skilled in the art will understand that variation from the embodiments and conditions described herein may be made without departing from the invention as defined in the appended claims. Any element in a claim that does not explicitly state “means for” performed a specific function, or “step for” performing a specific function, in not intended as a “means” or “step” clause as specified in 35 U.S.C. § 112, ¶ 6.
|
A device for applying artificial color to selected stands of human hair, the device comprising a handle, a means for selecting strands of human hair, and a hair color applicator. The device allows a user to quickly, accurately, and predictably apply artificial color to selected strands of human hair using only one hand.
| 0
|
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This is a continuation-in-part application of application No. PCT/AT2003/000371, filed Dec. 18, 2003; the application also claims the priority, under 35 U.S.C. §119, of Austrian patent application No. A 673/2003, filed May 5, 2003 and of Austrian patent application No. A 1895/2002, filed Dec. 18, 2002; the prior applications are herewith incorporated by reference in their entirety.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The invention relates to an aircraft comprising a fuselage and at least two substantially hollow cylindrical lifting bodies which are applied to the fuselage and comprise a plurality of rotor blades extending over the periphery of the lifting body, with the periphery of the lifting body being partially covered by at least one tail surface.
[0004] Such an aircraft is especially provided with a system of special lifting bodies which are configured as rotors, having a rotary axis which is arranged substantially parallel to the longitudinal axis of the aircraft. Each rotor is provided with a certain number of airfoil-like rotor blades which are substantially arranged on two disk-like end bodies in such a way that during a full rotation of the lifting body (rotor) the central axis of the rotor blade performs a circular movement spaced from the rotary axis as the radius, and that the rotor blade can be changed individually in its position during a full rotation. A defined action of force (e.g. lifting force, lateral force) can be produced on the aircraft in every momentary position of the rotor blade.
[0005] Numerous efforts have been undertaken to combine the advantages of an aircraft with those of a helicopter. Of special interest is the property of helicopters to be able to start and land vertically or to hover in the air whenever necessary in order to rescue people or in order to fulfill special transport and mounting flight maneuvers or similar tasks. The disadvantageous aspect in current helicopters is the high technical complexity, especially in the field of rotor control and the high risk of crashes even in the case of slight contact of the rotating rotor blades with obstructions such as the tips of trees or rock walls. Especially conditions during assignments in Alpine rescue operations are exceptionally critical because on the one hand a position as close as possible to a rock wall would be required, and on the other hand the slightest collision could lead to fatal consequences. Work can therefore only proceed by observing respectively large safety margins. A further disadvantage is the high fuel consumption of helicopters, even in cruising flight.
[0006] In order to avoid such disadvantages, so-called VTOL or STOL aircraft have been developed which with respect to their configuration are principally similar to airplanes, but are equipped with the ability, through various technical measures, to be able to start and land vertically, or can at least make do with extremely short take-off and landing runways.
[0007] Such a solution has been disclosed in EP 0 918 686 A (corresponding to U.S. Pat. No. 6,231,004) for example. This specification describes an airplane comprising airfoils which are substantially formed by cross-flow rotors. It is thus possible to produce a vertically downwardly directed air stream through a respective deflection of the air stream in order to enable a vertical take-off of the aircraft. The thrust can be deflected accordingly for cruising.
[0008] The disadvantageous aspect in this known solution is on the one hand that the airfoils which are optimized for generating lift have a high air resistance, so that fuel consumption is excessively high, especially at higher flight speeds, and that the aircraft in total has a relatively large wing span. It therefore requires much space and cannot be used or only with difficulty under conditions with limited available space.
[0009] Further aircraft have been described in U.S. Pat. No. 4,519,562 A. The solution is complex and has a low efficiency, so that such a system was never accepted on the market. The rotors described in U.S. Pat. No. 6,261,051 B are also not suitable for representing an aircraft with vertical take-off capabilities that can be used in practice.
[0010] A further aircraft which generates lift by using modified cross-flow fans is disclosed in DE 196 34 522 A. Apart from the question of the proper function of such an aircraft which is not obviously clear, it also comes with the disadvantages as explained above.
[0011] A further aircraft with a cross-flow rotor as a drive element is also known from U.S. Pat. No. 6,016,992 A. A very large cross-sectional surface in the direction of flight is also obtained in this case as a result of the cross-flow rotor, and the need for space is as high as in the solutions described above.
[0012] A further known aircraft with the possibility of vertical take-off is disclosed in U.S. Pat. No. 3,361,386 A. Extremely variable airfoils are provided in this aircraft which are provided with openings for gas outlet. Fuel consumption is extremely high as a result of the system-inherent adverse efficiency of such a system.
[0013] Close to the state of the art is also the drive concept for watercraft which is known as Voith-Schneider drive. This drive system which has already been known for approximately 75 years differs substantially in such a way that the swiveling movement of the individual blades during a full rotation of the live ring occurs at a fixed kinematic ratio with respect to each other. Thrust is thus always only possible in one direction. In contrast to this, a second force component in the transversal direction can be produced by the inventive rotating lifting body, irrespective of a first force component, e.g. an evenly remaining vertical lifting component.
[0014] The present invention relates to further embodiments of VTOL aircraft which are equipped with rotating lifting bodies whose rotary axis is arranged substantially parallel to the longitudinal axis of the aircraft.
SUMMARY OF THE INVENTION
[0015] It is the object of the present invention to provide an aircraft which allows vertical take-off and vertical landing, which is capable of hovering in the air, with a mobility which allows a slow forward, backward, parallel side movement to back-board or starboard, as well as a rotary movement about the vertical axis clock-wise and counter-clockwise, and which at the same time is suitable for high cruising speeds. As a result of the chosen configuration of the outside geometrical shape of the aircraft, the transition from a hovering state to a forward movement with high cruising speed must be ensured. In particular, high fuel economy shall be achieved with a comparatively low technical complexity. A further claim relates to the fulfillment of the highest safety standards which offer the aircraft the possibility to land securely even in the case of a total failure of the drive engines. Moreover, the rotating lifting bodies are to be protected with a covering in such a way that the aircraft can also be maneuvered very close to obstructions (e.g. rock walls, walls of high-rise buildings) and that even in the case of contact of the aircraft with an obstruction a crash can securely be pre-vented as a result of the rotating elements of the lifting body which are protected against collision. The pilot is provided with a secure and collision-free exiting of the aircraft by means of an ejection seat, which also represents a further claim.
[0016] These objects are achieved in accordance with the invention in such a way that the lifting bodies are driven by at least one drive unit and each comprise a cylindrical axis which is substantially parallel to a longitudinal axis of the aircraft. Each rotor is provided with a certain number of airfoil-like rotor wings which are substantially arranged on two disk-like end bodies in such a way that during a full rotation of the lifting body (rotor) the central axis of the rotor blade performs a circular movement spaced from the rotary axis as the radius, and the rotor blade preferably can be changed individually in its position during a full rotation. A defined action of force (e.g. lifting force, lateral force) can be generated on the air-craft in every momentary position of the rotor blade. This change in the position can occur as a whole. It is also possible that the rear section of the rotor blade is swivellable independent of the front section in order to thus achieve an optimal airfoil shape in every situation.
[0017] Through a suitable choice of the configuration of the lifting bodies in the aircraft it is also ensured that the space above the cockpit is kept free, thus enabling the pilot a secure and collision-free possibility to exit the aircraft by means of an ejection seat (this is not possible in a helicopter for example).
[0018] This configuration of the lifting bodies offers a further possibility for military applications. Radar and other optical devices can also be arranged above the aircraft for reconnaissance purposes. With this aircraft it is not necessary to leave a protective terrain formation without previously detecting and evaluating the action behind such terrain formation by means of a surveillance device which is flexibly mounted on the aircraft and can be extended upwardly vertically above the hovering aircraft and can thereafter be retracted again.
[0019] The solution in accordance with the invention allows maneuvering the aircraft even at low speeds or while hovering without having to change the speed of the drive unit, because the direction and strength of the lifting forces are variably within wide margins through the control of the rotor blades. An extremely high versatility is thus achieved.
[0020] Several advantages can be achieved simultaneously by arranging the lifting bodies parallel to the fuselage. On the one hand, the lifting bodies can be provided with a relatively large diameter without increasing the cross-sectional surface to a large extent in the direction of movement, thus leading to a lower need for fuel in rapid cruising flight. On the other hand, the aircraft in accordance with the invention is provided with a highly compact configuration and thus not only requires little space in a hangar or the like, but is also extremely maneuverable. This allows landing the aircraft on wood clearings or in urban regions between buildings for example where the landing of a helicopter due to the predetermined rotor diameter would no longer be possible. Moreover, the lifting bodies configured as rotors are especially sturdy in their design and apart from the rotor blades generally do not comprise any further movable parts, so that the technical complexity remains within acceptable limits. By applying the lifting bodies close to the fuselage, the mechanical strain upon the rotor suspensions is very low, thus allowing for a respective lightweight design which contributes to fuel savings.
[0021] An especially compact arrangement of the individual components is given when the lifting bodies are arranged in the upper region of the fuselage. This additionally contributes to an especially aerodynamically favorable configuration because the intake region can be accessed by flow in a fully free manner which re-mains unobstructed by other parts of the aircraft.
[0022] A further, especially advantageous embodiment of the invention provides that the lifting bodies are driven in opposite directions by gas turbines. As in helicopters, the use of gas turbines leads to an especially advantageous ratio of output to own weight. An additional advantage over helicopters is provided by the present invention in such a way that the rotary speeds of the rotating lifting bodies are substantially higher than those of conventional helicopter rotors, so that the constructional complexity of the transmissions is reduced substantially. Depending on the size, purpose and security regulations, the two rotors can be driven by one common gas turbine or each lifting body can be provided with its own gas turbine.
[0023] The efficiency of the lifting body can especially be improved further in such a way that the rotor blades which are movably arranged in the rotor consist of at least one fixed axis and two rotor blade segments which are movable independent from each other, so that the rotor blade geometry can be adjusted at every moment in each current position optimally to the respective situation. It is thus possible to optimize the lifting forces and the lateral forces and to minimize the resistance forces.
[0024] Especially high cruising speeds can be achieved in such a way that additional propulsive units for producing a thrust for the propulsion of the aircraft are provided. It is possible and also principally adequate for lower cruising speeds that the propulsion is generated by the adjustable rotor wings of the lifting bodies, such that the aircraft is brought to a position which is lowered forwardly and a thrust force is derived from the resulting lifting force. The cruising speed is limited in this case however, so that additional propulsive units need to be used advantageously for the higher cruising speeds. They can be configured as by-pass propulsive units for example. The takeoff and landing process can be supported in such a way that the additional propulsive units are arranged in a swivellable manner. On the one hand, the lifting force can thus be increased when the propulsive jet faces vertically downwardly, and on the other hand the maneuverability can be increased in addition to a respective control of the swiveling angle.
[0025] Fuel consumption during vertical takeoff and landing and during hovering is relevantly influenced by the shifted air quantity. It is therefore especially advantageous when the lifting bodies extend over at least 40%, preferably over at least 70% of the length of the fuselage.
[0026] In this way it is possible, with a predetermined cross-sectional surface, to achieve the highest possible lifting power of the lifting bodies.
[0027] The maneuverability, especially during hovering and during takeoff and landing, can be improved in such a way that adjustable guide blades are provided in the region of the air outlet openings. At a lower cruising speeds the possibility of control by the tailplane unit is strongly limited, so that a sufficient maneuverability is obtained through the individual adjustability of the rotor blades. In order to also enable a rotation of the aircraft about a vertical axis, it is especially advantageous in this connection that the adjustable rotor blades are arranged in two paired lifting bodies running in opposite directions and each consists of two segments which can be actuated independent from each other. Further adjustable guide blades which are swivellable about a transversal axis of the aircraft allow a forward and backward movement in the hovering state which can be controlled in an especially fine manner.
[0028] It is further especially preferable when the lifting bodies are provided with an external covering as a mechanical protection of the rotor blades against a collision with a solid obstruction. This means that the covering is not only configured for receiving the bearing of the rotor shaft but is also configured in a mechanically sturdy way in order to protect the lifting body against damage when the aircraft collides with an obstruction at a low relative speed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] FIG. 1 shows a schematic view of a first embodiment of an aircraft in accordance with the invention in an axonometric representation;
[0030] FIG. 2 shows a side view of the aircraft of FIG. 1 ;
[0031] FIG. 3 shows a sectional view of the aircraft of FIG. 1 along line A-A in FIG. 2 ;
[0032] FIG. 4 shows a sectional view of the aircraft of FIG. 1 along line A-A in FIG. 2 with the illustration of an opened and closed covering of the lifting body, as is provided for high cruising speeds;
[0033] FIG. 5 shows a view of the aircraft of FIG. 1 from the front;
[0034] FIG. 6 shows a view of the aircraft of FIG. 1 from above;
[0035] FIG. 7 , FIG. 7A and FIG. 7B schematically show a lifting body of the aircraft of FIG. 1 ;
[0036] FIG. 8 , FIG. 8A and FIG. 8B show the configuration, direction of rotation and function of the lifting body of FIG. 1 ;
[0037] FIG. 9 , FIG. 9A and FIG. 9B show a rotor blade with two movable segments in a cross-sectional view in the position of neutral lifting forces, maximum lift and negative lift of the aircraft of FIG. 1 ;
[0038] FIG. 10 , FIG. 10A , FIG. 10B , FIG. 10C and FIG. 10D show rotor blade incidences in selected positions along the direction of rotation of the lifting body of the aircraft of FIG. 1 ;
[0039] FIG. 11 shows the individual lifting forces of the lifting bodies for achieving a stable equilibrium in the air by the aircraft of FIG. 1 ;
[0040] FIG. 12A and FIG. 12B show the position of the individual and overall centers of mass of the aircraft of FIG. 1 ;
[0041] FIG. 13 shows the forwardly inclined position of the aircraft of FIG. 1 for achieving a forward drive component for slow forward movement;
[0042] FIG. 14 , FIG. 14A , FIG. 14B , FIG. 14C and FIG. 14D show the lifting body configuration and the incidence of the rotor blades for achieving lateral forces for the transversal movement of the aircraft of FIG. 1 ;
[0043] FIG. 15 shows the generation of a force component acting in pairs in opposite directions transversally to the longitudinal axis of the aircraft for generating a rotary movement of the aircraft about the vertical axis;
[0044] FIG. 16 , FIG. 16A , FIG. 16B and FIG. 16C show a special variant of a lifting body with “double” length and rotor blades capable of décalage for generating different lifting and transversal forces of the aircraft of FIG. 1 ;
[0045] FIG. 17 shows the incidence of the rotor blades during descent in free fall for the purpose of autorotation of the lifting body, e.g. after a motor failure of the aircraft of FIG. 1 ;
[0046] FIG. 18 and FIG. 18A to FIG. 18G show an embodiment of an aircraft with only two lifting bodies which are driven in opposite directions and are arranged successively in a central axis of the aircraft;
[0047] FIG. 19 , FIG. 19A and FIG. 19B show an embodiment of an aircraft with a system of oppositely rotating cross-flow rotors with a common rotary axis;
[0048] FIG. 20 shows a schematic view of an aircraft in accordance with the invention with an arrangement of a surveillance device which is flexibly linked to the aircraft;
[0049] FIG. 21 shows a further embodiment of the invention in a representation from the front;
[0050] FIG. 22 shows the embodiment of FIG. 21 from above;
[0051] FIG. 23 shows the embodiment of FIG. 21 in an axonometric view;
[0052] FIG. 24 shows a further embodiment of the invention in a side view;
[0053] FIG. 25 shows the embodiment of FIG. 24 from the front;
[0054] FIG. 26 shows a schematic representation to explain how the rotor blades are triggered;
[0055] FIG. 27 shows a detail of FIG. 26 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0056] The aircraft according to FIG. 1 to FIG. 6 consists of a fuselage 1 with a longitudinal axis 1 a and of four lifting bodies 2 , 3 , 4 and 5 which are arranged parallel to said longitudinal axis 1 a in a preferred manner above the center-of-gravity position and which are protected by a side protection means 6 against collision with a solid obstruction. In the rear section 9 there are in the known manner a horizontal tail unit 11 and a rudder unit 10 , and preferably also the drive unit such as one or two gas turbines and the transmission and additional drive units (not shown here in closer detail) which are configured here as by-pass propulsive units which provide the aircraft with a high cruising speed or can support the take-off and landing process in the case of a respective pivoting configuration. Skids or similar supports 12 support the aircraft on the ground. The rear section of the aircraft is joined with the front section by means of longitudinal struts 13 , 14 , which have a flow-optimized cross-sectional shape or a weight-optimized framework construction. Furthermore, a stable construction for a bearing (not shown here) for the lifting bodies 2 , 3 , 4 , 5 in the middle section is provided with the longitudinal struts and the side protection.
[0057] FIG. 2 shows the length ratios, according to which the length of the rotating lifting bodies 2 , 3 , 4 , 5 corresponds to approximately 50%, preferably 30 to 70%, of the total length of the aircraft. FIG. 3 shows the lifting bodies 2 , 3 , 4 , 5 with the rotary directions 20 a , 20 b rotating in opposite directions about the rotary axes 7 a , 7 B and the rotor blades 8 required for generating the lifting force. Additional drive units (not shown here in closer detail) are provided for a high cruising speed with simultaneous fuel economy. For reducing the air resistance, the lifting bodies 2 , 3 , 4 , 5 , which cannot produce the required lift at high cruising speeds, are covered by means of suitable covering skirts in a flow-optimized manner in the aircraft. In accordance with FIG. 4 , these covering skirts can be arranged as compact surfaces 40 a , 40 b (as shown in FIG. 4 for example in the opened state for an optimal effect of the lifting bodies) or as a system of lamellae 40 a ′, 40 b ′, 41 a ′, 41 b ′ which can be set optionally as a closed covering or for an unhindered passage of the air.
[0058] As is shown in FIG. 7 , a lifting body 2 , 3 , 4 , 5 substantially consists of a rotary axis 7 , two end disks 2 a - 2 b , 3 a - 3 b , 4 a - 4 b , 5 a - 5 b with the diameter D 23 b and a certain number (preferably 4 to 10) of rotor blades 8 which are arranged movably about a swiveling axis 8 A in the two end disks (e.g. 2 a - 2 b ) and describe a circular path 23 a with the radius R 23 during a full rotation. The depth of the rotor blade t 8 e depends on the size of the overall construction and is approximately 30 to 50% of the circular path radius R 23 . The length L 8 d of the rotor blade 8 is preferably approximately 25 to 35% of the total length of the aircraft. When in operation, the lifting body rotates at a nominal speed (preferably approximately 750 to 300 l/min) about the rotary axis 7 . During a full rotation, the rotor blades 8 are set in every momentary position individually with respect to the tangent 23 b of the circular path 23 a with the radius R 23 , so that in the region of the upper and lower extreme position maximum lifting forces can be generated and only flow resistance forces act upon the rotor blade in the two vertical extreme positions. The preferred arrangement of the direction of rotation 20 of the lifting bodies in the aircraft is in the opposite direction.
[0059] FIG. 8 shows the flow conditions in closer detail. The airfoil theory is relevant as a result of the rotor blade geometry, according to which at a defined relative speed a pressure increase is generated beneath the set rotor blade and a negative pressure above the same. The respective force components acting upon the rotor blade are the result of these two pressure components. Ambient air is preferably taken in from above 18 A at a respective incidence of the rotor blades relative to tangent 23 b of the circular path 23 a during a fill rotation of the lifting bodies 2 , 3 , 4 , 5 at nominal speed, pressed into the rotating lifting body 18 B, sucked downwardly 19 A and pressed out 19 B. An optimal embodiment is shown in FIG. 9 , FIG. 9A and FIG. 9B . In this embodiment the rotor blade 8 consists of at least three elements, which are a stable pivoting axis 8 A, a movable rotor blade nose 8 B and a movable rotor blade tip 8 c . For normal operations, the rotor blade nose 8 B is swivellable about the angle α 21 a , preferably by +/−3° to 10° relative to the tangent of the circular path 23 a and the rotor blade tip 8 c is swivellable about the angle β 21 b , preferably by +/−3° to 10° relative to the tangent of the circular path 23 a . The rotor blade tip and rotor blade nose are swivellable by >90°, preferably approximately 105°, for the special case of “autorotation”. Ac-cording to FIG. 9A , a vertical force component Fa 22 can be generated in the direction of the rotary axis 7 of the lifting body when at a nominal speed in the up-per extreme position the rotor blade nose 8 B is set at the angle α<0° and the rotor blade tip with the angle β>0°, each relating to the tangent direction 23 b of the rotary circular path 23 a , and vice-versa according to FIG. 9B a vertical force component Fa 22 can be generated against the direction of the rotary axis 7 of the lifting body when at a nominal speed in the upper extreme position the rotor blade nose 8 B is set at the angle α>0° and the rotor blade tip with the angle β<0°, each relating to the tangent direction 23 b of the rotary circular path 23 a . FIG. 10 shows in detail the two oppositely driven lifting bodies with the incidences of the rotor blades in different positions, which incidences are optimal for generating a maximum lifting force at nominal speed. FIG. 10A (a detail W of FIG. 10 ) shows the angular conditions of the rotor blade nose and the rotor blade tip upon entering the upper circular path after leaving the neutral vertical position. FIG. 10B (detail X of FIG. 10 ) shows the angular conditions of the rotor blade nose and rotor blade tip in the upper extreme position of the circular path. FIG. 10C (detail Y of FIG. 10 ) shows the angular conditions of the rotor blade nose and rotor blade tip in the upper circular path prior to the entrance in the neutral vertical position. FIG. 10D (detail Z of FIG. 10 ) shows the angular conditions of the rotor blade nose and rotor blade tip in the lower extreme position of the circular path.
[0060] A stable equilibrium position in FIG. 11 , FIG. 12A and FIG. 12B in the air is pro-vided in such a way that every single lifting body 2 , 3 , 4 , 5 can generate individual lifting forces A 1 through A 4 35 a , 35 b , 35 c and 35 d and thus an equilibrium state relative to the overall center of mass S 32 of the overall mass m 33 and to the bulk centers of mass 32 a of the partial mass of cockpit m 1 33 a , with the partial center-of-gravity distance s 3 34 a , and 32 b of the partial mass of the rear region of the aircraft m 2 33 b , with the partial center-of-gravity distance s 2 34 b , and the lateral center-of-gravity distance s 3 34 c of the overall center of mass S 32 of the overall mass m 33 can be produced in each situation. This allows responding at all times to any changing equilibrium position.
[0061] After reaching a defined height position, which can be assumed by means of the rotating lifting bodies 2 , 3 , 4 , 5 , a transition from a hovering state to a slow forward movement or rearward movement is thus enabled in such a way that the aircraft assumes an inclined position ( FIG. 13 ) and a force component 35 a ′, 35 b ′ can be derived from the resulting lifting force 35 a , 35 b of the lifting bodies, which force component allows a forward or rearward acceleration, whereas the vertical force component 35 a ″, 35 b ″ continues to keep the aircraft vertically in the equilibrium.
[0062] A movement of the aircraft transversally to the longitudinal axis is enabled in the hovering state through a special incidence of the rotor blades relative to the tangent direction 23 b of the path of movement 23 a of the rotor blades. FIG. 14 shows a transversal movement with the speed v x 36 which is achieved in such a way that according to FIG. 14A the rotor blades in the position of vertical extreme position are brought to a respective inclined position 21 , so that air is sucked in from one direction 18 A and is pressed out 19 B virtually transversally through the aircraft. The airfoil theory is applicable in this case too. FIG. 14B shows the rotor blade position in a neutral position, whereas according to the rotor blade incidence according to FIG. 14C a force component Fq 22 would act upon the aircraft away from the rotary axis and would have a movement with the speed v x 36 from the right to the left. According to the illustration according to FIG. 14D , a force component Fq 22 would act upon the aircraft in the opposite direction, in the direction of the rotary axis, and would lead to a movement with the speed v x 36 from the left to the right. A rotary movement 36 a in the hovering state about the vertical axis 1 b of the aircraft clockwise or counter-clockwise can be achieved by paired opposite generation of the force component Fq 22 in the forward and rearward region of the lifting body according to FIG. 15 .
[0063] The same as the above described effects and maneuvers can also be achieved in cases where instead of the four only two paired lifting bodies 2 , 3 are used which run in opposite directions and are provided with twice the length 2 L 8 d ( FIG. 16 ). In this embodiment, the rotor blades are elastically deformable about the pivoting axis 8 A. The rotor blade nose 8 B and the rotor blade tip 8 c can be displaced parallel at both ends or in a different way. FIG. 16A shows a neutral position of the rotor blade (sectional view II-II of FIG. 16 ), as is obtained in the case of a displacement in opposite direction of the two ends of the rotor blade according to FIG. 16B (sectional view I-I of FIG. 16 ) and FIG. 16C (sectional view III-III of FIG. 16 ). In an embodiment with only two lifting bodies rotating in opposite directions, this allows correcting different center-of-gravity positions during the flight, performing forward and rearward movements with low flight speed and rotary movements about the vertical axis.
[0064] In the case of a sufficiently large adjusting possibility of the pivoting movement of the rotor blade, an autorotation of the lifting bodies and thus a secure landing process is enabled after the failure of a drive unit for example above a critical flying height. FIG. 17 shows the respective angles of incidence α 21 of the rotor blades and the relative air flow 41 and the direction of rotation 20 of the lifting bodies when the aircraft drops with the speed of descent 40 in free fall in the vertical direction.
[0065] A further embodiment of an aircraft with two lifting bodies 2 , 3 rotating in opposite directions is shown in FIG. 18 . FIG. 18A shows a side view and FIG. 18B shows a front view. The two lifting bodies rotating in the opposite direction are arranged behind one another along the central axis of the aircraft along a common rotary axis. FIG. 18C shows a sectional view I-I of FIG. 18A , which show the bearing of the rotary axis of the lifting bodies 2 , 3 and the lateral protective covering. FIG. 18D shows the sectional view II-II of FIG. 18A and FIG. 18E shows the sectional view III-III of FIG. 18A , which show the arrangement and direction of rotation of the lifting bodies arranged behind one another, in the representation for a conventional hovering state or ascending flight. FIG. 18F shows the sectional view II-II of FIG. 18A , and FIG. 18G shows the sectional view III-III of FIG. 18A in the position of the rotor blades for achieving autorotation in free descent after failure of one drive unit for example.
[0066] FIG. 19 shows a further embodiment of an aircraft which is suitable for vertical take-off and landing, provided with lifting bodies 36 , 37 , 38 , 39 however which are arranged as cross-flow rotors. FIG. 19A shows the top view of such an aircraft and FIG. 19B shows a representation according to sectional view I-I of FIG. 19 . In this embodiment so-called cross-flow rotors are in use which are provided with external flow guide devices 6 which are arranged in a respectively adjustable way and thus allow achieving a virtually unlimited maneuverability (forward movement, backward movement, transversal movement, rotary movement about the vertical axis). These lifting bodies 36 , 37 , 38 , 39 , which are configured as cross-flow rotors, each consist of two round end disks which carry a plurality of rotor wings 36 a , 37 a and rotate about a rotary axis. In a preferred embodiment, an inner cross-flow rotor 37 with opposite direction of rotation is inserted in an external cross-flow rotor 36 each for increasing the flow efficiency.
[0067] As a result of the fact that there are no rotating units above the aircraft, the pilot can be allowed a safe and secure exit from the aircraft by ejection seat if so required. Moreover, a unit designated as a surveillance device 43 (radar, optical sensor) can be provided in accordance with FIG. 20 above the aircraft, which surveillance device, when the aircraft is in the hovering state, can be brought vertically upwardly by means of a flexible connection 44 and can thereafter be retracted again. This is useful in situations when the aircraft is to be used in military assignments to fly below enemy radar beams behind protective cover in the terrain or in aligned buildings and is to detect the military situation behind a protective terrain formation and, instead of a brief hazardous peek above the terrain, only upwardly extends the surveillance device 43 in a vertical direction, surveys the military situation and thereafter retracts the surveillance device again with the flexible connection securely into the fuselage of the aircraft.
[0068] The aircraft of FIG. 21 consists of a fuselage 1 with a longitudinal axis 1 a and two cross-flow rotors 2 and 3 which are arranged above said longitudinal axis 1 a . In the rear section of the fuselage there are in the known manner a horizontal tail unit 11 and a rudder unit 10 . Skids 46 support the aircraft on the ground. Two by-pass propulsive units 47 are provided behind the cross-flow rotors 2 , 3 in the region of the tailplane 4 , 5 in order to produce the respective thrust.
[0069] FIG. 22 shows that the length L 1 of the cross-flow rotors 2 , 3 corresponds to approximately 50% of the length L of the entire aircraft.
[0070] FIG. 25 shows the structure of the aircraft on an enlarged scale in a sectional view. The rotors 2 , 3 comprise a plurality of blades 8 which are arranged along the circumference. The rotors 2 , 3 are each covered on the circumference by a first guide surface 49 and a second guide surface 50 . The first tail surface 49 is configured as a part of the outside surface of the fuselage 1 , whereas the second guide surface 50 is configured as a flow guide plate. As a result of the rotation of the cross-flow rotors 2 , 3 along the arrows 51 , an air flow is induced so that the air is taken in along the arrows 52 and is ejected in the direction of the arrows 53 . The upper open region of the rotors 2 , 3 is thus used as an air intake opening 54 , and the lower open region is used as an air outlet opening 55 . The impulse of the downwardly ejected air quantities leads in total to a lifting force for the aircraft, which is represented by arrow 56 and which is sufficient, in the case of a respective configuration, to lift the aircraft from the ground.
[0071] Adjustable guide blades 17 are provided below the rotors 2 , 3 , which in the embodiments of FIG. 24 consist of several segments 17 a , 17 B, 17 c which can be pivoted independent from each other about an axis parallel to the longitudinal axis of the aircraft. As a result, a rotation of the aircraft about a vertical axis 1 b can be effected by the guide blades 17 . It can be seen that the guide blades 17 which are arranged below the air outlet openings are able to change the direction of the air jets along the arrows 53 . In the position as shown in FIG. 6 , a force component to backboard is generated by pivoting the movable guide blades 17 , which is indicated by the arrow 56 . Guide blades 58 can be used within the cross-flow rotors for improved guidance of the air flow. The guide blades 58 can be provided with a movable configuration, which improves the maneuverability at high efficiency.
[0072] The drive of the cross-flow rotors 2 , 3 can occur in principle by piston engines, but is preferably carried out by gas turbines, which is not shown in the drawings.
[0073] FIG. 26 shows that the individual rotor blades 8 are arranged in a pivoting way about a pivot 61 via a tow-bar. The tow-bars 60 are held in a common star point 62 which can be displaced relative to the axis 63 at will. An overall flow in any direction can thus be set. The rotor blades 8 are guided in pins 64 in connecting links 65 in order to guarantee respective stability.
[0074] FIG. 27 shows that an end region 66 of the rotor blade 8 is separately adjustable. A lever 67 connected with the end region 66 comprises a pin 68 which is guided in a second connecting link 69 , so that the rotor blade 8 assumes an asymmetric airfoil profile, which increases the conveying output and the efficiency. The stronger the incidence of the rotor blade 8 , the stronger the additional incidence of the end region 66 and thus the overall profiling of the rotor blade 8 .
[0075] The present invention describes an aircraft which offers the possibility of vertical take-off and vertical landing, allows a virtually unlimited maneuverability in the hovering state, offers a high cruising speed with simultaneous fuel economy, al-lows the pilot a secure exit from the aircraft if required, and houses a flexibly arranged surveillance device above the aircraft.
|
The invention relates to an aircraft comprising a fuselage and at least two substantially hollow cylindrical lifting bodies which are applied to the fuselage and comprise a plurality of rotor blades which extend over the periphery of the lifting bodies, the periphery of the lifting bodies being partially covered by at least one tail surface. The aim of the invention is to provide an aircraft with an extremely high degree of maneuverability, compact dimensions and economy of fuel. To this end, the lifting bodies are driven by at least one drive unit and respectively comprise a cylindrical axis which is substantially parallel to a longitudinal axis ( 1 a ) of the aircraft.
| 1
|
TECHNICAL FIELD
[0001] The present invention relates to novel 2-(optionally hetero)arylmethyl-3-(optionally hetero)arylamino-[2H]-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione compounds, processes for their production, their use as pharmaceuticals and pharmaceutical compositions comprising them. Of particular interest are novel compounds useful as inhibitors of phosphodiesterase 1 (PDE1), e.g., in the treatment of diseases involving disorders of the dopamine D1 receptor intracellular pathway, such as Parkinson's disease, depression, narcolepsy and damage to cognitive function, e.g., in schizophrenia or disorders that may be ameliorated through enhanced progesterone-signaling pathway, e.g., female sexual dysfunction.
BACKGROUND OF THE INVENTION
[0002] Eleven families of phosphodiesterases (PDEs) have been identified but only PDEs in Family I, the Ca 2+ -calmodulin-dependent phosphodiesterases (CaM-PDEs), have been shown to mediate both the calcium and cyclic nucleotide (e.g. cAMP and cGMP) signaling pathways. The three known CaM-PDE genes, PDE1A, PDE1B, and PDE1C, are all expressed in central nervous system tissue. PDE1A is expressed throughout the brain with higher levels of expression in the CA1 to CA3 layers of the hippocampus and cerebellum and at a low level in the striatum. PDE1A is also expressed in the lung and heart. PDE1B is predominately expressed in the striatum, dentate gyrus, olfactory tract and cerebellum, and its expression correlates with brain regions having high levels of dopaminergic innervation. Although PDE1B is primarily expressed in the central nervous system, it may be detected in the heart. PDE1C is primarily expressed in olfactory epithelium, cerebellar granule cells, and striatum. PDE1C is also expressed in the heart and vascular smooth muscle.
[0003] Cyclic nucleotide phosphodiesterases decrease intracellular cAMP and cGMP signaling by hydrolyzing these cyclic nucleotides to their respective inactive 5′-monophosphates (5′AMP and 5′GMP). CaM-PDEs play a critical role in mediating signal transduction in brain cells, particularly within an area of the brain known as the basal ganglia or striatum. For example, NMDA-type glutamate receptor activation and/or dopamine D2 receptor activation result in increased intracellular calcium concentrations, leading to activation of effectors such as calmodulin-dependent kinase II (CaMKII) and calcineurin and to activation of CaM-PDEs, resulting in reduced cAMP and cGMP. Dopamine D1 receptor activation, on the other hand, leads to activation of nucleotide cyclases, resulting in increased cAMP and cGMP. These cyclic nucleotides in turn activate protein kinase A (PKA; cAMP-dependent protein kinase) and/or protein kinase G (PKG; cGMP-dependent protein kinase) that phosphorylate downstream signal transduction pathway elements such as DARPP-32 (dopamine and cAMP-regulated phosphoprotein) and cAMP responsive element binding protein (CREB). Phosphorylated DARPP-32 in turn inhibits the activity of protein phosphates-1 (PP-1), thereby increasing the state of phosphorylation of substrate proteins such as progesterone receptor (PR), leading to induction of physiologic responses. Studies in rodents have suggested that inducing cAMP and cGMP synthesis through activation of dopamine D1 or progesterone receptor enhances progesterone signaling associated with various physiological responses, including the lordosis response associated with receptivity to mating in some rodents. See Mani, et al., Science (2000) 287: 1053, the contents of which are incorporated herein by reference.
[0004] CaM-PDEs can therefore affect dopamine-regulated and other intracellular signaling pathways in the basal ganglia (striatum), including but not limited to nitric oxide, noradrenergic, neurotensin, CCK, VIP, serotonin, glutamate (e.g., NMDA receptor, AMPA receptor), GABA, acetylcholine, adenosine (e.g., A2A receptor), cannabinoid receptor, natriuretic peptide (e.g., ANP, BNP, CNP), DARPP-32, and endorphin intracellular signaling pathways.
[0005] Phosphodiesterase (PDE) activity, in particular, phosphodiesterase 1 (PDE1) activity, functions in brain tissue as a regulator of locomotor activity and learning and memory. PDE1 is a therapeutic target for regulation of intracellular signaling pathways, preferably in the nervous system, including but not limited to a dopamine D1 receptor, dopamine D2 receptor, nitric oxide, noradrenergic, neurotensin, CCK, VIP, serotonin, glutamate (e.g., NMDA receptor, AMPA receptor), GABA, acetylcholine, adenosine (e.g., A2A receptor), cannabinoid receptor, natriuretic peptide (e.g., ANP, BNP, CNP), endorphin intracellular signaling pathway and progesterone signaling pathway. For example, inhibition of PDE1B should act to potentiate the effect of a dopamine D1 agonist by protecting cGMP and cAMP from degradation, and should similarly inhibit dopamine D2 receptor signaling pathways, by inhibiting PDE1 activity. Chronic elevation in intracellular calcium levels is linked to cell death in numerous disorders, particularly in neurodegerative diseases such as Alzheimer's, Parkinson's and Huntington's Diseases and in disorders of the circulatory system leading to stroke and myocardial infarction. PDE1 inhibitors are therefore potentially useful in diseases characterized by reduced dopamine D1 receptor signaling activity, such as Parkinson's disease, restless leg syndrome, depression, narcolepsy and cognitive impairment. PDE1 inhibitors are also useful in diseases that may be alleviated by the enhancement of progesterone-signaling such as female sexual dysfunction.
[0006] There is thus a need for compounds that selectively inhibit PDE1 activity, especially PDE1B activity.
SUMMARY OF THE INVENTION
[0007] The invention provides novel 2-(optionally hetero)arylmethyl-3-(optionally hetero)arylamino-[2H]-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-diones, in free, salt or prodrug form (hereinafter “Compounds of the Invention”). The (optionally)hetero aryl moiety at the 2-position is preferably benzyl or pyridyl methyl para-substituted relative to the point of attachment with aryl or heteroaryl, e.g., substituted with phenyl, pyridyl or thiadiazolyl. These compounds are surprisingly found to selectively inhibit phosphodiesterase 1 (PDE1) activity, e.g., PDE1A, PDE1B, and PDE1C activity, especially PDE1B activity.
[0008] Preferably, the Compounds of the Invention are pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-diones of formula I
[0000]
[0000] wherein
(i) R 1 is H or alkyl (e.g., methyl); (ii) R 2 is H, alkyl (e.g., isobutyl, 2-methylbutyl, 2,2-dimethyl propyl), cycloalkyl (e.g., cyclopentyl, cyclohexyl), haloalkyl (e.g., trifluoromethyl, 2,2,2-trifluoroethyl), alkylaminoalkyl (e.g., 2-(dimethylamino)ethyl), hydroxyalkyl (e.g., 3-hydroxy-2-methyl propyl), arylalkyl (e.g., benzyl), heteroarylalkyl (e.g., pyridylmethyl), or alkoxyarylalkyl (e.g., 4-methoxybenzyl); (iii) R 3 is a substituted heteroarylaklyl, e.g., substituted with haloalkyl or R 3 is attached to one of the nitrogens on the pyrazolo portion of Formula I and is a moiety of Formula A
[0000]
[0000] wherein X, Y and Z are, independently, N or C, and R 8 , R 9 , R 11 and R 12 are independently H or halogen (e.g., Cl or F); and R 10 is halogen, alkyl, cycloalkyl, haloalkyl (e.g., trifluoromethyl), aryl (e.g., phenyl), heteroaryl (e.g., pyridyl, (for example, pyrid-2-yl) or e.g., thiadiazolyl (for example, 1,2,3-thiadiazol-4-yl), diazolyl, triazolyl (e.g., 1,2,4-triazol-1-yl), tetrazolyl (e.g., tetrazol-5-yl), alkoxadiazolyl (e.g., 5-methyl-1,2,4-oxadiazol), pyrazolyl (e.g., pyrazol-1-yl), alkyl sulfonyl (e.g., methyl sulfonyl), arylcarbonyl (e.g., benzoyl), or heteroarylcarbonyl, alkoxycarbonyl, (e.g., methoxycarbonyl), aminocarbonyl; preferably phenyl or pyridyl, e.g., 2-pyridyl; provided that when X, Y or X is nitrogen, R 8 , R 9 or R 10 , respectively, is not present;
(iv) R 4 is aryl (e.g., phenyl) or heteroaryl; and (v) R 5 is H, alkyl, cycloalkyl (e.g., cyclopentyl), heteroaryl, aryl, p-benzylaryl (e.g., biphenyl-4-ylmethyl);
wherein “alk” or “alkyl” refers to C 1-6 alkyl and “cycloalkyl” refers to C 3-6 cycloalkyl; in free, salt or prodrug form.
[0016] The invention further provides compounds of Formula I as follows:
1.1 Formula I wherein R 1 is methyl; 1.2 Formula I or 1.1 wherein R 2 is C 1-6 alkyl; 1.3 Formula 1.2 wherein R 2 is isobutyl, 2,2-dimethyl propyl, or 2-methylbutyl; 1.4 Formula I or 1.1 wherein R 2 is hydroxy C 1-6 alkyl; 1.5 Formula I or 1.1 wherein R 2 is 3-hydroxy-2-methyl propyl; 1.6 Formula I or 1.1 wherein R 2 is C 1-6 alkoxy-benzyl; 1.7 Formula 1.6 wherein R 2 is p-methoxybenzyl; 1.8 Formula I or 1.1 wherein R 2 is C 3-6 cycloalkyl; 1.9 Formula 1.8 wherein R 2 is cyclopentyl or cyclohexyl; 1.10 Formula I or 1.1 wherein R 2 is C 1-6 haloalkyl; 1.11 Formula 1.10 wherein R 2 is 2,2,2-trifluoroethyl; 1.12 Any of the preceding formulae wherein R 3 is a moiety of Formula A wherein R 8 , R 9 , R 11 and R 12 are each H and R 10 is phenyl; 1.13 Any of the preceding formulae I-1.11 wherein R 3 is a moiety of Formula A wherein R 8 , R 9 , R 11 and R 12 are each H and R 10 is pyridyl or thiadizolyl; 1.14 Formula 1.13 wherein R 3 is a moiety of Formula A wherein R 8 , R 9 , R 11 and R 12 are each H and R 10 is 2-pyridyl; 1.15 Any of the preceding formulae wherein R 4 is phenyl; 1.16 Any of the preceding formulae wherein R 5 is H, 1.17 Any of the preceding formulae wherein X, Y and Z are all C; 1.18 Any of the preceding formulae wherein R 2 is tetrahydrofuran-2-ylmethyl; 1.19 Any of the preceding formulae wherein R 10 is pyrimidinyl; 1.20 A compound of formula 1.19 wherein the pyrimidinyl is 5-fluoropyrmidinyl; 1.21 Any of the preceding formulae wherein R 10 is pyrazol-1-yl; 1.22 Any of the preceding formulae wherein R 10 is 1,2,4-triazol-1-yl: 1.23 Any of the preceding formulae wherein R 10 is aminocarbonyl; 1.24 Any of the preceding formulae wherein R 10 is methylsulfonyl; 1.25 Any of the preceding formulae wherein R 10 is 5-methyl-1,2,4-oxadiazol-3-yl; 1.26 Any of the preceding formulae wherein R 10 is 5-fluoropyrimidin-2-yl; 1.26 Any of the preceding formulae wherein R 4 is 4-fluorophenyl; 1.27 Any of the preceding formulae wherein R 10 is trifluoromethyl; 1.28 Any of the preceding formulae wherein R 3 is a moiety of Formula A, X and Z are C, and Y is N; 1.29 A compound selected from the compounds of Examples 1-24 below; and/or 1.30 Any one of the preceding formulae wherein the compounds inhibit phosphodiesterase-mediated (e.g., PDE1-mediated, especially PDE1B-mediated) hydrolysis of cGMP, e.g., with an IC 50 of less than 1 μM, preferably less than 25 nM in an immobilized-metal affinity particle reagent PDE assay, for example, as described in Example 25; such compounds according to any of the preceding formulae being in free, salt or prodrug form.
[0049] In an especially preferred embodiment, the Compounds of the Invention are compounds of Formula I wherein
(i) R 1 is methyl; (ii) R 2 is C 1-6 alkyl; (iii) R 3 is a moiety of Formula A wherein X, Y and Z are all C and R 8 , R 9 , R 11 and R 12 are each H and R 10 is phenyl, pyridyl (for example, pyrid-2-yl), or thiadiazolyl (e.g., 1,2,3-thiadiazol-4-yl); (iv) R 4 is phenyl; and (v) R 5 is H; in free or salt form.
[0056] For example, preferred Compounds of the Invention include compounds according to Formula II
[0000]
wherein
R 2 is H, alkyl (e.g., isobutyl, 2-methylbutyl, 2,2-dimethyl propyl), cycloalkyl (e.g., cyclopentyl, cyclohexyl), heteroaryl (e.g., pyridyl), aryl (e.g., phenyl), haloalkyl (e.g., trifluoromethyl, 2,2,2-trifluoroethyl), alkylaminoalkyl (e.g., 2-(dimethylamino)ethyl), hydroxyalkyl (e.g., 3-hydroxy-2-methyl propyl), arylalkyl (e.g., benzyl), or alkoxyarylalkyl (e.g., 4-methoxybenzyl);
wherein “alk” or “alkyl” refers to C 1-6 alkyl; and
R 10 is phenyl, pyridyl (for example, pyrid-2-yl) or thiadiazolyl (for example, 1,2,3-thiadiazol-4-yl);
in free, salt or prodrug form.
[0062] In certain embodiments, the Compounds of the Invention are compounds of Formula II wherein
R 2 is H, alkyl (e.g., isobutyl, 2-methylbutyl, 2,2-dimethyl propyl), cycloalkyl (e.g., cyclopentyl, cyclohexyl, tetrahydrofuran-2-ylmethyl), heteroaryl (e.g., pyridyl), aryl (e.g., phenyl), haloalkyl (e.g., trifluoromethyl, 2,2,2-trifluoroethyl), alkylaminoalkyl (e.g., 2-(dimethylamino)ethyl), hydroxyalkyl (e.g., 3-hydroxy-2-methyl propyl), arylalkyl (e.g., benzyl), or alkoxyarylalkyl (e.g., 4-methoxybenzyl); and R 10 is phenyl, pyridyl (for example, pyrid-2-yl), pyrimidinyl (e.g., 5-fluoropyrimidin-2-yl), pyrazolyl (e.g. pyrazol-1-yl), thiadiazolyl (for example, 1,2,3-thiadiazol-4-yl), haloalkyl (e.g., trifluoromethyl), alkylsulfonyl (e.g., methylsulfonyl), oxadiazolyl (e.g., 5-methyl-1,2,4-oxadiazol-3-yl), aminocarbonyl (e.g., so as to form a 4-benzamide structure), triazolyl (e.g., 1,2,4-triazol-1-yl); wherein “alk” or “alkyl” refers to Ci −6 alkyl; in free, salt or prodrug form.
[0068] If not otherwise specified or clear from context, the following terms herein have the following meanings:
(a) “Alkyl” as used herein is a saturated or unsaturated hydrocarbon moiety, preferably saturated, preferably having one to six carbon atoms, which may be linear or branched, and may be optionally mono-, di- or tri-substituted, e.g., with halogen (e.g., chloro or fluoro), hydroxy, or carboxy. (b) “Cycloalkyl” as used herein is a saturated or unsaturated nonaromatic hydrocarbon moiety, preferably saturated, preferably comprising three to nine carbon atoms, at least some of which form a nonaromatic mono- or bicyclic, or bridged cyclic structure, and which may be optionally substituted, e.g., with halogen (e.g., chloro or fluoro), hydroxy, or carboxy. In certain embodiments, the cycloalkyl may optionally contain one or more heteroatoms e.g., nitrogen, oxygen or sulfur, in the ring or linking portion of the moiety, e.g., tetrahydrofuranylmethyl (c) “Aryl” as used herein is a mono or bicyclic aromatic hydrocarbon, preferably phenyl, optionally substituted, e.g., with alkyl (e.g., methyl), halogen (e.g., chloro or fluoro), haloalkyl (e.g., trifluoromethyl), hydroxy, carboxy, or an additional aryl or heteroaryl (e.g., biphenyl or pyridylphenyl). (d) “Heteroaryl” as used herein is an aromatic moiety wherein one or more of the atoms making up the aromatic ring is sulfur or nitrogen rather than carbon, e.g., pyridyl or thiadiazolyl, which may be optionally substituted, e.g., with alkyl, halogen, haloalkyl, hydroxy or carboxy. (e) For ease of reference, the atoms on the pyrazolo-pyrimidine core of the Compounds of the Invention are numbered in accordance with the numbering depicted in Formula 1, unless otherwise noted.
[0074] Compounds of the Invention may exist in free or salt form, e.g., as acid addition salts. In this specification unless otherwise indicated, language such as “Compounds of the Invention” is to be understood as embracing the compounds in any form, for example free or acid addition salt form, or where the compounds contain acidic substituents, in base addition salt form. The Compounds of the Invention are intended for use as pharmaceuticals, therefore pharmaceutically acceptable salts are preferred. Salts which are unsuitable for pharmaceutical uses may be useful, for example, for the isolation or purification of free Compounds of the Invention or their pharmaceutically acceptable salts, are therefore also included.
[0075] Compounds of the Invention may in some cases also exist in prodrug form. A prodrug form is compound which converts in the body to a Compound of the Invention. For example when the Compounds of the Invention contain hydroxy or carboxy substituents, these substituents may form physiologically hydrolysable and acceptable esters. As used herein, “physiologically hydrolysable and acceptable ester” means esters of Compounds of the Invention which are hydrolysable under physiological conditions to yield acids (in the case of Compounds of the Invention which have hydroxy substituents) or alcohols (in the case of Compounds of the Invention which have carboxy substituents) which are themselves physiologically tolerable at doses to be administered. As will be appreciated the term thus embraces conventional pharmaceutical prodrug forms.
[0076] The invention also provides methods of making the Compounds of the Invention, novel intermediates useful for making Compounds of the Invention, and methods of using the Compounds of the Invention for treatment of diseases and disorders as set forth below (especially treatment of diseases characterized by reduced dopamine D1 receptor signaling activity, such as Parkinson's disease, Tourette's Syndrome, Autism, fragile X syndrome, ADI-ID, restless leg syndrome, depression, and cognitive impairment of schizophrenia).
DETAILED DESCRIPTION OF THE INVENTION
Methods of Making Compounds of the Invention
[0077] The compounds of the formula I and their pharmaceutically acceptable salts may be made using the methods as described and exemplified herein and by methods similar thereto and by methods known in the chemical art. Such methods include, but not limited to, those described below. If not commercially available, starting materials for these processes may be made by procedures, which are selected from the chemical art using techniques which are similar or analogous to the synthesis of known compounds. All references cited herein are hereby incorporated in their entirety by reference.
[0078] The Compounds of the Invention include their enantiomers, diastereoisomers and racemates, as well as their polymorphs, hydrates, solvates and complexes. Some individual compounds within the scope of this invention may contain double bonds. Representations of double bonds in this invention are meant to include both the E and the Z isomer of the double bond. In addition, some compounds within the scope of this invention may contain one or more asymmetric centers. This invention includes the use of any of the optically pure stereoisomers as well as any combination of stereoisomers.
[0079] Melting points are uncorrected and (dec) indicates decomposition. Temperature are given in degrees Celsius (° C.); unless otherwise stated, operations are carried out at room or ambient temperature, that is, at a temperature in the range of 18-25° C. Chromatography means flash chromatography on silica gel; thin layer chromatography (TLC) is carried out on silica gel plates. NMR data is in the delta values of major diagnostic protons, given in parts per million (ppm) relative to tetramethylsilane (TMS) as an internal standard. Conventional abbreviations for signal shape are used. Coupling constants (J) are given in Hz. For mass spectra (MS), the lowest mass major ion is reported for molecules where isotope splitting results in multiple mass spectral peaks. Solvent mixture compositions are given as volume percentages or volume ratios. In cases where the NMR spectra are complex, only diagnostic signals are reported.
TERMS AND ABBREVIATIONS
[0000]
Bu t OH=tert-butyl alcohol,
CAN=ammonium cerium (IV) nitrate,
DIPEA=diisopropylethylamine,
DMF=N,N-dimethylforamide,
DMSO=dimethyl sulfoxide,
Et 2 O=diethyl ether,
EtOAc=ethyl acetate,
equiv.=equivalent(s),
h=hour(s),
HPLC=high performance liquid chromatography,
K 2 CO 3 =potassium carbonate,
MeOH=methanol,
NaHCO 3 =sodium bicarbonate,
NH 4 OH=ammonium hydroxide,
PMB=p-methoxybenzyl,
POCl 3 =phosphorous oxychloride,
SOCl 2 =thionyl chloride,
TFA=trifluoroacetic acid,
THF=tetrahedrofuran.
[0099] The synthetic methods in this invention are illustrated below. The significances for the R groups are as set forth above for formula I unless otherwise indicated.
[0100] In an aspect of the invention, intermediate compounds of formula IIb can be synthesized by reacting a compound of formula IIa with a dicarboxylic acid, acetic anhydride and acetic acid mixing with heat for about 3 hours and then cooled:
[0000]
[0101] wherein R′ is H or C 1-4 alkyl [e.g., methyl].
[0102] Intermediate IIc can be prepared by for example reacting a compound of IIb with for example a chlorinating compound such as POCl 3 , sometimes with small amounts of water and heated for about 4 hours and then cooled:
[0000]
[0103] Intermediate IId may be formed by reacting a compound of IIc with for example a P 1 —X in a solvent such as DMF and a base such as K 2 CO 3 at room temperature or with heating:
[0000]
[0000] wherein P 1 is a protective group [e.g., p-methoxybenzyl group (PMB)]; X is a leaving group such as a halogen, mesylate, or tosylate.
[0104] Intermediate IIe may be prepared by reacting a compound of IId with hydrazine or hydrazine hydrate in a solvent such as methanol and refluxed for about 4 hours and then cooled:
[0000]
[0105] Intermediate IIf can be synthesized by reacting a compound of IIe with for example an aryl isothiocyanate or isocyanate in a solvent such as DMF and heated at 110° C. for about 2 days and then cooled:
[0000]
wherein R 4 is (hetero)aryl or (hetero)arylmethyl [e.g., phenyl or benzyl].
[0107] Intermediate IIg may be formed by reacting a compound of Hf with for example a R 3 —X in a solvent such as DMF and a base such as K 2 CO 3 at room temperature or with heating:
[0000]
wherein R 3 is as defined previously [e.g. an optionally substituted benzyl group]; X is a leaving group such as a halogen, mesylate, or tosylate.
[0109] Intermediate IIh may be synthesized from a compound of IIg by removing the protective group P 1 with an appropriate method. For example, if P 1 is a p-methoxybenzyl group, then it can be removed with AlCl 3 in the presence of anisole at room temperature:
[0000]
[0110] Compound I may be formed by reacting a compound of IIh with for example a R 2 —X and/or R 5 —X in a solvent such as DMF and a base such as K 2 CO 3 at room temperature or with heating:
[0000]
wherein R 2 and R 5 are as defined previously [e.g. a cyclopentyl group]; X is a leaving group such as a halogen, mesylate, or tosylate.
[0112] There is an alternative approach for the synthesis of compound I.
[0113] Intermediate IIIa may be formed by reacting a compound of IIc with for example a R 2 —X in a solvent such as DMF and a base such as K 2 CO 3 at room temperature or with heating:
[0000]
[0114] Intermediate IIIb may be prepared by reacting a compound of IIIa with hydrazine or hydrazine hydrate in a solvent such as methanol and heated for about several hours and then cooled:
[0000]
[0115] Intermediate IIIc can be synthesized by reacting a compound of IIIb with for example an aryl isothiocyanate or isocyanate in a solvent such as DMF and heated at 110° C. for about 2 days and then cooled:
[0000]
[0116] Compound I may be formed by reacting a compound of IIIc with for example a R 3 —X in a solvent such as DMF and a base such as K 2 CO 3 at room temperature or with heating. The obtained product I (R 5 ═H) may further react with for example a R 5 —X under basic condition to give compound I:
[0000]
[0117] The invention thus provides methods of making Compounds of the Invention as described above, for example, comprising
(i) reacting a 2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione with a compound of formula X—R 3 wherein X is a leaving group, e.g., halogen, mesylate, or tosylate, and R 3 is optionally substituted arylalkyl or heteroarylalkyl, for example wherein R 3 is a substituted benzyl of formula A as defined above, e.g., under basic conditions, for example wherein the 2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione is a compound of Formula IIc:
[0000]
wherein R 1 , R 2 and R 4 are as defined above, e.g., with reference to Formula I;
and/or
(ii) reacting a 2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione with a compound of formula X—R 2 wherein X is a leaving group, e.g., halogen, mesylate, or tosylate, and R 2 is alkyl, cycloalkyl, arylalkyl or heterocycloalkyl, for example wherein R 2 is isobutyl; e.g., under basic conditions, for example wherein the 2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione is a compound of Formula IIh:
[0000]
wherein R 1 , R 3 and R 4 are as defined above, e.g., with reference to Formula I.
Methods of Using Compounds of the Invention
[0123] The Compounds of the Invention are useful in the treatment of diseases characterized by disruption of or damage to cAMP and cGMP mediated pathways, e.g., as a result of increased expression of PDE1 or decreased expression of cAMP and cGMP due to inhibition or reduced levels of inducers of cyclic nucleotide synthesis, such as dopamine and nitric oxide (NO). By preventing the degradation of cAMP and cGMP by PDE1B, thereby increasing intracellular levels of cAMP and cGMP, the Compounds of the Invention potentiate the activity of cyclic nucleotide synthesis inducers.
[0124] The invention provides methods of treatment of any one or more of the following conditions:
(i) Neurodegenerative diseases, including Parkinson's disease, restless leg, tremors, dyskinesias, Huntington's disease, Alzheimer's disease, and drug-induced movement disorders; (ii) Mental disorders, including depression, attention deficit disorder, attention deficit hyperactivity disorder, bipolar illness, anxiety, sleep disorders, e.g., narcolepsy, cognitive impairment, dementia, Tourette's syndrome, autism, fragile X syndrome, psychostimulant withdrawal, and drug addiction; (iii) Circulatory and cardiovascular disorders, including cerebrovascular disease, stroke, congestive heart disease, hypertension, pulmonary hypertension, and sexual dysfunction; (iv) Respiratory and inflammatory disorders, including asthma, chronic obstructive pulmonary disease, and allergic rhinitis, as well as autoimmune and inflammatory diseases; (v) Any disease or condition characterized by low levels of cAMP and/or cGMP (or inhibition of cAMP and/or cGMP signaling pathways) in cells expressing PDE1; and/or (vi) Any disease or condition characterized by reduced dopamine D1 receptor signaling activity,
comprising administering an effective amount of a Compound of the Invention, e.g., a compound according to any of Formula 1-1.30 or Formula II, to a human or animal patient in need thereof.
[0131] In an especially preferred embodiment, the invention provides methods of treatment or prophylaxis for narcolepsy. In this embodiment, PDE 1 Inhibitors may be used as a sole therapeutic agent, but may also be used in combination or for co-administration with other active agents. Thus, the invention further comprises a method of treating narcolepsy comprising administering simultaneously, sequentially, or contemporaneously administering therapeutically effective amounts of
(i) a PDE 1 Inhibitor, e.g., a compound according to any of Formula 1-1.30 or Formula II, and (ii) a compound to promote wakefulness or regulate sleep, e.g., selected from (a) central nervous system stimulants-amphetamines and amphetamine like compounds, e.g., methylphenidate, dextroamphetamine, methamphetamine, and pemoline; (b) modafinil, (c) antidepressants, e.g., tricyclics (including imipramine, desipramine, clomipramine, and protriptyline) and selective serotonin reuptake inhibitors (including fluoxetine and sertraline); and/or (d) gamma hydroxybutyrate (GHB).
to a human or animal patient in need thereof.
[0134] In another embodiment, the invention further provides methods of treatment or prophylaxis of a condition which may be alleviated by the enhancement of the progesterone signaling comprising administering an effective amount of a Compound of the Invention, e.g., a compound according to any of Formula 1-1.30 or Formula II, to a human or animal patient in need thereof. Disease or condition that may be ameliorated by enhancement of progesterone signaling include, but are not limited to, female sexual dysfunction, secondary amenorrhea (e.g., exercise amenorrhoea, anovulation, menopause, menopausal symptoms, hypothyroidism), pre-menstrual syndrome, premature labor, infertility, for example infertility due to repeated miscarriage, irregular menstrual cycles, abnormal uterine bleeding, osteoporosis, autoimmmune disease, multiple sclerosis, prostate enlargement, prostate cancer, and hypothyroidism. For example, by enhancing progesterone signaling, the PDE 1 inhibitors may be used to encourage egg implantation through effects on the lining of uterus, and to help maintain pregnancy in women who are prone to miscarriage due to immune response to pregnancy or low progesterone function. The novel PDE 1 inhibitors, e.g., as described herein, may also be useful to enhance the effectiveness of hormone replacement therapy, e.g., administered in combination with estrogen/estradiol/estriol and/or progesterone/progestins in postmenopausal women, and estrogen-induced endometrial hyperplasia and carcinoma. The methods of the invention are also useful for animal breeding, for example to induce sexual receptivity and/or estrus in a nonhuman female mammal to be bred.
[0135] In this embodiment, PDE 1 Inhibitors may be used in the foregoing methods of treatment or prophylaxis as a sole therapeutic agent, but may also be used in combination or for co-administration with other active agents, for example in conjunction with hormone replacement therapy. Thus, the invention further comprises a method of treating disorders that may be ameliorated by enhancement of progesterone signaling comprising administering simultaneously, sequentially, or contemporaneously administering therapeutically effective amounts of
(i) a PDE 1 Inhibitor, e.g., a compound according to any of Formula 1-1.30 or Formula II, and (ii) a hormone, e.g., selected from estrogen and estrogen analogues (e.g., estradiol, estriol, estradiol esters) and progesterone and progesterone analogues (e.g., progestins)
to a human or animal patient in need thereof.
[0138] The invention also provides a method for enhancing or potentiating dopamine D1 intracellular signaling activity in a cell or tissue comprising contacting said cell or tissue with an amount of a Compound of the Invention sufficient to inhibit PDE1B activity.
[0139] The invention also provides a method for enhancing or potentiating progesterone signaling activity in a cell or tissue comprising contacting said cell or tissue with an amount of a Compound of the Invention sufficient to inhibit PDE1B activity.
[0140] The invention also provides a method for treating a PDE1-related, especially PDE1B-related disorder, a dopamine D1 receptor intracellular signaling pathway disorder, or disorders that may be alleviated by the enhancement of the progesterone signaling pathway in a patient in need thereof comprising administering to the patient an effective amount of a Compound of the Invention that inhibits PDE1B, wherein PDE1B activity modulates phosphorylation of DARPP-32 and/or the GluR1 AMPA receptor.
[0141] The present invention also provides
(i) a Compound of the Invention for use as a pharmaceutical, for example for use in any method or in the treatment of any disease or condition as hereinbefore set forth, (ii) the use of a Compound of the Invention in the manufacture of a medicament for treating any disease or condition as hereinbefore set forth, (iii) a pharmaceutical composition comprising a Compound of the Invention in combination or association with a pharmaceutically acceptable diluent or carrier, and (iv) a pharmaceutical composition comprising a Compound of the Invention in combination or association with a pharmaceutically acceptable diluent or carrier for use in the treatment of any disease or condition as hereinbefore set forth.
[0146] The words “treatment” and “treating” are to be understood accordingly as embracing prophylaxis and treatment or amelioration of symptoms of disease as well as treatment of the cause of the disease.
[0147] Compounds of the Invention are in particular useful for the treatment of Parkinson's disease, narcolepsy and female sexual dysfunction.
[0148] Compounds of the Invention may be used as a sole therapeutic agent, but may also be used in combination or for co-administration with other active agents. For example, as Compounds of the Invention potentiate the activity of D1 agonists, such as dopamine, they may be simultaneously, sequentially, or contemporaneously administered with conventional dopaminergic medications, such as levodopa and levodopa adjuncts (carbidopa, COMT inhibitors, MAO-B inhibitors), dopamine agonists, and anticholinergics, e.g., in the treatment of a patient having Parkinson's disease. In addition, the novel PDE 1 inhibitors, e.g., as described herein, may also be administered in combination with estrogen/estradiol/estriol and/or progesterone/progestins to enhance the effectiveness of hormone replacement therapy or treatment of estrogen-induced endometrial hyperplasia or carcinoma.
[0149] Dosages employed in practicing the present invention will of course vary depending, e.g. on the particular disease or condition to be treated, the particular Compound of the Invention used, the mode of administration, and the therapy desired. Compounds of the Invention may be administered by any suitable route, including orally, parenterally, transdermally, or by inhalation, but are preferably administered orally. In general, satisfactory results, e.g. for the treatment of diseases as hereinbefore set forth are indicated to be obtained on oral administration at dosages of the order from about 0.01 to 2.0 mg/kg. In larger mammals, for example humans, an indicated daily dosage for oral administration will accordingly be in the range of from about 0.75 to 150 mg, conveniently administered once, or in divided doses 2 to 4 times, daily or in sustained release form. Unit dosage forms for oral administration thus for example may comprise from about 0.2 to 75 or 150 mg, e.g. from about 0.2 or 2.0 to 50, 75 or 100 mg of a Compound of the Invention, together with a pharmaceutically acceptable diluent or carrier therefor.
[0150] Pharmaceutical compositions comprising Compounds of the Invention may be prepared using conventional diluents or excipients and techniques known in the galenic art. Thus oral dosage forms may include tablets, capsules, solutions, suspensions and the like.
EXAMPLES
Example 1
2-(Biphenyl-4-ylmethyl)-7-isobutyl-5-methyl-3-(phenylamino)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0151]
(a) 1-Methylpyrimidine-2,4,6(1H,3H,5H)-trione
[0152] To a solution of malonic acid (80 g, 0.79 mol) and methylurea (50 g, 0.68 mol) in 180 ml of acetic acid at 70° C., acetic anhydride (130 ml, 1.37 mol) is added slowly. After the completion of the addition, the reaction mixture is stirred at 90° C. for 3 hours, and then cooled to room temperature. The solvent is removed under reduced pressure, and the residue is treated with 350 mL of ethanol to precipitate out yellowish solid. The solid is recrystallized from ethanol to give 63.1 g product as crystalline solids (Yield: 65.8%). m.p.=131.2-133.1° C. [Lit. 1 : m.p.=130-131.5° C.].
(b) 6-Chloro-3-methylpyrimidine-2,4(1H,3H)-dione
[0153] Water (2.7 mL) is added dropwise to a suspension of 1-methylpyrimidine-2,4,6(1H,3H,5H)-trione (14.2 g, 100 mol) in POCl 3 (95 mL) at 0° C. The reaction mixture is then heated at 80° C. for 5 hours. The resulting brownish solution is cooled, and POCl 3 is evaporated under reduced pressure. The residue is treated with MeOH, and the obtained solid is recrystallized from ethanol to give 11.5 g product (Yield: 71.6%). m.p.=279-282° C. (dec) [Lit. 2 : 280-282° C.]. 1 H NMR (400 MHz, DMSO-d 6 ) δ3.10 (S, 3H), 5.90 (S, 1H), 12.4 (br, 1H).
(c) 6-Chloro-1-isobutyl-3-methylpyrimidine-2,4(1H,3H)-dione
[0154] A mixture of 6-chloro-3-methylpyrimidine-2,4(1H,3H)-dione (3 g, 18.8 mmol), isobutyl iodide (5 mL, 43.5 mmol) and potassium carbonate (5.3 g, 38.4 mmol) in anhydrous DMF (200 mL) is heated at 50° C. for 8 hours. Additional isobutyl iodide (4.3 mL, 37.5 mmol) is added, and the reaction mixture heated at 50° C. for 24 hours. After hot filtration, the filtrate is evaporated to dryness under reduced pressure. The obtained oil is further purified by silica-gel flash chromatography to give 2.1 g of pure product (Yield: 52%).
(d) 6-Hydrazinyl-1-isobutyl-3-methylpyrimidine-2,4(1H,3H)-dione
[0155] To a solution of 6-chloro-1-isobutyl-3-methylpyrimidine-2,4(1H,3H)-dione (2.0 g 9.3 mmol) in EtOH (8 mL), hydrazine monohydrate (1.3 mL) in EtOH (3 mL) is added slowly. The reaction mixture is refluxed for 5 hours, and then cooled. A large amount of AcOEt is added into the reaction mixture, and then cooled and filtered to give 1.95 g of product as yellowish solids (Yield: 100%).
(e) 7-Isobutyl-5-methyl-3-(phenylamino)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0156] Phenyl isothiocyanate (0.17 mL, 1.4 mmol) is added to a solution of 6-hydrazinyl-1-isobutyl-3-methylpyrimidine-2,4(1H,3H)-dione (31 mg, 0.47 mmol) in DMF (10 mL). The reaction mixture is heated at 120° C. for 6 hours, and then evaporated to remove solvent under reduced pressure. The residue is further purified by silica-gel flash chromatography to give 20 mg of product (Yield: 41%). 1 H NMR (400 MHz, DMSO-d 6 ) 50.95 (s, 3H), 0.97 (s, 3H), 2.30 (m, 1H), 3.37 (s, 3H), 3.77 (d, 2H), 7.16-7.43 (m, 5H), 7.61 (s, 1H). MS (FAB) m/z 314.3 [M+H] + .
(f) 2-(Biphenyl-4-ylmethyl)-7-isobutyl-5-methyl-3-(phenylamino)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0157] A mixture of 7-isobutyl-5-methyl-1H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione (12.0 g, 0.0383 mmol), p-biphenylmethyl bromide (9.46 mg, 0.0383 mmol) and potassium carbonate (5.3 mg, 0.0383 mmol) in acetone (2.5 mL) is stirred at room temperature overnight. The solvent is evaporated under reduced pressure. The residue is directly purified by chromatography to give 7.0 mg product as white solids (Yield: 38.0%). 1 H NMR (400 MHz, CDCl 3 ) δ0.97 (s, 3H), 0.99 (s, 3H), 2.33 (m, 1H). 3.34 (s, 3H), 3.85 (d, 2H), 4.99 (s, 2H), 6.76 (s, 1H), 6.91-7.56 (m, 13H). MS (FAB) m/z 480.3 [M+H] + .
Example 2
2-(Biphenyl-4-ylmethyl)-7-(4-methoxybenzyl)-5-methyl-3-(phenylamino)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0158]
[0159] The synthesis method is analogous to example 1 wherein p-methoxybenzyl chloride is added in step (c) instead of isobutyl iodide. TLC R f =0.61 (AcOEt:Hexanes=1:1). 1 H NMR (CDCl 3 ) δ3.31 (s, 3H), 3.71 (s, 3H), 4.99 (s, 2H), 5.10 (s, 2H), 6.75-7.57 (m, 19H). MS (FAB) m/z 544.4 [M+H] +
Example 3
2-(Biphenyl-4-ylmethyl)-3-((biphenyl-4-ylmethyl)(phenyl)amino)-7-(4-methoxybenzyl)-5-methyl-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0160]
[0161] The synthesis method is analogous to example 1 wherein p-methoxybenzyl chloride is added in step (c) instead of isobutyl iodide. TLC R f =0.81 (AcOEt:Hexanes=1:1). 1 H NMR (CDCl 3 ) δ3.38 (s, 3H), 3.68 (s, 3H), 4.99 (s, 2H), 5.10 (s, 2H), 5.20 (s, 2H), 6.70-7.57 (m, 27H). MS (FAB) m/z 710.5 [M+H] +
Example 4
7-(4-Methoxybenzyl)-5-methyl-3-(phenylamino)-2-(4-(trifluoromethyl)benzyl)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0162]
[0163] The synthesis method is analogous to example 1 wherein p-methoxybenzyl chloride is added in step (c) instead of isobutyl iodide; and p-trifluoromethylbenzyl bromide is added in step (f) instead of p-biphenylmethyl bromide (Yield: 80%). MS (ESI) ink 536.5 [M+H] +
Example 5
7-(4-Methoxybenzyl)-5-methyl-3-(phenylamino)-2-(4-(pyridin-2-yl)benzyl)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0164]
[0165] The synthesis method is analogous to example 1 wherein p-methoxybenzyl chloride is added in step (c) instead of isobutyl iodide; and p-(pyridin-2-yl)benzyl bromide is added in step (f) instead of p-biphenylmethyl bromide (Yield: 60%). MS (ESI) m/z 545.2 [M+H] +
Example 6
5-Methyl-3-(phenylamino)-2-(4-(pyridin-2-yl)benzyl)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0166]
[0167] AlCl 3 (0.733 g, 5.50 mmol) is added to a solution of 7-(4-methoxybenzyl)-5-methyl-3-(phenylamino)-2-(4-(pyridin-2-yl)benzyl)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione (1.08 g, 1.98 mmol) and anisole (mL) in 1,2-dichloroethane (15 mL) under argon. The reaction mixture is stirred at room temperature overnight, and then quenched with water with cooling. The resulting suspension is treated with 20% NaOH (70 mL), and then extract with methylene chloride 5 times. The organic phase is combined and evaporated to dryness. The residue is further purified by chromatography to give 751 mg of pure product (Yield: 89%). MS (FAB) m/z 425.3 [M+H] + .
Example 7
7-Cyclopentyl-5-methyl-3-(phenylamino)-2-(4-(pyridin-2-yl)benzyl)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0168]
[0169] Methylethylketone (1.2 mL) was added into a 0.5-5 mL reaction vessel containing 5-methyl-3-(phenylamino)-2-(4-(pyridin-2-yl)benzyl)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione (25 mg, 0.0589 mmol), iodocyclopentane (8.2 μL, 0.0707 mmol) and K 2 CO 3 (9.8 mg, 0.0707 mmol). The sealed vessel was put onto a Biotage Microwave instrument and the microwave reaction was carried out at 140° C. for 1 hour. The obtained crude product was then purified by silica-gel flash chromatography to give 14.9 mg of pure product (Yield: 51.4%). TLC R f =0.72 (AcOEt:Hexanes=2:1). MS (ESI) m/z 493.4 [M+H] +
Example 8
3-(Cyclopentyl(phenyl)amino)-5-methyl-2-(4-(pyridin-2-yl)benzyl)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0170]
[0171] Methylethylketone (1.2 mL) was added into a 0.5-5 mL reaction vessel containing 5-methyl-3-(phenylamino)-2-(4-(pyridin-2-yl)benzyl)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione (25 mg, 0.0589 mmol), iodocyclopentane (8.2 μL, 0.0707 mmol) and K 2 CO 3 (9.8 mg, 0.0707 mmol). The sealed vessel was put onto a Biotage Microwave instrument and the microwave reaction was carried out at 140° C. for 1 hour. The obtained crude product was then purified by silica-gel flash chromatography to give 5.2 mg of pure product (Yield: 17.9%). TLC R f =0.50 (AcOEt:Hexanes=2:1). MS (ESI) m/z 493.4 [M+H] +
Example 9
7-Isobutyl-5-methyl-3-(phenylamino)-2-(4-(pyridin-2-yl)benzyl)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0172]
[0173] The synthesis method is analogous to example 7 wherein isobutyl iodide is added instead of iodocyclopentane (Yield: 95.8%). MS (ESI) m/z 481.4 [M+H] +
Example 10
7-Cyclohexyl-5-methyl-3-(phenylamino)-2-(4-(pyridin-2-yl)benzyl)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0174]
[0175] The synthesis method is analogous to example 7 wherein iodocyclohexane is added instead of iodocyclopentane (Yield: 10%). MS (ESI) m/z 507.4 [M+H] +
Example 11
5-Methyl-7-neopentyl-3-(phenylamino)-2-(4-(pyridin-2-yl)benzyl)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0176]
[0177] The synthesis method is analogous to example 7 wherein 1-iodo-2,2-dimethylpropane is added instead of iodocyclopentane (Yield: 4.1%). MS (ESI) m/z 495.4 [M+H] +
Example 12
(S)-5-Methyl-7-(2-methylbutyl)-3-(phenylamino)-2-(4-(pyridin-2-yl)benzyl)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0178]
[0179] The synthesis method is analogous to example 7 wherein (S)-1-iodo-2-methylbutane is added instead of iodocyclopentane (Yield: 81.8%). MS (ESI) m/z 495.4 [M+H] +
Example 13
5-Methyl-3-(phenylamino)-2-(4-(pyridin-2-yl)benzyl)-7-(2,2,2-trifluoroethyl)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0180]
[0181] The synthesis method is analogous to example 7 wherein 1,1,1-trifluoro-2-iodoethane is added instead of iodocyclopentane (Yield: 14.8%). MS (ESI) m/z 507.3 [M+H] +
Example 14
(R)-7-(3-Hydroxy-2-methylpropyl)-5-methyl-3-(phenylamino)-2-(4-(pyridin-2-yl)benzyl)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0182]
[0183] The synthesis method is analogous to example 7 wherein (S)-3-bromo-2-methylpropan-1-ol is added instead of iodocyclopentane (Yield: 86.3%). MS (ESI) m/z 497.4 [M+H] +
Example 15
7-(2-(Dimethylamino)ethyl)-5-methyl-3-(phenylamino)-2-(4-(pyridin-2-yl)benzyl)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0184]
[0185] The synthesis method is analogous to example 7 wherein 2-bromo-N,N-dimethylethanaminium bromide is added instead of iodocyclopentane (Yield: 64.4%). MS (ESI) m/z 496.3 [M+H] +
Example 16
2-(4-(1H-pyrazol-1-yl)benzyl)-7-isobutyl-5-methyl-3-(phenylamino)-2H-pyrazolo-[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0186]
[0187] The synthesis method is analogous to example 1 wherein 1-(4-(bromomethyl)phenyl)-1H-pyrazole is added in step (f) instead of/?-biphenylmethyl bromide. MS (ESI) m/z 470.1 [M+H] +
Example 17
2-(4-(1H-1,2,4-triazol-1-yl)benzyl)-7-isobutyl-5-methyl-3-(phenylamino)-2H-pyrazolo pyrimidine-4,6(5H,7H)-dione
[0188]
[0189] The synthesis method is analogous to example 1 wherein 1-(4-(bromomethyl)phenyl)-1H-1,2,4-triazole is added in step (f) instead of p-biphenylmethyl bromide (Yield: 89.2%). MS (ESI) m/z 471.1 [M+H] +
Example 18
4-((7-isobutyl-5-methyl-4,6-dioxo-3-(phenylamino)-4,5,6,7-tetrahydropyrazolo[3,4-d]pyrimidin-2-yl)methyl)benzamide
[0190]
[0191] The synthesis method is analogous to example 1 wherein 4-(chloromethyl)benzamide is added in step (f) instead of p-biphenylmethyl bromide. MS (ESI) m/z 447.1 [M+H] +
Example 19
7-isobutyl-5-methyl-2-(4-(methylsulfonyl)benzyl)-3-(phenylamino)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0192]
[0193] The synthesis method is analogous to example 1 wherein 1-(bromomethyl)-4-(methylsulfonyl)benzene is added in step (f) instead of p-biphenylmethyl bromide. MS (ESI) m/z 482.1 [M+H] +
Example 20
7-isobutyl-5-methyl-2-(4-(5-methyl-1,2,4-oxadiazol-3-yl)benzyl)-3-(phenylamino)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0194]
[0195] The synthesis method is analogous to example 1 wherein 3-(4-(bromomethyl)phenyl)-5-methyl-1,2,4-oxadiazole is added in step (f) instead of p-biphenylmethyl bromide. MS (ESI) m/z 486.1 [M+H] +
Example 21
2-(4-(5-fluoropyrimidin-2-yl)benzyl)-7-isobutyl-5-methyl-3-(phenylamino)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0196]
[0197] The synthesis method is analogous to example 1 wherein 2-(4-(bromomethyl)phenyl)-5-fluoropyrimidine is added in step (f) instead of p-biphenylmethyl bromide. MS (ESI) m/z 500.0 [M+H] +
Example 22
5-methyl-3-(phenylamino)-2-(4-(pyridin-2-yl)benzyl)-7-((tetrahydrofuran-2-yl)methyl)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0198]
[0199] The synthesis method is analogous to example 7 wherein 2-(bromomethyl)-tetrahydrofuran is added instead of iodocyclopentane. MS (ESI) m/z 509.2 [M+H] +
Example 23
5-methyl-7-neopentyl-3-(phenylamino)-2-((6-(trifluoromethyl)pyridin-3-yl)methyl)-2H-pyrazolo[3,4d]pyrimidine-4,6(5H,7H)-dione
[0200]
[0201] The synthesis method is analogous to example 1 wherein 1-iodo-2,2-dimethylpropane is added in step (c) instead of isobutyl iodide; and 5-(bromomethyl)-2-(trifluoromethyl)pyridine is added in step (f) instead of p-biphenylmethyl bromide. MS (ESI) m/z 487.2 [M+H] +
Example 24
3-(4-fluorobenzylamino)-7-isobutyl-5-methyl-2-(4-(trifluoromethyl)benzyl)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione
[0202]
[0203] The synthesis method is analogous to example 7 wherein 3-(4-fluorobenzylamino)-5-methyl-2-(4-(trifluoromethyl)benzyl)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione is used instead of 5-methyl-3-(phenylamino)-2-(4-(pyridin-2-yl)benzyl)-2H-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-dione, and isobutyl iodide is added instead of iodocyclopentane. MS (ESI) m/z 490.2 [M+H] +
Example 25
Measurement of PDE1B Inhibition In Vitro Using IMAP Phosphodiesterase Assay Kit
[0204] Phosphodiesterase 1B (PDE1B) is a calcium/calmodulin dependent phosphodiesterase enzyme that converts cyclic guanosine monophosphate (cGMP) to 5′-guanosine monophosphate (5′-GMP). PDE1B can also convert a modified cGMP substrate, such as the fluorescent molecule cGMP-fluorescein, to the corresponding GMP-fluorescein. The generation of GMP-fluorescein from cGMP-fluorescein can be quantitated, using, for example, the IMAP (Molecular Devices, Sunnyvale, Calif.) immobilized-metal affinity particle reagent.
[0205] Briefly, the IMAP reagent binds with high affinity to the free 5′-phosphate that is found in GMP-fluorescein and not in cGMP-fluorescein. The resulting GMP-fluorescein—IMAP complex is large relative to cGMP-fluorescein. Small fluorophores that are bound up in a large, slowly tumbling, complex can be distinguished from unbound fluorophores, because the photons emitted as they fluoresce retain the same polarity as the photons used to excite the fluorescence.
[0206] In the phosphodiesterase assay, cGMP-fluorescein, which cannot be bound to IMAP, and therefore retains little fluorescence polarization, is converted to GMP-fluorescein, which, when bound to IMAP, yields a large increase in fluorescence polarization (Δmp). Inhibition of phosphodiesterase, therefore, is detected as a decrease in Δmp.
[0207] Enzyme Assay
[0208] Materials: All chemicals are available from Sigma-Aldrich (St. Louis, Mo.) except for IMAP reagents (reaction buffer, binding buffer, FL-GMP and IMAP beads), which are available from Molecular Devices (Sunnyvale, Calif.).
[0209] Assay: 3′,5′-cyclic-nucleotide-specific bovine brain phosphodiesterase (Sigma, St. Louis, Mo.) is reconstituted with 50% glycerol to 2.5 U/ml. One unit of enzyme will hydrolyze 1.0 μmole of 3′,5′-cAMP to 5′-AMP per min at pH 7.5 at 30° C. One part enzyme is added to 1999 parts reaction buffer (30 μM CaCl 2 , 10 U/ml of calmodulin (Sigma P2277), 10 mM Tris-HCl pH 7.2, 10 mM MgCl 2 , 0.1% BSA, 0.05% NaN 3 ) to yield a final concentration of 1.25mU/ml. 99 μl of diluted enzyme solution is added into each well in a flat bottom 96-well polystyrene plate to which 1 μl of test compound dissolved in 100% DMSO is added. The compounds are mixed and pre-incubated with the enzyme for 10 min at room temperature.
[0210] The FL-GMP conversion reaction is initiated by combining 4 parts enzyme and inhibitor mix with 1 part substrate solution (0.225 μM) in a 384-well microtiter plate. The reaction is incubated in dark at room temperature for 15 min. The reaction is halted by addition of 60 μl of binding reagent (1:400 dilution of IMAP beads in binding buffer supplemented with 1:1800 dilution of antifoam) to each well of the 384-well plate. The plate is incubated at room temperature for 1 hour to allow IMAP binding to proceed to completion, and then placed in an Envision multimode microplate reader (PerkinElmer, Shelton, Conn.) to measure the fluorescence polarization (Amp).
[0211] A decrease in GMP concentration, measured as decreased Amp, is indicative of inhibition of PDE activity. IC 50 values are determined by measuring enzyme activity in the presence of 8 to 16 concentrations of compound ranging from 0.0037 nM to 80,000 nM and then plotting drug concentration versus ΔmP, which allows IC 50 values to be estimated using nonlinear regression software (XLFit; IDBS, Cambridge, Mass.).
Example 26
PDE1 Inhibitor Effect on Sexual Response in Female Rats
[0212] The effect of PDE1 inhibitors on Lordosis Response in female rats is measured as described in Mani, et al., Science (2000) 287: 1053. Ovariectomized and cannulated wild-type rats are primed with 2 μg estrogen followed 24 hours later by intracerebroventricular (icy) injection of progesterone (2 pg), PDE1 inhibitors of the present invention (0.1 mg, 1.0 mg or 2.5 mg) or sesame oil vehicle (control). The rats are tested for lordosis response in the presence of male rats. Lordosis response is quantified by the lordosis quotient (LQ=number of lordosis/10 mounts×100). The LQ for estrogen-primed female rats receiving compounds 1 or 2, even at 0.1 mg, is over 75, similar to estrogen-primed rats receiving progesterone and significantly higher (p<0.001) than for estrogen-primed rats receiving vehicle.
|
2-benzyl-3-(optionally hetero)arylamino-[2H]-pyrazolo[3,4-d]pyrimidine-4,6(5H,7H)-diones, in free, salt or prodrug form, are useful as pharmaceuticals, particularly as phosphodiesterase 1 inhibitors.
| 2
|
FIELD OF THE INVENTION
[0001] The present invention relates to the field of internal combustion engines, and, more particularly, to internal combustion engines having exhaust aftertreatment devices.
BACKGROUND OF THE INVENTION
[0002] Internal combustion engines come in a number of forms, the most common of which are spark-ignited gasoline fueled engines and compression-ignition, diesel-fueled engines. The compression-ignition, or diesel-type engine is used in many commercial and industrial power applications because its durability and fuel economy are superior to the spark-ignited gasoline-fueled engines. A diesel engine utilizes the heat of the compression of the intake air, into which a timed and metered quantity of fuel is injected, to produce combustion. The nature of the diesel engine cycle is that it has a variable air-fuel ratio that can, under partial power conditions, rise to levels significantly above stoichiometric. This results in enhanced fuel economy since only the quantity of fuel needed for a particular power level is supplied to the engine.
[0003] One of the issues with a diesel-type engine is the impact on emissions. In addition to the generation of carbon monoxide and nitrous oxide, there is a generation of particulates in the form of soot. A number of approaches are employed to reduce particulates while, at the same time, reducing oxides of nitrogen to ever more stringent levels as mandated by government regulations. Stoichiometric engines have been proposed to achieve this balance since they enable the use of an automotive type catalyst to reduce oxides of nitrogen. By operating the engine at or near stoichiometric conditions, a three-way catalyst may be utilized. However, operation in this manner causes a substantial increase in diesel particulates. Accordingly, a particulate filter (PF) in the form of a diesel particulate filter (DPF) must be employed to filter out the particulates, but the generation of particulates in a significant amount require that frequent regeneration of the filters, through temporary heating or other means, is necessary to remove the collected particulate matter. A wall-flow DPF will often remove 85% or more of the soot during operation. Cleaning the DPF includes utilizing a method to burn off the accumulated particulate either through the use of a catalyst or through an active technology, such as a fuel-burner, which heats the DPF to a level in which the soot will combust. This may be accomplished by an engine modification which causes the exhaust gasses to rise to the appropriate temperature. This, or other methods, known as filter regeneration, is utilized repeatedly over the life of the filter. One item that limits the life of the DPF is an accumulation of ash therein that will cause the filter to require replacement or some other servicing, such as a cleaning method, to remove the accumulated ash. The accumulated ash causes a reduction in the efficiency of the DPF and causes increased back pressure in the exhaust system of the diesel engine system.
[0004] U.S. Patent Application Pub. No. US 2007/0251214 discloses an apparatus for detecting a state of a DPF with a differential pressure sensor. An electronic control unit estimates an amount of ash remaining in the DPF based on the output of the differential pressure sensor immediately after the regeneration process. Alternatively, the residue ash amount may be calculated based on the difference between a ratio of the variation rate of the input manifold pressure with the variation rate of the differential pressure immediately after the regeneration process and an equivalent ratio regarding a thoroughly new or almost new diesel particulate filter. The residue ash amount is calculated every time a regeneration process is carried out and stored in memory. This method is problematic since the backpressure assessment after regeneration can be misleading if the soot has not been entirely removed and since the backpressure due to the ash accumulation measured after each regeneration can vary leading to misleading assumptions about the ash content.
[0005] U.S. Pat. No. 6,622,480 discloses a DPF unit and regeneration control method that adjusts the start timing of a regeneration operation. The method includes an estimate of the ash accumulated quantity that is in the exhaust gas and accumulated in the filter and the correction of the exhaust pressure judgment value for judging the regeneration operation start based on the ash accumulated estimation value. The ash quantity is determined from the quantity of lubricant oil consumed according to the engine operation state. The effective accumulation in the filter with ash is reflected in the judgment of regeneration start timing because the exhaust pressure judgment value to be used for judging the regeneration operation start is corrected with the ash accumulation estimation value. The use of oil consumption is problematic since the lubricant oil may be consumed in ways other than being combusted. Further, even if the oil is not combusted, it is not necessarily passed through the DPF.
[0006] It is also possible that direct-injected gasoline engines may require the use of a PF in the future, as a result of ever increasing governmental emissions standards.
[0007] What is needed in the art is a system that maximizes the life of a PF, such as a DPF, while ensuring that the regeneration process is done in an efficient, economical manner.
SUMMARY
[0008] In one form, the invention includes a particulate filter ash loading prediction method including the steps of determining a maximum average time for the filter; performing a calculation of a running average of time between regenerations of the filter; calculating an end-of-service life ratio of the filter dependent upon the maximum average time and the running average. The method further includes the steps of determining a delta pressure adjustment factor to compensate for ash loading of the filter depending upon the end-of-service life ratio; and comparing the delta pressure adjustment factor to a predetermined maximum delta pressure value, and, if the delta pressure adjustment factor exceeds the predetermined maximum normalized delta pressure adjustment factor, then indicating that a service or replacement of the filter is needed due to the ash loading.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] The above-mentioned and other features and advantages of this invention, and the manner of attaining them, will become more apparent and the invention will be better understood by reference to the following description of an embodiment of the invention taken in conjunction with the accompanying drawings, wherein:
[0010] FIG. 1 is a schematic drawing of a vehicle with an internal combustion engine employing an embodiment of an ash loading prediction method of the present invention; and
[0011] FIGS. 2A and 2B depict a schematical representation of the method utilized in the vehicle of FIG. 1 .
[0012] Corresponding reference characters indicate corresponding parts throughout the several views. The exemplification set out herein illustrates one embodiment of the invention and such exemplification is not to be construed as limiting the scope of the invention in any manner.
DETAILED DESCRIPTION
[0013] Referring now to the drawings, and more particularly to FIG. 1 , there is shown a vehicle 10 , which may be an agricultural work vehicle, a forestry work vehicle or a construction type vehicle utilizing an engine system that includes an air intake 12 , an engine 14 , a fuel supply system 16 (labeled FUEL in FIG. 1 ), and an exhaust system 18 (labeled EXHAUST in FIG. 1 ). Engine 14 has at least one piston reciprocating within an engine block that is connected to a crankshaft for producing a rotary output (not shown). Each piston is movable within a variable volume combustion chamber that receives air for combustion from air intake 12 and fuel from fuel supply system 16 . The products of combustion pass through exhaust system 18 .
[0014] The engine system additionally includes a diesel particulate filter (DPF) 20 (labeled DPF in FIG. 1 ) and a catalyst 22 (labeled CAT in FIG. 1 ). Although the embodiment of the invention illustrated in the drawings and described herein is with reference to a diesel engine having a DPF, it is understood that the present invention can likewise apply to other types of engines using a PF, such as a direct-injected gasoline engine, etc. An air intake flow 24 passes into engine 14 for the purposes of combustion, having an exhaust flow 26 that passes through DPF 20 and a gas flow 28 that continues through catalyst 22 and is exhausted in the form of gas flow 30 to the environment. DPF 20 and catalyst 22 may be combined into one unit or catalyst 22 may be positioned at a different location or omitted from the engine system. A controller 32 interacts with sensors 34 and 36 as well as fuel supply system 16 to control the flow of fuel and to sense the pressure drop across DPF 20 . DPF 20 may be regenerated as directed by controller 32 with input of the sensors 34 and 36 , each of which provide pressure readings so that the pressure drop across DPF 20 can be calculated by controller 32 based on the difference in pressure measurements between sensors 34 and 36 . Controller 32 provides input to fuel supply system 16 , which may cause engine 14 to change the exhaust temperature flowing through exhaust system 18 to DPF 20 , causing a regeneration of DPF 20 .
[0015] Now, additionally referring to FIGS. 2A and 2B , there is shown an ash loading prediction method 100 utilized within controller 32 , which may be interconnected to other sensors and control systems. Controller 32 may have other functions unrelated or indirectly related to the functions of method 100 of the present invention. Method 100 includes a step 102 in which the DPF service age p, as well as the time between regenerations Ψ are separately integrated by a process of integration or summing. This summing of the DPF service age ρ and this step also keeps track of the time between regenerations Ψ. At step 104 , a decision is made as to whether DPF 20 requires a regeneration. This may be decided upon the delta pressure across DPF 20 as sensed by sensors 34 and 36 under the control of controller 32 and upon other portions of method 100 , such as the compensation for the ash loading that is occurring in DPF 20 . With the ash loading prediction being made by the present invention, then the contribution of backpressure in DPF 20 that is attributed to the particulate matter that is to be cleaned from DPF 20 can be accurately assessed to determine if it is time for a regeneration of DPF 20 to take place. If no regeneration is needed, step 104 proceeds back to step 102 but the time continues to be tracked for the DPF service age ρ and the time between regenerations Ψ. If a DPF regeneration needs to take place as decided at step 104 , method 100 proceeds to step 106 in which a DPF regeneration cycle is initiated and takes place.
[0016] A predetermined minimum DPF age τ, schematically shown as step 108 is used in step 110 to compare to the DPF service age ρ to see if ρ is greater than or equal to τ. If the integrated DPF service age ρ is not greater than or equal to the minimum DPF age τ, then method 100 resets the time between regenerations Ψ to be equal to zero, at step 112 , so that it will then start re-accumulating time at step 102 . This portion of method of 100 ensures that at least a minimum age for DPF 20 is realized before establishing a service life for DPF 20 . In the event that the DPF service age ρ exceeds or is equal to the minimum DPF age τ, method 100 proceeds to step 114 to determine if a maximum average time α has been set. If the answer is no, then the maximum average time is set to the most recent time between regenerations Ψ and Ψ AVG is also set equal to Ψ, at step 116 . If the maximum average time a has been previously set, then method 100 proceeds from step 114 to step 118 in which the running average of the time between regenerations Ψ AVG is calculated by the equation of Ψ AVG being set equal to (Ψ AVG +Ψ)/2. Then at step 120 , an end-of-service life ratio Λ is set equal to the running average of time between regenerations Ψ AVG divided by the maximum average time α and the time between regenerations Ψ is set to zero. Method 100 then proceeds to step 122 , in which it is determined whether the end-of-service life ratio Λ is less than or equal to the end-of-service life ratio maximum Λ L . If the answer is no, then method 100 proceeds to step 102 . If the end-of-service life ratio Λ is less than or equal to end-of-service life ratio maximum Λ L , then method 100 proceeds to step 126 in which the percent end-of-service life μ is set using the end-of-service life Λ is an input to a two-dimensional lookup table as illustrated in step 124 where the end-of-service life ratio Λ is used to determine the percent end-of-service life μ. Method 100 then proceeds to step 134 .
[0017] Steps 128 , 130 , and 132 are carried out as an input to step 134 . A DPF delta pressure reading is taken at step 128 by way of sensors 34 and 36 measuring the delta pressure across DPF 20 . The DPF delta pressure reading at step 128 is converted to a normalized delta pressure (Norm-DP) at step 130 using equations from Konstandopoulos, et al., which is contained in SAE 2002-01-1015. The output of step 130 is Norm-DP as illustrated in step 132 , which serves as an input to step 134 . At step 134 , the normalized delta pressure adjustment factor δ is established using Norm-DP and the percent end-of-service life μ as inputs. Normalized DP adjustment factor table 136 is utilized with Norm-DP and percent end of service life μ as inputs to a three dimensional lookup table. At step 140 , it is determined whether the normalized delta pressure adjustment factor δ is greater than or equal to the maximum normalized delta pressure adjustment factor δ L established at step 138 . If the normalized delta pressure adjustment factor δ is greater than the maximum normalized delta pressure adjustment factor δ L , then method 100 proceeds to step 142 in which an adjusted normalized DPF delta pressure is calculated using the normalized delta pressure adjustment factor δ and Norm-DP and then method 100 proceeds back to step 102 . If the normalized delta pressure adjustment factor δ is greater than or equal to the maximum normalized delta pressure adjustment factor δ L , then method 100 proceeds from step 140 to step 144 in which an indication is made that service or the replacement of the DPF 20 is necessary. The indication may be in the form of an illuminated warning light on a console supervised by an operator or some other form of communication of the information to the operator of vehicle 10 or to maintenance personnel. Additionally, at step 144 , when the service or replacement of DPF 20 takes place, variables are set to zero such as Ψ AVG , ρ, α, Λ, μ, δ.
[0018] DPF 20 may be in the form of a wall-flow filter that traps soot with a very high efficiency, even above 90%. When the soot cake layer has been established within DPF 20 , filling the inlet channel walls, the pressure increases across DPF 20 and a soot trapping efficiency of higher than 99% may be achieved. It is common to measure a pressure drop across DPF 20 through the use of a delta pressure sensor, which may include two sensors, such as those illustrated in FIG. 1 as sensors 34 and 36 . The readings from sensors 34 and 36 are used to predict DPF 20 soot loading. These predictions can be made with models, such as those developed by Konstandopoulos, et al., (SAE 2002-01-1015). A high filtration efficiency DPF 20 also traps ash, which can come from high ash lube oil, excessive oil consumption, and high ash fuels, such as biodiesel. As ash gradually accumulates in DPF 20 , the DPF 20 delta pressure signal received by controller 32 at a given soot level will be higher. This behavior is due to ash occupying space in the inlet channels of DPF 20 , leaving less surface/volume for soot distribution.
[0019] Overall, ash accumulation is generally a slow process. Total exhaust system back pressure due to ash starts to become noticeable above 2,500 hours of engine operation for greater than 130 kilowatt applications, and above 1,500 hours of operation for less than 130 kilowatt applications. However, in addition to the effect on engine performance due to higher back pressure, the delta pressure sensor readings increase as a result of the ash loading. Without any compensation for ash loading, the time interval between regenerations starts to decrease since the aftertreatment control system will determine that a DPF 20 regeneration needs to occur based on delta pressure readings.
[0020] It is known that ash loading of DPF 20 will cause higher delta pressure readings across DPF 20 to become progressively higher with soot loading and that such effects cannot be remedied by merely averaging. Also, ash accumulation can take a significant amount of engine operation time to show substantial effects on DPF delta pressure signals and exhaust back pressures.
[0021] Method 100 deals with ash that is accumulated in DPF 20 with time, and recognizes the normalized delta pressure readings will tend to increase, leading to more frequent regenerations. The increase in the number of regenerations can be tied in direct proportion to the overall average time between regenerations. The maximum average time α is calculated early on in engine and aftertreatment service life. Although it can be calculated from the first several samples of time between regenerations, waiting for DPF age ρ to pass a minimum DPF age τ allows there to be ample time for the maximum average time α to be established and thereby avoid a possible over calculation of the maximum average time between regenerations.
[0022] After the maximum average time α is calculated, it will be continuously referenced to calculate the end-of-service life ratio Λ using the ongoing calculation of the running average of time between regenerations Ψ AVG . As DPF 20 loads with ash and the regeneration frequency increases, Λ decreases from 1.0. However, as ash accumulates in DPF 20 , the normalized and non-normalized delta pressure will trend at higher levels for the same soot loading than if there was no ash present in DPF 20 .
[0023] From experimental testing, it has been found that the end-of-service life ratio Λ can be used as an input to a percentage end-of-service life μ lookup table. The percent end-of-service life μ is then used as an input to a three-dimensional table to calculate the normalized DPF 20 delta pressure adjustment factor δ to compensate for the ash loading effect on the normalized DPF delta pressure calculation. The other input to the three-dimensional table is the normalized DPF delta pressure Norm-DP, which is derived using a measured DPF delta pressure and the equations from Konstandopoulos, et al. As ash continues to accumulate, the necessary compensation for the normalized DPF delta pressure will increase in order to accurately measure DPF 20 soot loading. Once the normalized delta pressure adjustment factor δ exceeds a maximum normalized delta pressure adjustment factor δ L , DPF 20 will reach the end-of-service life.
[0024] Advantageously, the present invention provides a statistically based ash model to monitor and verify the ash prediction that is not based on operation hours or fuel consumption history, as utilized in prior art systems. Further, the method is also capable of flagging excessive oil consumption or poor fuel quality that results in excessive loading of DPF 20 . Additionally, the present invention reduces the number of DPF regenerations when the DPF 20 is approaching the end-of-service life. The method can also generate an input for a monitor after determining that an ash service warning or engine degradation is occurring or may occur. Yet further, the present invention can compensate for the use of biodiesel, which has a tendency to create additional ash over petroleum based diesel.
[0025] While this invention has been described with respect to at least one embodiment, the present invention can be further modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims.
|
A particulate filter ash loading prediction method including the steps of determining a maximum average time for the filter; performing a calculation of a running average of time between regenerations of the filter; calculating an end-of-service life ratio of the filter dependent upon the maximum average time and the running average. The method further includes the steps of determining a delta pressure adjustment factor to compensate for ash loading of the filter depending upon the end-of-service life ratio; and comparing the delta pressure adjustment factor to a predetermined maximum delta pressure value, and, if the delta pressure adjustment factor exceeds the predetermined maximum normalized delta pressure adjustment factor, then indicating that a service or replacement of the filter is needed due to the ash loading.
| 5
|
BACKGROUND OF THE INVENTION
Internal combustion engine oil pans are provided with threaded drain plugs whereby engine oil may be drained from the oil pan. However, repeated removal and insertion of the threaded drain plugs sometimes results in the threads in the oil pan being damaged to the extent that the threaded plug may no longer form a fluid-tight closure for the oil pan drain bore. Accordingly, various forms of replacement plug assemblies previously have been provided.
Some of these replacement plug assemblies include lengthwise stretchable, and thus radially contractable, resilient plugs, self-threading plugs and plastic plugs. However, these previously known forms of replacement plugs are either difficult to remove when an oil change becomes necessary, require special tools for removal and/or insertion and are themselves limited in effective life span. Accordingly, a need exists for an improved form of replacement oil pan plug which may be repeatedly removed with ease and enjoy an extended expected lifetime of effective operation.
Various forms of plugs, couplings and other structures including some of the general structural and operational features of the instant invention are disclosed in U.S. Pat. Nos. 2,824,945, 2,935,338, 3,097,867, 3,229,069, 3,422,390, 3,423,110 and 3,761,117. However, these previously known structures also fail to provide an effective readily removable and repeatedly usable replacement oil pan plug.
BRIEF DESCRIPTION OF THE INVENTION
The threadless replacement oil pan plug of the instant invention includes a tubular sleeve for permanent or semi-permanent sealed securement through the drain opening of an oil pan and a plug member including a head and an elongated shank projecting lengthwise outwardly from one side of the head and removably telescopingly received in the sleeve from the end thereof on the exterior of the associated oil pan. The shank includes seal structure for establishing a slidable fluid-tight seal between the shank and the sleeve bore and the exterior end portion of the sleeve and the head of the plug member include coacting structure releasably securing the plug member in position with the shank thereof disposed within the longitudinal bore of the sleeve.
The main object of this invention provide an aftermarket replacement oil pan plug assembly which may be readily installed with a minimum of tools.
Another object of this invention is to provide a replacement oil pan plug assembly including a plug member therefor which may be substantially instantly removed for ready draining of oil from the associated oil pan.
Another object of this invention, in accordance with the immediately preceding object is to provide an oil pan plug assembly including a plug member therefor which may be substantially instantly reinstalled after being removed and is automatically self-locking upon reinstallation.
Still another object of this invention is to provide an oil pan plug assembly including a removable plug member which may be readily removed and installed without the utilization of tools.
A final object of this invention to be specifically enumerated herein is to provide a replacement oil pan plug assembly in accordance with the preceding objects and which will conform to conventional forms of manufacture, be of simple construction and easy to use so as to provide a device that will be economically feasible, long lasting and relatively trouble fre in operation.
These, together with other objects and advantages which will become subsequently apparent, reside in the details of construction and operation as more fully hereinafter described and claimed, reference being had to the accompanying drawings forming a part hereof, wherein like numerals refer to like parts throughout.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a fragmentary perspective view of the drain plug area of a conventional oil pan with a first form of plug assembly constructed in accordance with the present invention operatively associated therewith;
FIG. 2 is a fragmentary vertical sectional view of the assemblage illustrated in FIG. 1 as seen from the inside of the oil pan;
FIG. 3 is an enlarged fragmentary vertical section view taken substantially upon the plane indicated by the section line 3--3 of FIG. 1 and with a removed position of the plug member of the plug assembly illustrated in phantom lines;
FIG. 4 is an enlarged horizontal sectional view taken substantially upon the plane indicated by the section line 4--4 of FIG. 1;
FIG. 5 is a perspective view of the sleeve portion of the oil pan plug assembly with the securing nut therefor removed;
FIG. 6 is a fragmentary perspective view similar to FIG. 1 but illustrating a second form of oil pan plug pan assembly constructed in accordance with the present invention;
FIG. 7 is an enlarged fragmentary vertical sectional view taken substantially upon the plane indicated by the section line 7--7 of FIG. 6;
FIG. 8 is a fragmentary vertical sectional view similar to FIG. 7 but with the sleeve retaining nut and plug member removed;
FIG. 9 is a perspective view of the sleeve seal structure of the second form of the oil pan plug assembly;
FIG. 10 is a fragmentary perspective view similar to FIG. 6 but illustrating a third form of oil pan plug assembly constructed in accordance with the present invention;
FIG. 11 is an enlarged vertical sectional view taken substantially upon the plane indicated by the section line 11-11 of FIG. 10;
FIG. 12 is a perspective view of the sleeve portion of the third form of oil pan plug assembly; and
FIGS. 13 and 14 are side elevational views of alternate sleeve portions which may be utilized in the third form of oil pan plug assembly.
DETAILED DESCRIPTION OF THE INVENTION
Referring now more specifically to the drawings, the numeral 10 generally designates an oil pan having a conventional drain opening 12 formed therein. An annular reinforcing member 14 is secured to the inner surface of the oil pan 10. Conventionally, the drain opening and reinforcing member are internally coextensively threaded to receive a conventional threaded oil pan plug. However, the threads in the drain opening 12 and the reinforcing member 14 sometimes become damaged and are no longer capable of retaining a conventional threaded oil pan in tightly closed position sealing the drain opening 12.
The first form of replacement plug assembly of the instant invention is referred to in general by the reference numeral 16 and includes an elongated sleeve 18 including first and second ends 20 and 22. The first end 20 of the sleeve 18 is provided with a diametric slot 24 and the sleeve defines a central longitudinal bore 26 opening outwardly of the second end 22 of the sleeve and terminating inwardly of the first end 20 of the sleeve 18, but opening into the slot 24. The sleeve 18 includes an enlarged head 28 adjacent the first end thereof and is externally threaded as at 30 from the head 28 to the second end 22 of the sleeve 18.
A resilient combined sleeve and washer 32 constructed of any suitable material such as neoprene is threaded onto the exterior of the sleeve 18 and includes a circumferentially extending and axailly projecting flange 34. A retaining nut 36 is provided and includes a diametrically reduced sleeve portion 38 projecting outwardly from one end thereof and the sleeve portion 38 includes a circumferential groove 40.
A plug member referred to in general by the reference numeral 42 is also provided and includes a cylindrical shank 44 having a circumferential groove 46 and an O-ring 48 seated in the groove 46. The groove 46 is formed in the shank 44 centrally intermediate its opposite ends and one end of the shank 44 includes a diametrically enlarged head 50 including an axially projecting cylindrical skirt 52 provided with circumferentially spaced inwardly tapering radial bores 54 in which spherical lock members 56 are seated. A locking sleeve 58 is telescoped over the exterior of the head 50 and the skirt 52 and includes a diametrically reduced mid-portion 60 retained on the skirt 52 at one end by a locking ring 62 and spring biased by spring 64 toward a position with the diametrically reduced portion 60 engaged with the locking ring 62 by a compression spring 64. The compression spring 64, when totally compressed, limits shifting of the sleeve 58 to the right relative to the head 50 as viewed in FIG. 3 and the locking ring 62 limits shifting of the sleeve 58 to the right as viewed in FIG. 3. When the sleeve 58 is shifted to its limit of movement to the left as viewed in FIG. 3 against the collapsed spring 64, the diametrically reduced portion 60 of the locking sleeve 58 uncovers the outer sides of the spherical members 56 and thus enables the latter to unseat themselves from the groove 40 to thereby enable the plug member 42 to be withdrawn from the sleeve 18. Of course, an outward pull on the locking sleeve 58 releases the plug member 42 for disengagement from the sleeve 44 and the nut 36 and thereby enables merely an outward pull on the locking sleeve 58 to effect total disengagement of the plug member 42 from the sleeve 18. When it is desired to reinstall the plug member 42, the sleeve 58 is shifted to its limit position of movement to the left as viewed in FIG. 3 of the drawings, and the plug member 42 is then inserted into the sleeve 18. Thereafter, the locking sleeve 58 may be released in order that the diametrically reduced portion 60 may cam the lock members 56 into seated engagement in the groove 40.
The O-ring seal 48 establishes a fluid-tight seal between the shank 44 and the bore 26 and the flange 34 and radial expansion of the combined sleeve and the washer 32 effect a fluid-tight seal between the sleeve 18 and the annular reinforcing member 14.
From FIG. 5 of the drawings, it may be seen that the flange 34 is collapsible into a substantially cylindrical condition within an annular recess provided therefor and with an outside diameter substantially equal to the outside diameter of the cylindrical head 28. When it is desired to install the oil pan plug assembly 16, the assemblage comprising the sleeve 18 and the combined sleeve and washer 32 is inserted into the opening 12 and the annular reinforcing member 14. Then, when the flange 34 has cleared the inner side of the reinforcing member 14, the nut 36 is threaded onto the end of the sleeve 18 remote from the head 28 on the exterior of the pan 10. The nut 36 includes a diametrically reduced portion 66 which is snugly received within the drain opening 12 and the combined sleeve and washer is axially compressed and radially expanded between the head 28 and the nut 36 so as to tightly expand within the reinforcing member 14. Further, as the nut 36 is tightened, the head 28 is drawn toward the reinforcing member 14 and the flange 34 has its free end flexed outward and expanded over the inner end of the annular reinforcing member 14. Thus, a reliable fluid tight seal is defined between the sleeve 18 and the reinforcing member 14. Once the sleeve 18, combined sleeve and washer 32 and nut 36 have been installed, it is merely necessary to insert the plug member 42 in the manner hereinbefore set forth.
It is also pointed out that the slot 24 is sufficiently narrow that the blade of a conventional screwdriver of a size to be received through the bore 26 may be received in the slot 24. When the nut 36 is tightened during installation of the sleeve 18, the aforementioned screwdriver blade may be utilized to hold the sleeve 18 against rotation while the nut 36 is tightened.
With attention now invited more specifically to FIGs. 6-9 of the drawings, a second form of plug assembly referred to in general by the reference numeral 116 may be seen. The plug assembly 116 is substantially identical to the plug assembly 16 and therefore has its components corresponding to the various components of the plug assembly 16 referred to by similar reference numerals in the 100 series.
The plug assembly 116 differs from the plug assembly 16 in that three coaxial sleeve members 117, 119 and 121 are utilized in lieu of the combined sleeve and washer 32. The sleeve member 119 is constructed of resilient material and is snugly telescoped within the sleeve member 121. Further, the sleeve member 117 is constructed of resilient material and is snugly telescoped over the sleeve member 121. The sleeve member 121 includes an accordion folded axially compressible and radially expandable portion 123 of a size to be received through the annular reinforcing member 14 and the cylindrical portion of the sleeve member 121 is axially shorter than the sleeve members 117 and 119. Accordingly, as the nut 136 is tightened, the accordion folded portion 123 is axially compressed. In addition, the diametrically reduced portion 166 of the sleeve 136 axially compresses the sleeve members 117 and 119 and when the accordion folded portion 123 is axially compressed, it is increased in outside diameters so that it overlies the inner surface of the annular reinforcing member 14. Thus, at the same time the sleeve retaining accordion folded portion 123 is being axially compressed and radially expanded over the inner surface of the annular reinforcing member 14, the sleeve members 119 and 121 are being axially compressed so as to be radially expanded and thus establish a fluid-tight seal between the annular reinforcing member 14 and the sleeve 118.
Referring now more specifically to FIGS. 10, 11 and 12 of the drawings, there may be seen a third form of oil pan plug assembly referred to in general by the reference numeral 216. The plug assembly 216 is substantially identical to the plug assembly 16 and therefore has its various components referred to by corresponding reference numerals in the 200 series.
The plug assembly 216 differs from the plug assembly 16 in that the sleeve 218 includes a diametrically enlarged threaded mid-portion 225 into which circumferentially spaced longitudinal slots 227 formed in the inner end of the sleeve 218 extend. The inner end portion of the sleeve 227 includes an external taper 229 to facilitate starting of the sleeve in the drain opening 12 and the reinforcing member 14. The nut 236 is threaded onto the outer end of the sleeve 218 until it abuts the shoulder 231 defined by he diametrically enlarged mid-portion 225 and the nut 236 is then utilized to thread the tapered forward end portion and the threaded mid-portion 225 into the opening 12 and the reinforcing member 14, an annular sealing washer 233 being disposed between the inner side of the nut 236 and the outer surfaces of the oil pan 10 extending about the opening 12. It will be noted that the nut 236 does not include a portion corresponding to the diametrically reduced portion 66 inasmuch as the nut 236 is designed to axially compress the sealing washer 232 between the nut 236 and oil pan 10.
With attention now invited more specifically to FIGS. 13 and 14 of the drawings, it may be seen from FIG. 13 that a second form of sleeve 318 may be provided. The sleeve 318 does not include the equivalent of the diametrically enlarged portion 225 of the sleeve 218, but the corresponding portion of the sleeve 318 includes different external threads 319 whereby a nut corresponding to nut 236 may not be threaded onto the threaded portion 319. Of course, the sleeve 318 is designed to be utilized in conjunction with an oil pan drain opening 12 which is somewhat smaller in diameter than the drain opening 12.
With attention now invited more specifically to FIG. 14 of the drawings, a third form of sleeve referred to in general by the reference numeral 418 is illustrated. The sleeve 418 is substantially identical to the sleeve 218, except that the diametrically enlarged mid-portion 425 thereof corresponding to the diametrically enlarged mid-portion 225 is of even greater diameter. Accordingly, the sleeve member 418 is designed to be utilized in conjunction with larger drain plug openings.
In each of the disclosed forms of the drain plugs, the plug member thereof may be readily removed merely by pulling outwardly on the locking sleeve thereof corresponding to the locking sleeves 58, 158 and 258. The outward pull on the locking sleeve uncovers the outer side with the corresponding lock members 56, 156 and 256 thereby enabling the latter to unseat from the corresponding grooves 40, 140 and 240 and the associated plug member to be readily withdrawn from its supporting sleeve. Of course, reinstallation of either plug member may be as readily accomplished.
The foregoing is considered as illustrative only of the principles of the invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described, and accordingly all suitable modifications and equivalents may be resorted to, falling within the scope of the invention.
|
A plug assembly is provided including an elongated sleeve defining a longitudinal bore therethrough and including structure thereon for at least semi-permanent sealed securement through the drain bore of an oil pan. The plug assembly further includes a plug member defining an enlarged head and an elongated shank projecting lengthwise outwardly from one side of the head and removably telescopingly receivable in the longitudinal bore through the sleeve. Seal structure is carried by the shank and establishes a slidable fluid tight seal between the shank and the adjacent surfaces of the sleeve bore. The head of the plug member and the adjacent end of the sleeve include coacting structure releasably securing the plug member against outward displacement relative to the sleeve end and thus lengthwise retraction of the shank and the seal structure from the sleeve bore.
| 5
|
BACKGROUND OF THE INVENTION
The invention relates to cleaning equipment for puncture-resistant gloves and the like, puncture-resistant gloves are used in the meat- and fish-processing industry and protect the personnel, working with cutting tools, against hand injuries.
It is understandable that such puncture-resistant gloves become soiled during work, that is, become clogged with meat fibers, meat residues, blood etc. Because of the hygiene regulations in force, it is necessary that these puncture-resistant gloves, which have been soiled during the work, are cleaned thoroughly.
Until now, puncture-resistant gloves were cleaned by taking off the gloves and cleaning them manually with a hose.
This cleaning is difficult and time-consuming and therefore also unfavorable with respect to the working time spent. Furthermore, with the manual cleaning of the puncture-resistant gloves described, it is also very difficult to achieve very thorough cleaning of the puncture-resistant gloves and, with that, to comply with the corresponding hygiene regulations, which are imposed on the food processing industry.
In slaughterhouses, there is a large number of butchers and employees and, accordingly, a large number of puncture-resistant gloves are used. It is understandable that, with the large number of puncture-resistant gloves, which are used and which have to be cleaned, the previously known method of manually cleaning each individual puncture-resistant glove is time consuming and difficult.
SUMMARY OF THE INVENTION
It is an object of the invention to make possible an easier, less expensive and time-saving cleaning of the puncture-resistant gloves and other equipment, as found in the food processing industry.
The invention starts out particularly from the concept of cleaning the soiled puncture-resistant gloves automatically, that is, of making it possible, for example, to suspend several soiled puncture-resistant gloves in an apparatus and, after the cleaning apparatus is started, to clean the soiled puncture-resistant gloves automatically. This automatic cleaning has the advantage that the cleaning takes place according to previously specified criteria and does not depend on the time available or the care of an individual. In addition, this apparatus has the advantage that several puncture-resistant gloves can be cleaned simultaneously, which is advantageous particularly where, because of the large number of meat-processing persons, there is a large number of soiled puncture-resistant gloves, which must be cleaned.
An embodiment of the proposed equipment is shown in the accompanying drawings.
FIG. 1 shows cleaning equipment for puncture-resistant gloves in a perspective view;
FIG. 2 shows a holding device for the puncture-resistant gloves, which are to be cleaned;
FIG. 3 is a partial cross sectional view of the washing device;
FIG. 4 is a partial plan view of the support plate;
FIG. 5 is a partial plan view of the base which underlies the support plate.
FIG. 6 is a side view of a washing nozzle showing interior structure thereof in dashed lines.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The cleaning equipment in this embodiment is constructed in the form of a carousel, with apertures 1; in which the puncture-resistant gloves 9 are suspended, and disposed in a round holding plate 2. In this embodiment, the holding plate 2 is constructed round. However, it may also have other shapes. On the other hand, it is also possible to transport objects which are to be cleaned, such as puncture-resistant gloves 9, on a different type of conveying equipment, such as an appropriate conveyor belt, conveyor chain, etc.
The holding plate 2 is disposed on a support 17. In a lower region of the support 17, a base plate 3 is disposed which has a diameter smaller than that of the holding plate 2. The holding plate 2, as well as the base plate 3, are driven by a driving mechanism, which is not shown. Moreover, they are driven in the same direction and at the same speed.
Below the holding plate 2, a semi-circular basin 7 is disposed, which is open at top and closed off at sides by side walls, the side walls having an approximately U-shaped opening 8 which is open at the top.
Of course, the basin 7 can also have a different shape or be constructed longer or shorter. On one side of the proposed cleaning equipment, there is a washing unit 19 which is disposed on a support 20; so that the washing unit 19 is extends at a small distance above the rotating holding plate 2. The washing unit includes of a washing nozzle, 23 which is constructed approximately peg-shaped. The outer periphery of this washing nozzle 23 has holes and water under high pressure can be passed into the whole of the washing nozzle, so that this water emerges from the nozzles and cleaning of the puncture-resistant glove is achieved. The washing nozzle in the washing unit 19 is movable and, when there is the aperture below the washing nozzle and the aperture 1 is "filled" with a puncture-resistant glove 9, is lowered into the suspended puncture-resistant glove 9 as indicated in broken lines in FIG. 3. After spray washing with water under high pressure, the washing nozzle 23 is raised once again out of the puncture-resistant glove 9 and, thereupon, lowered into and raised out of the glove a few times once again and, at the same time, sprayed with water or cleaning liquid in order to achieve intensive cleaning of the puncture-resistant glove 9 as a whole by this oscillatory movement. The washing unit 19 also has washing equipment 24 which, is disposed stationarily and sprays water onto the suspended puncture-resistant glove 9 in order to bring about cleaning of the puncture-resistant glove 9 also from the outside. On the other hand, the washing nozzle 23 cleans the puncture-resistant glove 9 from the inside toward the outside in order to achieve an optimum cleaning effect.
Below the base plate 3, metal contacts 25 are disposed in each case to correspond to the apertures 1 in the holding plate 2 above. A sensor 26, which is disposed below the base plate 3, brushes over these contacts. Depending on the information of this sensor, the holding plate 2 is clock controlled by a motorized driving mechanism, that is, whenever there is an aperture 1 below the washing nozzle 23 of the washing unit 19, the driving mechanism of the holding plate 2 stops and the washing nozzle can now be lowered into the aperture 1 and into the glove suspended therein. The arrangement of the sensor and of the individual contact surfaces below the base plate 3 has the advantage that the space below the base plate 3 is protected from spray water and contamination of this technical equipment is therefore prevented.
A second sensor 27 is located in the washing unit 19 and senses whether a puncture-resistant glove 9 is suspended in the aperture 1. If a glove is not suspended, this is recognized by a second sensor and, accordingly, there is no lowering of the washing nozzle 23. Instead, the holding plate 2 is advanced in order to check whether a puncture-resistant glove 9 is suspended in the next aperture 1.
The actual cleaning of the suspended glove 9 takes place under a high pressure of, for example, 200 bar. Either water or a special cleaning solution is suitable for the cleaning. Below the washing unit 19, a discharge pipe 14 is provided, through which the consumed wash water is discharged to a discharging basin 15, which is provided with a screen in order to filter off the coarser components of the effluent. The filtered water is carried away through a discharge pipeline 21.
After the puncture-resistant glove 9 is cleaned, the whole of the holding plate 2 is advanced by means of the motor-driven mechanism. The freshly cleaned glove first of all passes into the region of the basin 7 in which the liquid, dripping from the cleaned glove, is collected.
In order to suspend the gloves 9, the gloves are provided at their cuffs with a textile tape having three openings are. The aperture 1 are provided, in each case, with three upwardly directed hooks 22, as shown FIG. 2. The openings in the cuffs of the puncture-resistant gloves 9 are pushed onto the hooks 22, so that, as can be seen from FIG. 1, the gloves hang down from the holding plate 2 accommodating them.
After the aperture have been loaded with gloves 9 outside of the basin 7, the holding plate 2, by depressing pedal 4, is set in motion, so that it carries out half a revolution, that is, after this movement of the holding plate 2, the aperture 1, loaded with gloves 9, are in the region of the basin 7, and the aperture 1, which are still free, are available to the user and can thus easily be loaded with gloves 9, since the loading is not made difficult by the basin 7 below. After all or most of the aperture 1 have been loaded with gloves 9, the equipment shown is set in motion by pressure on the pedal 5.
The support 17 is constructed like a cupboard and therefore protected against contamination. A door 6 is disposed at the support 17, so that the electronics and the gearing within the support 17 can be attended to. An emergency switch 12 is provided so that the equipment shown can be stopped quickly. The gearing for the movable washing nozzle of the washing unit 19 is located in the housing 11. Two lamps 13 signal if the equipment shown is being operated. When two lamps are lit, water, with a cleaning liquid, is sprayed into the glove 9. After the first washing step, only water is introduced into the glove 9 in order to remove the cleaning liquid and only one lamp 13 is still lit. Of course, the cleaning processes for the puncture-resistant gloves 9 can be adjusted individually as required and depending on the degree of contamination, that is, the nature and number of cleaning processes can be preprogrammed.
With the equipment shown, it is also possible to wash and rinse other devices, which turn up in such slaughter houses, fish-processing plants and the like, such as knives, aprons, etc. By changing the type of suspension for the objects to be cleaned, that is, by not using a hook 22 and using, instead, a flatware holder or the like, it is easily possible to employ this arrangement, for example, for cleaning cutlery.
|
The invention relates to cleaning equipment for puncture-resistant gloves and the like and to a support, which accommodates one or several holding mechanisms for puncture-resistant gloves, the support being constructed movably, so that each holding mechanism can be brought into the sphere of activity of a washing nozzle, which is connected with a supply of cleaning liquid.
| 3
|
FIELD OF THE INVENTION
The present invention relates generally to the field of electric motors. More particularly, the present invention relates to determining electric motor performance using a sensed internal temperature of the motor.
BACKGROUND OF THE INVENTION
Conventional brushless direct current (DC) motors rely on the magnetic flux created by permanent magnets located on the rotor interacting with magnetic fields from the stator to generate a mechanical torque. Indeed, the output mechanical torque generated by a brushless DC motor is directly proportional to the magnetic flux density of the rotor magnets. Often, performance characteristics of a brushless DC motor are evaluated based on the output mechanical torque generated by the motor as a function of the input stator current. In many applications, it is critical to accurately determine the output mechanical torque produced by a motor for a known stator current.
The magnetic flux of the rotor magnets and its relationship with the magnetic fields induced by the stator current is a function of the motor temperature. It is well known that the magnetic flux density of magnetic materials (i.e., rotor magnets) decreases as temperature increases, resulting in degradation of motor performance. Herethereto, conventional approaches to this problem have been to simply recognize a performance degradation during high-temperature operation and attempt to try to regulate the ambient temperature, or to recommend only certain operating temperature conditions.
It would therefore be desirable to provide systems and methods for accurately sensing the temperature of the rotor magnets to provide more accurate output torque information.
SUMMARY OF THE INVENTION
The foregoing needs are met, to a great extent, by the present invention, wherein in one aspect an apparatus is provided to sense the temperature of the rotor magnets of a brushless DC motor.
In accordance with one embodiment of the present invention, an electric motor system is provided having an electric motor with a temperature sensor mounted inside the motor capable of measuring local temperature and a processor that utilizes a temperature signal from the temperature sensor to determine an output mechanical torque generated by the motor.
In accordance with another embodiment of the present invention, a centrifuge system is provided, comprising an electric motor having at least one temperature sensor, a motor shaft, and a specimen holder connected to the motor shaft a processor in communication with the temperature sensor to determine an output mechanical torque generated by the motor,
In accordance with another embodiment of the present invention, a method is provided for determining the output mechanical torque generated by an electric motor having rotor magnets. The method comprises the steps of sensing local temperature at a location inside the motor and calculating an output mechanical torque generated by the motor based on the determined temperature.
In accordance with yet another embodiment of the present invention, a system is provided for determining the output mechanical torque generated by an electrical motor having rotor magnets. The system comprises means for sensing local temperature at a location inside the motor, and means for calculating an output mechanical torque generated by the motor based on the determined temperature.
There has thus been outlined, rather broadly, certain embodiments of the invention in order that the detailed description thereof herein may be better understood, and in order that the present contribution to the art may be better appreciated. There are, of course, additional embodiments of the invention that will be described below and which will form the subject matter of the claims appended hereto.
In this respect, before explaining at least one embodiment of the invention in detail, it is to be understood that the invention is not limited in its application to the details of construction and to the arrangements of the components set forth in the following description or illustrated in the drawings. The invention is capable of embodiments in addition to those described and of being practiced and carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein, as well as the abstract, are for the purpose of description and should not be regarded as limiting.
As such, those skilled in the art will appreciate that the conception upon which this disclosure is based may readily be utilized as a basis for the designing of other structures, methods and systems for carrying out the several purposes of the present invention. It is important, therefore, that the claims be regarded as including such equivalent constructions insofar as they do not depart from the spirit and scope of the present invention. The invention will now be described with reference to the drawing figures, in which like reference numerals refer to like parts throughout.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view of a conventional brushless DC motor.
FIG. 2 is a temperature vs. magnetic flux density graph for four permanent magnet materials.
FIG. 3 is a cross-sectional view of a brushless DC motor illustrating exemplary temperature sensor locations according to an embodiment of this invention.
FIG. 4 is a block diagram of an exemplary temperature sensor device.
FIG. 5 is a flowchart illustrating an exemplary process for determining performance characteristics of a brushless DC motor.
FIG. 6 is a block diagram of an exemplary centrifuge.
DETAILED DESCRIPTION
In some preferred embodiments, the invention provides a system and method that determines electrical motor performance using at least one sensed internal temperature of the motor. Preferably, the temperature of one or more rotor magnets is sensed. Preferred embodiments of the invention will now be described with reference to the drawing figures in which like reference numbers refer to like elements throughout.
FIG. 1 . is a cross-sectional view of a conventional brushless DC motor 10 having a rotor 12 , rotor magnets 14 , a stator 16 , and a motor housing 18 . An output mechanical torque is produced on the rotor 12 as a result of the interaction of the magnetic flux of the rotor magnets 14 and the rotating magnetic flux induced by the stator current. These components of brushless DC motors are well known in the art, and therefore for the purposes of this discussion is not further discussed herein.
Typically employed magnetic materials experience a decrease in flux density as the temperature of the magnetic material increases. Therefore, as the temperature of the rotor magnets 14 increases, the magnetic flux density Br of the rotor magnets 14 decreases.
FIG. 2 is a graphical illustration of the relationship between magnetic flux density and temperature over the range 0-120° C. for four permanent magnet materials commonly employed as rotor magnets in brushless DC motors. Over the operating range of most brushless DC motors, for example 0-140° C., the inverse relationship between temperature and magnetic flux density is considered to be generally linear for most permanent magnet materials. From FIG. 2 , it is evident that ceramic ferrite 20 experiences a drop in magnetic flux density of 0.2% per degree Celsius over the range 0-120° C. Similarly, fully dense Nd 2 Fe 14 B, 22 , exhibits a drop in magnetic flux density of 0.10% per degree Celsius, where sintered SmCo 5 , 24 , exhibits a drop in magnetic flux density of 0.045% per degree Celsius, and sintered Sm 2 Co 17 26 exhibits a drop in magnetic flux density of 0.03% per degree Celsius over the range 0-120° C.
Although FIG. 2 illustrates the relationship between magnetic flux density and temperature for four permanent magnet materials commonly employed as rotor magnets in brushless DC motors, it should be appreciated that other permanent magnet materials can be used as rotor magnets as deemed suitable by one ordinary skill in the art.
Often, motor performance characteristics are evaluated based on the output mechanical torque τ generated as a function of input stator current I S . Moreover, in many applications, it is critical to accurately determine the output mechanical torque τ of a brushless DC motor 10 as a function of stator current I S . For example, in a centrifuge system energy calculations are based on assumed motor torque based on the input stator current I S . Calculations of acceleration rates, deceleration rates, system energy, and rotational inertia are based on an accurate estimate of the output mechanical torque. If these calculations are incorrect because of an inaccurate output mechanical torque, then the centrifuge material may be improperly centrifuged.
It is well known in the art that the output mechanical torque of a brushless DC motor 10 is directly proportional to I S . This relationship is expressed empirically as
τ=k t I s , (Eq. 1)
where the torque constant k t of the motor 10 is a function of and directly proportional to the magnetic flux density B of the rotor magnets 14 . Therefore, because an increase in the temperature of the rotor magnets 14 causes a decrease in the magnetic flux density B r of the rotor magnets 14 , an increase in temperature of the rotor magnets 14 causes a decrease in the value of the torque constant k t . Thus, the torque constant k t is inversely proportional to the temperature of the rotor magnets 14 . Consequently, an increase in the temperature of the rotor magnets 14 results in a diminished output mechanical torque τ. Therefore, knowing the temperature of the rotor magnets 14 permits determination of the output mechanical torque τ, of a brushless DC motor.
In order to determine the relationship between the temperature of the rotor magnets 14 and the output mechanical torque τ of a brushless DC motor 10 , a first step is to determine the maximum value of the torque constant k t of the motor 10 . The maximum value of the torque constant k t is the value of the torque constant k t of the cold motor 10 operating at room temperature (20° C.). The torque constant k t of a brushless DC motor 10 is proportionally equivalent to the voltage constant k E of the back electromotive force (EMF) of the motor. Accordingly, the voltage constant k E value of the motor 10 is directly related to the magnetic flux density B r of the rotor magnets 14 and is thus inversely proportional to the temperature of the rotor magnets 14 . Therefore, once the voltage constant k E value of a cold brushless DC motor 10 operating at 20° C. is known, a simple conversion of units yields the maximum torque constant k t , in-lbs/amp, of the motor 10 .
As disclosed in U.S. Provisional Patent Application 60/381,824, filed May 21, 2002 titled “Back EMF Measurement to Overcome the Effects of Motor Temperature Change”, the disclosure of which is hereby incorporated by reference in its entirety, the voltage constant k E value of a brushless DC motor 10 is readily determined by driving the rotor with a second motor and measuring the back EMF (i.e., the voltage across two stator phases) and the revolutions per minute (RPM) of the rotor. The torque constant of the motor 10 is then easily calculated from the voltage constant k E value of the motor 10 .
Equipped with the maximum torque constant k t of a brushless DC motor 10 , the relationship between the temperature of the rotor magnets 14 and the output mechanical torque τ is readily determined. Due to the inverse relationship between magnetic flux density B r and magnet temperature and the direct relationship between output mechanical torque τ and the magnetic flux density B r of the rotor magnets 14 , the percent decrease in output mechanical torque τ for a brushless DC motor 10 operating with rotor magnets 14 at a particular temperature T M1 , for example, is given by
Δτ=( T M −T M1 )·(Δ B r ), (Eq. 2)
where Δτ represents the percent decrease in output mechanical torque, T M represents the current temperature of the rotor magnets 14 , T M1 represents the temperature at the first test point, and ΔB r represents the percent decrease in magnetic flux density of the permanent magnet material used for the rotor magnets 14 . Using the result of Eq. 2, the percent of motor torque remaining at a particular temperature τ remaining is then calculated from
τ remaining =(100−Δτ). (Eq. 3)
Finally, from Eq. 1, the actual output torque τ of the motor 10 for a known stator current I S and particular rotor magnet 14 temperature is found from
τ=[ k t(20° C.) I S ]·τ remaining (Eq. 4)
In a preferred embodiment of the present invention, it is possible to accurately determine the temperature of the rotor magnets 14 of a brushless DC motor 10 using sensors mounted inside of the motor 10 . FIG. 3 . is a cross-sectional view of a brushless DC motor 30 illustrating exemplary locations for mounting temperature sensors. As demonstrated by FIG. 3 , temperature sensors 32 can be mounted on the commutation board 34 or in the motor housing 36 as close to the rotor magnets 14 as reasonably possible to obtain a relatively accurate temperature. Additionally, the temperature sensor(s) 32 maybe situated adjacent to the stator 16 , as desired. It should be appreciated by one of ordinary skill in the art that the temperature sensors 32 can be located in other positions, as according to design preferences, without departing from the scope and spirit of this invention. That is, the temperature sensor(s) may be placed at any position inside the envelope of the motor.
FIG. 4 depicts a block diagram of an exemplary temperature sensor circuit 40 according to this invention. A temperature sensor 42 —preferably, but not necessarily, an integrated circuit (IC) type sensor—is used to determine the local temperature at the sensor position inside the motor 10 . It should be apparent that though this preferred embodiment employs the use of an IC-type sensor to sense the rotor magnet 14 temperature, other devices capable of sensing temperature may be used as deemed suitable by one of ordinary skill in the art, such as, for example, optical, chemical, pressure, methods or schemes that are directly or indirectly capable of detecting temperature or changes in temperature.
In operation, if the output of the temperature sensor 42 is a digital signal, the temperature signal is passed directly to logic/decision device 46 , illustrated here as a processor. If the output of the temperature sensor 32 is an analog signal, the signal is fed to the analog-to-digital (A/D) converter 44 . The converted digital temperature signal is then passed from the A/D converter 44 to the processor 46 . The processor 46 is then used to determine the actual temperature of the rotor magnets 14 . While FIG. 4 is discussed in the context of using digital signals or digital processing, it should be appreciated that a completely analog, hybrid, or analog-digital system may be used without departing from the spirit and scope of the invention.
In order to determine with a described accuracy the temperature of the rotor magnets 14 from the temperature signal relayed by the temperature sensor 42 , the offset between the local temperature sensed by the sensor 42 and the actual temperature of the rotor magnets 14 may be first determined through experimental measurements or an initial calibration or preset. To determine the offset of the rotor magnet 14 temperature from the temperature sensor 42 readings, the rotor magnets 14 may be heated to at least two different known temperatures, T M1 and T M2 , and the corresponding temperatures measured by the temperature sensor 42 T S1 , and T S2 , respectively, would be recorded. Using this data and assuming that the offset of the temperature sensor 42 readings from the rotor magnet 14 temperature exhibits a linear relationship, it is possible to accurately determine the temperature T M of the rotor magnets 14 , for a temperature sensor 42 reading T S using the expression
T M =[( T M2 −T M1 )/( T S2 −T S1 )]· T S +T M2 −[( T M2 −T M1 )/( T S2 −T S1 )]· T S2 . (Eq. 5)
It should be appreciated that although this embodiment uses a linear interpolation algorithm to account for the offset of the rotor magnet 14 temperature from the temperature sensor 42 reading, other algorithms, whether linear or non-linear, for determining the offset of the rotor magnet 14 temperature from the temperature sensor 42 reading may be used as deemed suitable by one of ordinary skill in the art.
After determining the actual temperature of the rotor magnets 14 , the processor 46 is used to determine the output mechanical torque τ for the known input stator current I S and the determined rotor magnet 14 temperature using Eqs. 2-4. From the determined value of the output mechanical torque, the processor 46 can be used to calculate other performance characteristics of the motor 10 , including, but not limited to acceleration rates, deceleration rates, system energy of an unknown load.
FIG. 5 is a flowchart illustrating an exemplary process 50 for determining changes in the performance characteristics of a motor 10 according to this invention. The exemplary process 50 begins at step 52 , whereby one or a plurality of temperature sensors 42 mounted inside of the motor 10 are used to sense the local temperature at the designated sensor position(s) at step 54 . Using the reading of the temperature sensor(s) 42 at step 54 , the exemplary process 50 proceeds to step 56 whereby the actual rotor magnet 14 temperature is determined according to the process described in FIG. 4 , or any other suitable process. Once the actual temperature of the rotor magnets 14 has been accurately determined in step 56 , the output torque of the motor 10 is calculated in step 57 based on the input stator current and the accurately determined rotor magnet 14 temperature from step 56 . The process 50 then proceeds to step 58 where performance characteristics of the motor 10 can be calculated. Such performance characteristics can include, but are not limited to acceleration rates, deceleration rates, system energy, or the rotational inertia of an unknown load. After the completion of step 58 , the exemplary process 50 may proceed to step 59 to end the process, or optionally cycle to step 54 and repeat itself periodically or aperiodically, as desired.
While FIG. 5 illustrates one exemplary process for determining changes in performance characteristics of an electric motor, it should be appreciated by one of ordinary skill in the art that other processes can be employed to use the data collected by the temperature sensor 42 to determine changes in performance without departing from the spirit or scope of this invention. For example, the order of the steps in FIG. 5 could be rearranged, the number of steps could be reduced, or additional steps could be added.
Furthermore, although FIGS. 3-5 describe the use of a temperature sensor 42 to determine the temperature of the rotor magnets 14 , of a motor, it should be appreciated by one of ordinary skill in the art that the temperature sensor 42 could also be used to accurately determine the temperature of other components of the motor that affect motor performance such as, but not limited to, the stator 16 or motor housing 18 temperatures without departing from the spirit and scope of this invention.
In addition, while the above figures illustrate the invention as being described in the context of sensing rotor magnet 14 temperatures in a brushless DC motor 10 , it should be appreciated by one of ordinary skill in the art that the invention could also be used to accurately determine magnet temperature in other types of permanent magnet electric motors.
Electric motors are often used in centrifuges, such as for example laboratory centrifuges. FIG. 6 is a block diagram of an exemplary centrifuge 60 according to this invention. The exemplary centrifuge 60 has a motor 62 , turntable shaft 64 , and centrifuge rotor 66 . The output torque generated by the centrifuge motor 60 drives the turntable shaft 64 which in turn causes the centrifuge rotor 66 to rotate. In the exemplary centrifuge system 60 , energy calculations are based on the motor torque which is calculated from sensing the rotor magnet temperature according to systems and methods according to this invention. The systems and methods described above may be used to increase the accuracy of the estimate of the output mechanical torque generated by the motor, thus increasing the accuracy of the energy calculations for centrifuge applications. Therefore, parameters such as acceleration rates, deceleration rates, system energy, and rotational inertia, are accurately determined based on the output mechanical torque generated by the motor 60 .
Furthermore, it should be appreciated by one of ordinary skill in the art that other uses and functions may be arrived at by utilizing the internal temperature information or flux determination. For example, if the temperature sensed by the temperature sensors is over a predetermined over temperature value, the exemplary centrifuge 60 may initiate a shutdown or recovery operation. Thus, in addition to accurately determining the mechanical torque (or other temperature affected metrics), safety considerations may be exploited.
The many features and advantages of the invention are apparent from the detailed specification, and thus, it is intended by the appended claims to cover all such features and advantages of the invention which fall within the true spirit and scope of the invention. Further, since numerous modifications and variations will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation illustrated and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention.
|
A method and apparatus is herein disclosed for determining the motor performance of an electric motor through monitoring the temperature of rotor magnets. The temperature is determined by initially heating the rotor magnets to two known temperatures and subsequently recording the temperature at each known temperature. From the known and recorded temperatures, an offset, if any, is calculated. An actual temperature is then determined from the subsequent temperatures of the magnets and the offset. The actual temperature is then used as a basis to determine the motor performance.
| 6
|
BACKGROUND OF THE INVENTION
This invention relates to a nonvolatile, integrated-circuit memory array such as a flash erasable, electrically programmable read-only-memory (flash EPROM or flash EEPROM) array. In particular, this invention relates to on-chip control of operations such as programming, erasing and threshold-voltage compaction of such memories.
Flash EPROMs of the type discussed herein are described in: (a) "A Single Transistor EEPROM cell and its implementation in a 512K CMOS EEPROM", S. Mukherjee et al., IEDM 1985 (p. 616-619) and (b) "A 90ns 100K Erase/Program Cycle Megabit Flash Memory", V. Kynett et al., ISSCC 1989 (p. 140-141). The topic of reference (a) is also discussed in U.S. Pat. No. 4,698,787.
Early flash memories require complex commands from a separate-chip microprocessor when performing write and erase operations. For example, instead of a simple erase command from the microprocessor, the microprocessor is required to furnish the length of the erase pulse and, in addition, a test routine to check for proper erasure. While the commands for write and erase operations may be changed to accommodate manufacturing variations among chips of the same type, those changes must be programmed by system users. Those programming changes require additional system manufacturing time. In addition, after exceeding the maximum number of program/erase cycles, replacement of flash memories is made difficult because replacement memories having different characteristics require re-programming of the separate-chip microprocessor, which is often burdensome for an end-user.
As flash memory technology evolves, the demand by end users for increasing ease of installation, use and replacement has led to the development of automated control instructions for programming and erasing FLASH memories. The automated program and erase control instructions are embedded in the write state machine (WSM) architecture of such flash EPROMs. The codes for those control instructions are stored in a control-read-only-memory (CROM) in the write state machine. With the automated program and erase instructions embedded in the write state machine, the external-to-chip microprocessor need only furnish a simple "erase" command. That is, it is not necessary for the external-to-chip microprocessor to furnish pulse length directions or other complex information necessary to perform the write and erase operations. The embedded program and erase control instructions allow the memory manufacturer to alter the program and erase control instructions to compensate for manufacturing variations.
Because of the limited space outside of the memory array, it is not practical to form a microprocessor on a memory chip if that microprocessor has most of the features of an external-to-memory-chip microprocessor.
Prior-art implementations of embedded program and erase control instructions generally fall into three groups, random-logic implementation, programmed logic-array-based implementation (PLA-based implementation), and microcode ROM-based implementation.
The first group, random-logic implementation, generally consumes a large surface area on a memory chip, such as a flash EPROM chip. Using random-logic implementation, both the program and erase/compaction instructions are generally limited to simple operations because of the required high number of logic gates needed to implement those instructions.
The second group, programmed-logic-array-based implementation, also generally consumes a large chip area. Typically, a separate programmed logic array is dedicated to each mode of operation when used to implement an automated instruction. This requires a minimum of four programmed logic arrays for a flash EPROM chip--one for the control operation, one for the program operation, one for the erase operation, and one for the compaction operation. While more complex instructions can be implemented using this second group rather than the first group, the state density is not high. In addition, instruction changes to compensate for manufacturing variations are generally difficult to make.
The third group, microcode ROM-based implementation, provides maximum flexibility and relatively smaller chip area than the other two implementation groups, especially for complicated operations or instructions. This type of implementation includes a control-read-only-memory (CROM), containing micro-instructions and control data, a program counter multiplexer (PCM) to select instructions from the control-read-only-memory (CROM), a micro-instruction decoder (MID), an input test input multiplexer (TIM) to test control signals, an optional status output register (SOR) to generate control signals, and an optional subroutine stack (SS) to allow function calls. The microcode ROM-based implementation of the type discussed herein are described in U.S. Pat. No. 5,491,660 issued Feb. 13, 1996 to Benjamin H. Ashmore, Jr., assigned to Texas Instruments Incorporated and in U.S. Pat. No. 5,359,570.
Due to the "fixed" syntax of the microcodes and the nature of the on-chip operations or procedures of the prior-art devices, about two-thirds of the seventy-five bits used for prior-art overall program codes are not used for actual control of the internal circuit operation of the flash EPROM. Instead, those bits are used for such things as branching, testing and other controls internal to the microsequencer. In addition, only about one third of the fifty-eight control bits of the prior-art flash EPROMs switch at the same time because the program, erase and compaction operations are completely independent of each other. As a result, only one-third of the output field is effectively used, while two-thirds is idle, therefore wasted.
There is a need for reducing the size of the control-read-only-memory used in the third group (the microcode ROM-based implementation), particularly if the reduction can be accomplished without degrading the performance or speed of the control.
SUMMARY OF THE INVENTION
The memory control this invention is an improved version of the invention disclosed in the above-referenced U.S. Pat. No. 5,491,660. The improved memory control includes a control-read-only-memory (CROM), containing micro-instructions and data, a program counter multiplexer (PCM) to select instructions from the control-read-only-memory (CROM), a micro-instruction decoder and BILBO control (MID/BC), an input test input multiplexer (TIM) to test control signals, an optional status output register (SOR) to generate control signals, and an optional subroutine stack (SS) to allow function calls.
As in the prior-art, this improved on-chip flash EPROM control offers advantages that include:
a) Information density in the control-read-only-memory is high. Therefore, complex program, erase, and compaction instruction are implemented using a relatively small number of control-read-only-memory locations and thus yielding smaller chip size; and
b) All control instructions are easily modified by simply changing the microcode contained in the control-read-only-memory and thus providing maximal design flexibility with minimal cost.
The memory control this invention includes a microprogram-read-only-memory containing micro-instructions for operation of an integrated-circuit memory, a program counter multiplexer to select instructions from the control-read-only-memory, a micro-instruction decoder with BILBO control, a test input multiplexer to test control signals, an optional status output register to generate control signals, and a subroutine stack to allow function calls. A program counter takes an index signal from the micro-instruction decoder with BILBO control and a signal from the program counter multiplexer, and from those signal, generates a next microcode address. Complex program, erase, and compaction instructions for the integrated-circuit memory are implemented using a relatively small number of control-read-only-memory locations and using a relatively small surface area on the memory chip. Control instructions are easily modified to compensate for process and structure enhancements are made during the production lifetime of an integrated-circuit memory.
The improved control of this invention is one-third of the size of the prior-art control-read-only-memory. The reduction in size does not degrade the performance or the speed of control operation. This is done by redefining the micro-instruction or microcode syntax and modifying the design of the circuits described in the above-referenced U.S. Pat. No. 5,359,570 and U.S. Pat. No. 5,491,660. Specifically, this invention uses three additional separate sets of latches as compared to circuits described in the referenced patents. However, the number of BILBO SRLs in this invention is reduced to twenty-four from the previous seventy-five. The three sets of latches are primarily used for control signals for programming, erasing and compaction operations.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is an electrical schematic diagram, in partial block form, of a memory cell array;
FIG. 2 is a circuit, in block form, illustrating the prior-art control method: and
FIG. 3 is a circuit, in block form, illustrating an embodiment of the control method of this invention.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1, an example array of memory cells 10, which is an integral part of a memory chip, is shown for the purpose of illustrating use of the method and circuitry of this invention. Each cell is a floating-gate transistor 10 having a source 11, a drain 12, a floating gate 13, a control gate 14. Each of the control gates 14 in a row of cells 10 is connected to a wordline 15, and each of the wordlines 15 is connected to a wordline decoder 16. Each of the sources 11 in a row of cells 10 is connected to a source line 17. Each of the drains 12 in a column of cells 10 is connected to a drain-column line 18. Each of the source lines 17 is connected by a common-column line 17a to a column decoder 19 and each of the drain-column lines 18 is connected to the column decoder 19.
In the read mode, the wordline decoder 16 functions, in response to wordline address signals on lines 20R and to signals from Read/Write/Erase control circuit 21 (or external microprocessor 21), to apply a preselected positive voltage VCC (approx. +5 V) to the selected wordline 15, and to apply a low voltage (ground or VSS) to deselected wordlines 15. The column decoder 19 functions to apply a preselected positive voltage VSEN (approx. +1 V) to at least the selected drain-column line 18 and to apply a low voltage (0 V) to the source line 17. The column decoder 19 also functions, in response to signals on address lines 20D, to connect the selected drain-column line 18 of the selected cell 10 to the DATA IN/OUT terminal 22. The conductive or nonconductive state of the cell 10 connected to the selected drain-column line 18 and the selected wordline 15 is detected by a sense amplifier (not shown) connected to the DATA IN/OUT terminal 22.
During a flash-erase mode, the column decoder 19 functions to leave all drain-column lines 18 floating (connected to a high impedance such as field-effect transistor biased in "OFF" condition). The wordline decoder 16 functions to connect all the wordlines 15 to VSS, which may be ground or 0 V. The column decoder 19 also functions to apply a positive voltage VEE (approx. +10 V to +15 V) to all the source lines 17. These erasing voltages create sufficient field strength across the gate oxide region to generate a Fowler-Nordheim tunnel current that transfers charge from the floating gate 13, erasing the memory cell 10. Since the potential on the wordline 15 is at reference voltage VSS, the cell 10 remains in the nonconducting state during erase. Over-erased cells 10 are corrected by one of several compaction procedures.
In a write or program mode, the wordline decoder 16 may function, in response to wordline address signals on lines 20R and to signals from Read/Write/Erase control circuit 21, (or external microprocessor 21) to place a preselected first programming voltage VPP (approx. +12 V) on a selected wordline 15, including a selected control-gate 14. Column decoder 19 also functions to place a second programming voltage VBL (approx. +5 to +10 V) on a selected drain-column line 18 and, therefore, the drain 12 of selected cell 10. Source lines 17 are connected to reference potential VSS, which may be ground. All of the deselected drain-column lines 18 are connected to reference potential VSS or are floated. These programming voltages create a high current (drain 12 to source 11) condition in the channel of the selected memory cell 10, resulting in the generation near the drain-channel junction of channel-hot electrons and avalanche-breakdown electrons that are injected across the channel oxide to the floating gate 13 of the selected cell 10. The programming time is selected to be sufficiently long to program the floating gate 13 with a negative program charge of approximately -2 V to -6 V with respect to the channel region (with the control gate 14 at 0 V). For memory cells 10 fabricated in accordance with the example embodiment, the coupling coefficient between a control gate 14/wordline 15 and a floating gate 13 is approximately 0.6. Therefore, a programming voltage VPP of 12 V, for example, on a selected wordline 15, including the selected control gate 14, places a voltage of approximately +7.2 V on the selected floating gate 13. The voltage difference between the floating gate 13 (at approx. +7.2 V) and the grounded (approx. 0 v) source line 17 is insufficient to cause a Fowler-Nordheim tunneling current across the gate oxide between source 11 and floating gate 13 to charge the floating gate 13 of a selected or deselected cell 10. The floating gate 13 of the selected cell 10 is charged with hot electrons injected during programming, and the electrons in turn render the source-drain path under the floating gate 13 of the selected cell 10 nonconductive with +5 V on its control gate 14, a state which is read as a "zero" bit. Non-programmed cells 10 have source-drain paths under the floating gate 13 that are conductive with +5 V on their control gates 14, and those cells 10 are read as "one" bits.
For convenience, a table of read, write and erase voltages is given in TABLE I below:
TABLE I______________________________________Connection\Operation Read Flash Erase Program______________________________________Selected Wordline +5 V 0 V (All) +12 VDeselected Wordlines 0 V -- 0 VSelected Drain Line +1 V Float (All) +5 V to +10 VDeselected Drain 0 V or Float -- FloatLinesSource Lines 0 V +10 V or +15 V 0 V______________________________________
The device of this invention is included in the on-chip part Read/Write/Erase control circuit 21 of FIG. 1. FIG. 2 illustrates, in block diagram form, the prior-art as described in U.S. Pat. No. 5,491,660. FIG. 3 illustrates, also in block diagram form, an embodiment of this invention. The circuit of FIG. 3 includes the following:
A) A Microprogram-Read-Only-Memory or Control-Read-Only-Memory CROM. In this example implementation, the microprogram memory CROM is only a 256×24 array including rows and columns of mask-programmable memory cells as compared to the 256×75 array described in the above-referenced U.S. Pat. No. 5,491,660. In the prior art illustration of FIG. 2, the width of the micro-instruction or microcode is fixed at seventy-five bits, which has the following general "fixed" format or syntax and which is similar to that described in U.S. Pat. No. 5,359,570:
ooopsssssaaaaaaaac . . . c
The seventy-five-bit microcode includes a three-bit opcode field (ooo), a one-bit test condition polarity select field (p), a five-bit field (sssss) for selecting one of thirty-two test inputs, an eight-bit next microcode-address field (aaaaaaaa), and a remaining fifty-eight bit field (c . . . c) for control of internal circuit operation of the flash EPROM of FIG. 1. Since the primary purpose of the microsequencer is simply to supply control signals to operate the flash EPROM, the other fields may be reduced to a minimum in order to decrease the number of codes or ROM bits, and thus chip area. However, due to the "fixed" syntax of the microcodes and the nature of the on-chip operations or algorithms, there are many wasted bits (bits not used for operation control) in the overall codes. In fact, about two-thirds of the program codes of the prior art are used for branching, testing and other controls internal to the microsequencer, leaving only one-third of the programs for actual control of the internal circuit operation of the flash EPROM. In addition, not all of the fifty-eight control bits (actually less than about one-third of the control bits) switch at the same time since all program, erase and compaction operations are completely independent of each other. For example, during programming, only signals for programming operation are switched, while signals for erasing or compaction remain unchanged. Therefore, only one-third of the output field is effectively used, while two-thirds is idle and therefore wasted.
Instead of the seventy-five bit microcode of the prior-art, this invention uses, for example, one of the following variable-syntax, twenty-four bit microcodes to reduce the number of unused ROM bits:
Type A: oooopsssssaaaaaaaaxxxxxx
Type B: oooocccccccccccccccccccc
While similar to the syntax used in the prior-art device, the Type A syntax has an extra bit (o) in the opcode field (oooo) to provide compatibility with that prior-art device. The extra bit is necessary for reasons explained later. The "don't care" bit field (xxxxxx) of the Type A syntax is used, for example, as either an optional expanded opcode or as control output signals. The Type B syntax also has a four-bit opcode field (oooo), but has a twenty-bit control output field (c . . . c). Based on the opcode in Type B syntax, a different set of control outputs is programmed for controlling the internal circuit operation of the flash EPROM. To be compatible with the prior-art device, three sets are sufficient. As mentioned previously, because the program, erase and compaction operations are completely independent of each other, the output signals controlling these operations may be sorted into three exclusive groups, each group assigned as one of the three sets defined by the opcode field. Again, since more micro-instructions are added in comparison to the previous invention, an extra bit for opcode field (oooo) is necessary. However, the overall ROM size is reduced by a factor of more than three.
B) A Microsequencer Circuit MC. In this example implementation, the Microsequencer Circuit MC including a Program Counter PC; an Adder ADD; a Program Counter Multiplexer PCM; a Micro-Instruction Decoder and Built-In-Logic-Block-Observation (BILBO) Control MID/BC; a Test Input Multiplexer TIM; a Subroutine Stack SS including a first Stack Multiplexer SMUX1, a first Stack Register SREG1, a second Stack Multiplexer SMUX0, and a second Stack Register SREG0; and an Status Output Register SOR.
The Program Counter PC is reset to zero at the start of each embedded control operation. The Program Counter PC contains the address of the currently addressed microcode word. The construction and operation of such program counters is well-known in this art.
The adder ADD adds the INDEX value generated from MID/BC to the current Program Counter PC value and, from it, generates the next microcode address. The INDEX value depends on the current opcode being decoded and few other external controls such as wait-timer time out status. For example, if the current state is to switch the output signals, then the next address is added by one. If the current state is to turn on the wait-timer and wait, then the next address is added by zero to stay at the current microcode address. As soon as the wait-timer has timed out, the next address is added by one to go to next microcode address. The construction and operation of such adder devices is well-known in this art.
The Program Counter Multiplexer PCM of this example is a three-to-one multiplexer. Under the control of the Micro-Instruction Decoder MID (described in the next paragraph) the Program Counter Multiplexer PCM selects either a field from the current microcode word, the current value of second stack register SREG0, or the incrementer INC as the address into the microprogram memory CROM.
The Micro-Instruction Decoder and BILBO Control MID/BS decodes the operation code field of the microcode word from the Test Input Multiplexer TIM and other inputs and controls the input state of Program Counter Multiplexer PCM, the first Stack Multiplexer SMUX1, the second Stack Multiplexer SMUX0, the Status Output Register SOR, the value added to the next microcode address in the adder ADD, and the BILBO. The RCLK signal used inside this block is only for synchronizing the control signal for the control output in the BILBO. The construction and operation of such decoders is well-known in this art.
The Test Input Multiplexer TIM selects one of n inputs (thirty-one inputs, for example) to test for condition branch instructions. The construction and operation of such multiplexers is well-known in this art.
The Subroutine Stack SS consists of first Stack Multiplexer SMUX1, first Stack Register SREG1, second Stack Multiplexer SMUX0 and second Stack Register SREG0. The Subroutine Stack SS allows nesting of subroutine calls two deep. The construction and operation of such multiplexers and stack, or shift, registers is well-known in this art.
The Status Output Register SOR is, for example, a twenty-bit register whose bits can be set or cleared (there were only thirteen bits in previous art due to a different syntax). The construction and operation of such registers is well-known in this art.
The inputs T1-Tn to the Test Input Multiplexer TIM are test condition inputs from other logic circuitry on the chip, the other logic circuitry being triggered by input from an off-chip microprocessor. The test condition inputs T1-Tn include a reset input, a programmable-timer time-out input, a programmable-counter end-of-count input, a row-address end-of-count input, a column-address end-of-count input, a sector/block end-of-count input, a high-array-source voltage detection input, a data-comparison approval input, a write-request input, a block-protection input, a low-power program-mode input, special-mode input, a checker-board program-mode input, a full-chip-mode-only input, a one-byte-mode-only mode input, a precondition-word-program mode input, a precondition-word-program-verify mode input, an erase-mode input, an erase-verify-mode input, a compaction-mode input, a compaction-verify-mode input, program-option-for-precondition mode input, a number of select-compaction-option mode inputs, a select-autocycle mode input, and a redundant-replacement input for the auto-cycle mode.
In the example circuit of FIG. 3 the outputs of the microprogram memory CROM are connected to special Built-In-Logic-Block-Observation BILBO registers that furnish clock signals and check to see that the information in the microprogram memory is correct. An example of such BILBO circuitry is described in U.S. patent application Ser. No. 08/315,526, filed Sep. 30, 1994, also assigned to Texas Instruments Incorporated. The outputs of the BILBO registers include, for example, outputs indicating activation or deactivation of the high-voltage circuitry on the chip, instruction of the address counter and decoder circuitry, and activation of the data comparison circuitry. Three additional separate sets of latches are used in the circuit of this invention as compared to the previous invention. However, the number of BILBO SRLs used in this invention is reduced to twenty-four from the seventy-five used in the prior art circuit. The three sets of latches are used primarily for the control signals for programming, erasing and compaction operations, respectively.
The outputs from Status Output Register SOR include, for example, outputs for microsequencer status (completed or not), for an overlay block, for program/erase failure, for stop clock oscillator, for select column, for increment sector counter, for timer override, for increment counter, for set-signature test mode, for override pulse timer by external clock, for force row-redundant match, for force column-redundant match, for select bit or byte correction, and for access to overlay block.
This invention is useful for any device that requires embedded control instructions for operation.
While this invention has been described with respect to an illustrative embodiment, this description is not intended to be construed in a limiting sense. In particular, this invention is applicable to use with power supplies having voltage outputs less than three-volt example used herein. Upon reference to this description, various modifications of the illustrative embodiment, as well as other embodiments of the invention, will be apparent to persons skilled in the art. It is contemplated that the appended claims will cover any such modifications or embodiments that fall within the scope of the invention.
|
The memory control this invention includes a microprogram-read-only-memory (CROM) containing micro-instructions for operation of an integrated-circuit memory, a program counter multiplexer (PCM) to select instructions from the control-read-only-memory, a micro-instruction decoder with BILBO control (MID/BC), a test input multiplexer (TIM) to test control signals, an optional status output register (SOR) to generate control signals, and a subroutine stack (SS) to allow function calls. A program counter (PC) takes an index signal from the micro-instruction decoder with BILBO control (MID/BC) and a signal from the program counter multiplexer (PCM), and from those signal, generates a next microcode address. Complex program, erase, and compaction instructions for the integrated-circuit memory are implemented using a relatively small number of control-read-only-memory locations and using a relatively small surface area on the memory chip. Control instructions are easily modified to compensate for process and structure enhancements are made during the production lifetime of an integrated-circuit memory.
| 6
|
This is a continuation-in-part of application Ser. No. 07/868,996 filed Apr. 15, 1992, now abandoned which is a continuation of application Ser. No. 07/672,672, filed Mar. 20, 1991, now abandoned.
FIELD OF THE INVENTION
The present invention relates to a process for generating sodium carbonate compounds and ammonium sulfate and more particularly, the present invention relates to a process for generating the above-mentioned compounds in a substantially pure form.
BACKGROUND OF THE INVENTION
There have been numerous processes previously proposed for the manufacture of alkaloid carbonate, various sulfates, etc. One of the primary difficulties with the known procedures for manufacturing, for example, sodium bicarbonate and ammonium sulfate is the fact that a pure product is difficult to obtain when one employs the methods previously set forth in the art.
Typical of the previously proposed methods includes that taught in Canadian Patent No. 543107, issued Jul. 2, 1957, to Downes. The reference teaches a method of separating polybasic acids from their aqueous solutions and the recovery of ammonium sulfate from aqueous solutions. The disclosure indicates that the treatment of sodium sulfate for the production of sodium bicarbonate and ammonium sulfate may be achieved by exposing the aqueous solution of sulfate to ammonia and carbon dioxide. The result is the precipitation of sodium bicarbonate. Although the Downes method is useful to recover the sodium bicarbonate, there is no teaching in the disclosure concerning how an uncontaminated product of sodium bicarbonate and ammonium sulfate, since these are reciprocal salt pairs capable of formation of a double salt by following the method. In addition, the method as set forth in this reference would appear to be susceptible to the formation of hydrates one being known as Glauber salt when using these salt pairs.
Stiers, in U.S. Pat. No. 3,493,329, issued Feb. 3, 1970, teaches a method of making sodium carbonate. The Stiers method is a co-precipitation method and cannot provide for selective precipitation of desired products since the salts are reciprocal salts and form a double salt. In the Stiers method, the desire is to remove the sulfate anion to use it for the transportation of sodium cations from sodium chloride to the bicarbonating process as sodium sulfate. In addition to the above, the Stiers process involves the continuous recycling of the mother liquor which requires that the ammonium sulfate in the liquor be continuously removed or reduced from the process stream. If the ammonium sulfate reaches a saturation point in the bicarbonating stage, ammonium sulfate will co-precipitate with the sodium sulfate in the form of a double salt compound or two inseparable salts.
Stiers demonstrates a process to generate two salts and double salts rather than a pure single salt, the latter being much more desirable from a commercial point of view.
In view of what has been Previously proposed in the art, it is clear a need exists for a process of recovering sodium carbonate compounds and the formation ammonium sulfate from a source of sulfate which overcomes the limitations regarding purity, precipitation, selectivity and other such limitations. The present invention is directed to circumventing the previously encountered difficulties of reciprocating salt pairs.
It is clear that there has been a long felt need for an effective process for preparing ammonium sulfate as a substantially uncontaminated product from reciprocating salt pairs.
SUMMARY OF THE INVENTION
One object of one embodiment of the present invention is to provide an improved process for the recovery of sodium bicarbonate and the formation of ammonium sulfate.
Another object of one embodiment of the present invention is to provide a process for generating an uncontaminated high purity ammonium sulfate compound.
A further object of one embodiment of the present invention is to provide a process for generating high quality, relatively pure sodium bicarbonate suitable for commercial purposes.
A still further object of one embodiment of the present invention is a method of recovering sodium bicarbonate and forming ammonium sulfate from a source containing sodium sulfate, comprising the steps of:
(a) providing a source of sodium sulfate in solution;
(b) contacting said sodium sulfate solution with carbon dioxide and a compound containing ammonia;
(c) maintaining said solution temperature of at least 32° C. to form a single precipitate of sodium bicarbonate in said solution;
(d) removing said sodium bicarbonate precipitate from said solution;
(e) forming a saturated solution of ammonium sulfate at a temperature of at least 32° C.; and
(f) precipitating ammonium sulfate.
By practising the above-mentioned method, it has been found that selective precipitation of single salts is possible and that the selected precipitate can be precipitated with a high degree of purity.
Advantageously, the use of solubility data for sodium bicarbonate, ammonium sulfate and sodium sulfate provides the necessary information for effecting selective precipitation without the contamination of one precipitate effecting a further precipitate as was conventional with the prior art processes. By making use of a solubility data, it is possible to precipitate sodium bicarbonate without precipitating sodium sulfate as a contaminant.
By controlling temperatures and pressures, once a bicarbonate precipitate is formed, the filtrate may be subjected to a purification step wherein the remaining sodium ions are substantially removed or made to be held in solution prior to the precipitation of ammonium sulfate. This results in a cleaner precipitate of ammonium sulfate and therefore results in a more commercially desirable product, which product exceeds purity measures not previously encountered with the prior art processes. In a purification possibility, the filtrate may be supersaturated with ammonia in a conditioning reactor which operates at a substantially cooler temperature, for example, 7° C. This is one example of an appropriate temperature, a suitable range is between about 20° C. to about -40° C. This procedure results in the formation of a mixed salt of ammonium sulfate and sodium sulfate, both of which are insoluble at this temperature and this excess of ammonia. Once precipitated, the filtrate, therefore having a lower concentration of sodium cations inherently leads to a less contaminated precipitated ammonium sulfate.
According to a further object of the present invention, there is provided a method of recovering sodium bicarbonate and forming ammonium sulfate from a source containing sodium sulfate, comprising the steps of:
(a) providing a source of sodium sulfate;
(b) contacting said sodium sulfate solution with carbon dioxide gas and an ammonia gas;
(c) maintaining said solution temperature of at least 32° C. to form a single precipitate of sodium bicarbonate in said solution;
(d) removing said sodium bicarbonate precipitate from said solution;
(e) forming a saturated solution of ammonium sulfate at a temperature of at least 32° C.; and
(f) precipitating ammonium sulfate.
Desirable results have been obtained when the conditioning step increases the ammonium concentration from about 10% to about 50%. The mixed salt precipitate, double salt or pure sodium sulfate may be recycled back into the original feed stream with the source of sodium sulfate.
It has been found that by making use of the basic bicarbonate recovery process, that the process can be augmented for additional fields of utility, for example, tail gas desulfurization. This has been broadly indicated hereinabove with respect to the desulfurization of the acid gas stream.
According to a further object of the present invention, there is provided a method of desulfurizing a sulfur containing gas stream comprising:
(a) exposing said stream to oxidizing conditions to generate a sulfur containing compound;
(b) contacting said sulfur containing compound with a sodium carbonate compound to generate an intermediate sulfur containing product; and
(c) processing the intermediate sulfur containing product according to the method of claim 1.
It is well known to those skilled in the art that the Claus process is an effective process for recovering elemental sulfur from hydrogen sulfide (H 2 S).
Flue gas desulfurization (FGD), an example of which employs dry sorbent is generally known in the art. This employs the use of sodium bicarbonate typically for 10% to 90% sulfur component reduction. The bicarbonate is initially calcined by the flue gas heat, which is typically in the range of 350° F. to 750° F., to sodium carbonate. This then reacts to form sodium sulfate. Because the sorbent is dry, finely ground powder, there is no negligible cooling effect with the flue gas and as such, the stack temperature can be maintained for emission dispersion. Also, the sodium sulfate may be recovered in a baghouse or an electrostatic precipitator with or without the flyash. The sorbent must be processed to a fine particle size, typically 15 μm and then must be stored under dry conditions to prevent holdup and enhance manageability of the dried sorbent in silos and other equipment.
This is acceptable for new plants or existing plants with electrostatic precipitators, baghouses, or other recovery means, but many flue gas desulfurization (FGD) systems currently operating are wet scrubbing systems usually using lime as a reagent to reduce sulfur dioxide emissions. One of the primary difficulties is that these systems tend to be expensive and are plagued with operational difficulties such as corrosion, and disposal problems of products, etc.
A further embodiment of the present invention is directed to a process which can utilize a wet scrubbing system and eliminate the corrosion problems, landfill problems and other handling difficulties associated with lime.
The method may employ either bicarbonate or carbonate or a mix thereof. As a further advantage, the process according to the present invention eliminates the drying and sizing step previously encountered in prior art methods.
Furtherstill, utility has been found in application of the overall procedure in making gypsum, for example, of a commercial or landfill grade. By adding lime into the saturated solution of ammonium sulfate, gypsum can be removed as a precipitate.
A further object of the present invention is to provide a method of scrubbing sulfur compounds from flue gas comprising the steps of:
(a) a hydrated sodium sulfate solution;
(b) contacting said solution with carbon dioxide and ammonium to precipitate sodium bicarbonate;
(c) maintaining the temperature of the solution at a temperature of at least 32° C. to form a single precipitate of sodium bicarbonate;
(d) removing precipitated sodium bicarbonate;
(e) washing residual sodium sulfate out of said precipitated sodium bicarbonate;
(f) dehydrating said sodium bicarbonate;
(g) rehydrating the precipitated sodium bicarbonate to form a concentrated solution; and
(h) introducing into a conditioning vessel said solution for the removal of a sulfur oxide compound.
The contacting vessel may comprise any vessel suitable for the treatment of the gas. Examples which are well known include wet scrubbers and spray dryers. It will be appreciated that the conditioning vessel may comprise at least one of each of the above or a combination of many of these.
As will be appreciated by those skilled in the art, the precipitation of the above-mentioned precipitates involves exothermic reactions and accordingly, the heat generated may be recovered for further temperature regulation in the process. Further, the refrigeration effect nature of carbon dioxide gas and ammonia under pressure reduction is useful for temperature adjustment and regulation in the process, both directly in the process or indirectly by external means.
Having thus generally described the invention, reference will now be made to the accompanied drawings illustrating preferred embodiments.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graphical representation of the solubility of sodium bicarbonate, ammonium sulfate and sodium sulfate expressed as a function of solution temperature;
FIG. 2 is a flow chart illustrating one possible process route for effecting the method according to the present invention;
FIG. 3 is an alternate embodiment of FIG. 2;
FIG. 4 is an alternate embodiment of FIG. 2;
FIG. 5 is a further alternate embodiment of the process as set forth in FIG. 2;
FIG. 6 is a still further alternate embodiment of the process of FIG. 2;
FIG. 7 is a further alternate embodiment of the process as set forth in FIG. 6;
FIG. 8 is a further alternate embodiment of the process where gypsum is produced; and
FIG. 9 is yet another embodiment of the process according to the present invention illustrating a scrubbing process.
Similar numerals in the drawings denote similar elements.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The chemistry involved according to the present invention can be resolved into the following equations:
CO.sub.2 +H.sub.2 O=H+HCO.sub.3
NH.sub.3 +H.sub.2 O=NH.sub.4 +0H
Na.sub.2 SO.sub.4 +2NH.sub.3 +2H.sub.2 O+2CO.sub.2 =2NaHCO.sub.3 +(NH.sub.4).sub.2 SO.sub.4
Referring now to FIG. 1, shown is a graphical representation of the solubility curves for sodium bicarbonate, ammonium sulfate and sodium sulfate. The data are expressed as a function of solution temperature. As is evident from the drawing, the solubility of the bicarbonate and the sodium sulfate have an overlapping area in which there will be a precipitation of both of these compounds. As indicated herein previously, this has posed a significant amount of difficulty in the prior art when one was to obtain a substantially pure precipitate of sodium bicarbonate without the formation of a sodium sulfate precipitate.
It has been found that if one simply obeys the solubility data, sodium bicarbonate and ammonium sulfate can be precipitated from a solution containing the molecular species indicated herein above without contamination of one precipitate with the other and further without the precipitation of the sodium sulfate as an intermediate precipitate.
It has been found that if the sodium bicarbonate is maintained at a temperature of at least 32° C., under the conditions as set forth with respect to the data in FIG. 1, that the sodium bicarbonate can be precipitated while the unreacted sodium sulfate remains in solution. If the temperature drops prior to the precipitation of the sodium bicarbonate, the result is that a precipitate of sodium sulfate solvate or decahydrate will plate out of solution offering tremendous operating difficulties.
In a chemical system as set forth with respect to the above equations, the system is generally a complex quateranary system, having a receiprocal salt pair relationship as follows:
2(NH.sub.4)HCO.sub.3 +Na.sub.2 SO.sub.4 =2NaHCO.sub.3 +(NH.sub.4).sub.2 SO.sub.4
In aqueous solutions above approximately 30° C. (100° F.) ammonium bicarbonate is unstable and dissociates in solution as ions. This reduces the system to a complex tertiary system with complications related to hydrate formation and double salt formation. The system and phase equilibria can be represented on an isothermal diagram which can be employed to obtain higher purity levels of single components.
The first step in the process is to complete the reaction to drive the equilibrium in the final equation such that the saturated sodium sulfate brine solution reacts to produce substantially pure sodium bicarbonate crystals. As is known in the art, numerous possible methods can be practised for contacting the ammonia and the carbon dioxide with the sodium sulfate. As an example, the ammonia may be introduced into a solution of the sodium sulfate and carbon dioxide dispersed through the solution or the carbon dioxide may be dispersed through the saturated sodium sulfate solution and the ammonia subsequently added or both components may be dispersed through the solution simultaneously. Another possible alternative includes the use of ammonium carbonate.
Referring now to FIG. 2, shown is one possible process route according to the present invention. A source of sodium sulfate, such as flyash, for example, from commercial steam boilers containing various levels of sodium sulfate may be collected from hot flue gas streams and transferred into a collection silo, globally denoted by numeral 10 in the drawings. From the silo, the flyash may be transferred at a controlled rate into an atmospheric mixing container 12, which container is maintained at a temperature from between about 32° C. and 42° C. The light and heavy insolubles are removed in a slurry form from the mixing container 12 at 14. The brine or filtrate is then transferred to a clarifier 16 and further filtered if necessary to polish the solution free of fine insolubles. Fine insolubles are removed from the clarifier at 18.
It has been found that one of the main difficulties which previously plagued methods practised in the prior art, was that the temperature of the sodium bicarbonate formation reaction was not maintained within the above-mentioned parameters. The result of this is the formation of a hydrate commonly referred to as Glauber salt (Na 2 SO 4 .10H 2 O). Another difficulty which previously plagued methods practises in prior art, was the formation of ammonium bicarbonate. It has been found that by maintaining the temperature within the above-stated range, the Glauber salt and ammonium bicarbonate does not form and therefore, does not affect the sodium bicarbonate formation process. In addition, at this temperature, a maximum amount of salt can be put in solution and thereby reduces the feed circulation rate.
Once the insolubles have been removed by the clarifier 16, the solution or brine which contains a small percentage of ammonia is passed into a first main reactor 20 where the formation of the sodium bicarbonate occurs. The temperature within the reactor may vary depending on the reactor configuration. The final temperature of the solution will be progressively reduced to from about 18° C. to about 21° C. with the brine feed temperature to the reactor being maintained above 32° C. The final temperature of this solution maximizes bicarbonate yield. This parameter prevents contamination with Na 2 SO 4 . Any suitable solvent may be employed and it will be apparent to those skilled in the art which are suitable possibilities to cover all pressure, temperature and other operating conditions. Pressure in reactor 20 will preferably be maintained at approximately 50 to almost 250 psig. This ensures the ammonia remains dissolved in solution to effect the reaction. A crystallizer may be included downstream to effect crystallization of the sodium bicarbonate. Once the crystals have formed, they may be removed from the reactor through a filter means 22 which may comprise a pressure or nonpressure-type filter. Once the crystals are removed, they may be passed to a further filtration medium, an example of which may be a filtration screen 24, at which point the formed crystals may be washed with saturated cold sodium bicarbonate brine or methanol. A high yield is achievable. The wash may be then returned via line 26 to the mixing container 12. The formed bicarbonate crystals may be then removed from the system via line 28 for further uses.
The filtrate or brine from the first reactor is reheated back to approximately 32° C. and the addition of water consumed by the bicarbonate reaction may be added to the solution to maintain a process material balance. The water may be added by a source thereof. The solution is maintained at a temperature of at least 32° C. and then passed into reactor 32. Once in reactor 32, the brine solution is subjected with excess ammonium at a concentration of approximately 20 weight percent.
The pressure in the reactor is carefully controlled by varying the injection of ammonia (approximately 70 psig) thereby controlling the desired concentration of excess ammonium. In reactor 32, the injection of the solution with ammonia shifts the equilibrium solubility of the solution of the reaction, denoted hereinabove, to favour the formation of ammonium sulfate precipitate. The temperature in the reactor is maintained at 32° C. to keep free sodium cations soluble and therefore to prevent contamination of the ammonium sulfate with undesirable solvates. When desired, the ammonia concentration can be altered by changing the pressure control. Similar to the description for reactor 20, reactor 32 may include a crystallizer downstream to effect the formation of ammonium sulfate crystals. Once formed, the crystals may be passed onto a pressure filter medium 34 and washed with saturated cold ammonium sulfate brine wash. The so-formed ammonium sulfate crystals can then be removed by line 36 for further uses. The wash solution may be returned to the mixing container 12 via line 38 for further uses. The ammonia containing filtrate remaining after the precipitation of the ammonium sulfate crystals, may be flashed off, compressed and condensed and collected in to a surge drum 40 as is known in the art. Once collected, the ammonia solution may be used for reinjection in the system.
The final recovered solution, containing soluble levels of ammonia can be recycled to the mixing container 12 to complete the continuous operation.
By practising the above method, a purity of ammonium sulfate greater than 50% by weight is achievable.
Advantageously, the ammonia can be substantially recovered for reuse which has positive economic advantages for the entire process.
FIG. 3 shows a further variation on the process according to FIG. 2. In FIG. 3, the brine conditioning step is employed between reactors 20 and 32. The brine conditioning step is effective to purify the feed stream for introduction into reactor 32 for eventual formation of ammonium sulfate by the further reduction of sodium ion concentration from the feed stream entering into reactor 32.
Once the sodium bicarbonate reaction has been completed, the bicarbonate precipitate is removed as set forth herein with respect to FIG. 3, and the brine is transferred to intermediate reactor 42. In reactor 42, the concentration of the ammonia is increased to saturate the solution while the temperature of the reactor is lowered to approximately 7° C. This results in the formation of a precipitate comprising either pure sodium sulfate, or a mixed precipitate of sodium sulfate and ammonium sulfate. These precipitates are then filtered by filter 44 and the crystals eventually passed back into contact with mixing container 12. The filtrate is then fed to reactor 32, maintained under at least the same pressure conditions as indicated for FIG. 3. Once in reactor 20, the filtrate undergoes the reaction as indicated herein above, the result is the formation of ammonium sulfate precipitate, however, the precipitate is formed in an environment where the sodium cation concentration is significantly reduced in view of the intermediate process using intermediate reactor 42. The result of the process is a solution concentration of a ammonium sulfate which will effect a precipitate of a concentration greater than 73% by weight.
Referring now to FIG. 4, shown is a further alternate arrangement by which the process may be practised. In FIG. 4, the overall process may include a separate washing step for washing the sodium bicarbonate and ammonium sulfate precipitates separately. In one possible configuration, the sodium bicarbonate which is formed in reactor 20, may be passed into contact with a washing material, an example of which may be a source of methanol 50. The resulting filtrate may then be returned to mixing container 12 via line 52.
Similarly, the ammonium sulfate crystals formed in reactor 42, may be passed through a second independent source of methanol 54 with the filtrate being returned to mixing container by line 56. The ammonium sulfate crystals and bicarbonate can then be used for further uses.
Although the process as discussed herein has been indicated to be primarily conducted in water, it will be understood by those skilled in the art that any suitable solvent can be used provided the choice of solvent does not vary the solubility relationship necessary to effect the process. As one possible alternative, glycol may be employed as the solvent.
Referring now to FIG. 5, shown is a further variation on the schematic process shown in FIG. 1. In the process shown in FIG. 5, the filtrate recovered from the sodium bicarbonate reaction can be made to be a commercially substantially pure liquid product, e.g. a fertilizer in the near saturated state. This affords the user the opportunity of blending the liquid product with other fertilizer components and further permits crystallization of the product in the desired form. As is illustrated in FIG. 5, the liquid product may be passed from reactor 20 to the brine conditioning container 42 where the temperature of the ammonia is reduced to approximately 7° C. as set forth herein previously with respect to FIG. 3. In this embodiment, the ammonia concentration is increased from about 10% to about 50% or greater by weight to therefore provide a supersaturated solution. The result is the precipitation of contaminated sodium sulfate or mixed salts of ammonium and sodium sulfate. The filtrate in this situation is substantially saturated liquid ammonium sulfate which can then be passed on to a storage unit 63. As a further alternative, a user may simply pick up the liquid ammonium sulfate or alternatively, the ammonium sulfate may be pumped into a conventional evaporator (crystallizer) 65 which would afford the user the opportunity to mix the liquid with additional fertilizer components etc. and have the final product crystallized.
The brine conditioning can be performed in a single step or it may be conditioned in multiple steps to achieve increased removal of sodium cations; this inherently leads to increased purity of the ammonium sulfate fertilizer. The above-mentioned steps can be any combination of known (salting out) steps i.e. evaporation, addition of excess ammonia, etc.
FIG. 6 shows a variation on the process where the bicarbonate recovery systems as set forth herein previously can be combined to be useful in a sulfur recovery plant. Generally speaking, the area designated by numeral 70 in FIG. 6 illustrates conventional apparatus employed for sulfur recovery from an acid gas stream by employing the modified Claus reaction, consisting of a single or multiple variation of thermal and catalytic recovery steps.
It is well known to those skilled in the art that the Claus process is useful for desulfurization. Generally speaking, the process is effected in two steps, namely: ##EQU1## This generally results in a sulfur recovery of approximately 90% to 96% in a liquid sulfur state. The remaining sulfur containing component is recovered in sulfur recovery techniques such as Tail Gas units. By employing the recovery process as set forth herein previously, sodium bicarbonate can be introduced into the tail gas stream containing residual sulfur compounds and results can therefore be the production of ammonium sulfate as indicated in FIG. 6. As is illustrated in FIG. 6, the overall modified Claus process, denoted by numeral 70 can be combined with the overall process for producing ammonium sulfate, the group of steps of which is generally indicated by numeral 115 in the figure. The broad steps as illustrated in the figure are generally common steps to those shown in FIGS. 2 and 3. By combining the modified Claus process with the processes as set forth herein, the result is sulfur removal of the order of at least 95% or greater.
Turning to FIG. 7, shown is a variant on the process schematically illustrated in FIG. 6, but for a lower volume production sulfur plant, typically having production levels of less than 10 MTD where economic constraints preclude the system shown in FIG. 6. The steps for the process are similar to those for FIG. 6 and the treatment of the sulfur compound is generally denoted by the sequence of events as indicated by numeral 115.
The acid gas stream may be as an alternative directly treated with liquid sodium bicarbonate or carbonate solution for desulfurization and form an alternate sulfur product.
Turning to FIG. 8, showing schematically is a further embodiment according to the present invention. The embodiment shown, a lime mixing container 60 is provided for retaining lime in any form, e.g. a slurry or powder form to be introduced into reactor 32 via line 62. By providing this addition to the recovery unit, commercial or landfill gypsum can be produced along with sodium bicarbonate as illustrated in the flow chart in FIG. 8. As a further feature, the arrangement shown may include ammonia recovery unit 64 which will include the usual gaseous recovery means well known to those skilled in the art. This is useful since the ammonia is liberated subsequent to precipitation of gypsum and therefor can be easily recovered.
Turning to FIG. 9, shown is a further variation on the overall process according to the present invention. In FIG. 9, a flue gas desulfurization (FGD) process using a wet scrubbing system for desulfurization, employs sodium carbonate or bicarbonate as the active reagent. This is schematically illustrated in flow chart form.
In the embodiment illustrated, flue gas from the industrial boiler or tail gas unit, globally denoted by numeral 90, is passed onto an electrostatic precipitator or baghouse 92 or other recovery device to remove flyash at 93. A water wash container 94 is provided to circulate wash water in the upper section of the scrubber and accumulated levels of precipitates and fluids are drawn off from container 94 and passed to the lower section of the scrubber 95. Once sodium sulfate is collected from the bottom of scrubber 95 as a product of the scrubbing procedure, it is then further transferred to mixing container 12 for thickening and clarification to a saturated state for feeding into reactor 20. From reactor 20, sodium bicarbonate is filtered from the solution and washed in either open screen, pressure type, vacuum type, centrifuge or cyclone type filters or any combination of these (generally shown at 97). The bicarbonate precipitate is washed and reduced to less than 10% liquid and then fed as a slurry into a bicarbonate slurry container 96 at approximately 100 psig. At this point, the bicarbonate slurry in container 96 is mixed with clean boiler feed water supplied to container 96 from a feed water supply container 98. The feed water is maintained at a temperature of approximately 120° F. (48° C.). The slurry is continually mixed and ranges in a concentration of between about 20% by weight to about 40% by weight. The slurry is then transferred to a high pressure solution container 100 at a pressure of approximately 150 psig, where a saturated solution is formed. A saturated bicarbonate solution is created using additional boiler feed water from container 98 which is heated to approximately 350° F. (176° C.) by an injection water heater 102. The final saturated concentrated solution is then injected into wet scrubber 95 for sulfur dioxide removal.
It will be appreciated by those skilled in the art, that sodium carbonate can be used as a replacement to sodium bicarbonate. The conversion can easily be accomplished by calcining the bicarbonate in a dry form or by increasing the temperature in a liquid form. The ammonia used in the process can be recovered in a recovery process as set forth herein with respect to other embodiments and this is equally true of the ammonium sulfate and other compounds in the process.
The temperature, pressure and concentration of reagent in the final injection solution can be varied to control the level of SO 2 removed and the final flue gas temperature exiting the wet scrubbing process. As a further example, the temperature and pressure can be reduced to near atmospheric conditions prevalent in the scrubber. The temperature can be reduced to 120° F. to eliminate water heater 102 and the high pressure reactor 100. This will result in a cooler final flue gas temperature resulting from the evaporative cooling effect which may or may not be detrimental to any specific application.
In addition, it will be appreciated by those skilled in the art, that the wet scrubber 95 can take any form of contacting the reactant solution with the sulfur containing fluid gas, for example spray driers, etc.
It will be readily appreciated by those skilled that the solubility shift discussed herein can be effected by regular evaportion, or by the addition of any suitable compound which provides a salting out effect without effecting the chemical composition of the desired product salts.
As a consequence of reactor vessel size, temperature stratification may exist within the reactors as set forth herein or the crystallizing vessels to enhance the crystal growth, stability and yield. In order to avoid undesirable effects caused by hydrate or solvate precipitation, the process can be performed in multiple vessels to circumvent these difficulties.
Although embodiments of the invention have been described above, it is not limited thereto and it will be apparent to those skilled in the art that numerous modifications form part of the present invention insofar as they do not depart from the spirit, nature and scope of the claimed and described invention.
|
There is disclosed a process for recovering sodium bicarbonate and forming ammonium sulfate from a source containing sodium sulfate. The method involves contacting the sodium sulfate in solution with carbon dioxide and a compound containing ammonia. Sodium bicarbonate is precipitated in high purity from the solution. It is important to maintain the temperature of the source solution at or above 32° C. This provision eliminates contamination of hydrates or ammonium bicarbonate components. The filtrate of the sodium bicarbonate reaction can be further processed to yield an ammonium sulfate product in the concentrated liquid or precipitated form in high purity. The basic process can be expanded to be combined with a conventional Claus process for sulphur recovery as a Tail Gas Unit, combined with lime injection to result in gypsum precipitation or can be further employed in a wet scrubbing process for FGD schemes.
| 8
|
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to U.S. Provisional Application No. 61/883,618, filed Sep. 27, 2013, which is hereby incorporated by reference in its entirety.
FIELD
[0002] This disclosure relates to compositions that selectively disintegrate in media of different ionic strengths.
BACKGROUND
[0003] There are multiple conditions where protection of a material or surface in high ionic strength systems would be advantageous. For example, within the home care market, brand owners have moved to more concentrated delivery systems, such as high efficiency concentrated laundry detergents and unit dose products. In these cases, the products as sold are significantly higher in ionic strength than during use. Another area in which a composition is exposed to high ionic strength media is in marine coatings. Thus, there is a need for compositions that do not dissolve in high ionic strength media.
BRIEF SUMMARY
[0004] In one aspect, a composition is provided, comprising an ethylene (meth)acrylic acid copolymer, wherein at least a portion of the carboxylic acid groups in the (meth)acrylic acid component are neutralized and an anti-fouling agent.
[0005] In another aspect, a film composition is provided, comprising an ethylene (meth)acrylic acid copolymer and an anti-fouling agent, wherein at least a portion of the carboxylic acid groups in the (meth)acrylic acid component are neutralized, and wherein the ratio of the ethylene component to the (meth)acrylic acid component is about between about 50:50 to 90:10.
[0006] In yet another aspect, a coated article is provided, comprising an article, a coating composition comprising an ethylene (meth)acrylic acid copolymer, wherein at least a portion of the carboxylic acid groups in the (meth)acrylic acid component are neutralized and an anti-fouling agent. The coating composition does not disintegrate in a high ionic strength media, and disintegrates in a low ionic strength media.
DETAILED DESCRIPTION
[0007] The present disclosure relates to a chemical composition of an ethylene (meth)acrylic acid copolymer. As used herein, the term “composition” may mean, for example, a mixture, solution, or dispersion. “(Meth)acrylic,” as used herein, means acrylic, methacrylic, or mixtures thereof Ethylene (meth)acrylic acid (EAA) copolymers can be used in a wide variety of applications including high-performance adhesives, flexible packaging films, pouches, and extrusion coating and extrusion lamination applications. The free acid form of ethylene (meth)acrylic acid copolymers can be neutralized to the desired degree with a suitable base. Ethylene (meth)acrylic acid copolymers can be obtained with varying water dispersibility depending on the degree of neutralization. For example, complete water dispersibility, or under certain conditions, complete water solubility, is obtained when the (meth)acrylic acid moiety is completely neutralized with a stoichiometric amount of base whereas partially neutralized EAA copolymers can be water dispersible, water sensitive, or water insensitive depending on the application for which it is aimed.
[0008] The copolymer may be used in various compositions, for example, liquid compositions or film compositions. Such a film could also be physically reduced in size via grinding or other means to provide an encapsulated active ingredient with higher surface area. Similarly sized particles can also be produced from a liquid composition by methods known in the art, such as spray-drying and lyophilization. The composition may comprise a copolymer composition or may comprise a composition and one or more additional materials to provide application specific physical properties (tensile strength, durability, adhesion, etc.). The additional materials may include crosslinking agents, plasticizer agents, disintegrating agents, and/or surfactants.
[0009] The crosslinking agent may include, for example, Ca 2+ , Mg 2+ , Al 3+ or Zn 2+ . In addition to the crosslinking agent, the composition may include at least one additional additive, such as a plasticizing agent, a disintegrating agent, and/or a surfactant, The plasticizing agent may be a hydrophobic plasticizer, a hydrophilic plasticizer, or a combination thereof. For example, the plasticizing agent may be benzyl alcohol, UCON® LB-65 (a polyalkylene glycol (PAG)-based synthetic water insoluble lubricant) T-BEP (tris(butoxyethyl) phosphate, an alkyl phosphate film forming aid and plasticizer), among others. The disintegrating agent may be, for example, acrylic acid, PVOH, a starch, cellulose, or a second co-polymer. The surfactant may be, for example, an anionic surfactant, a non-ionic surfactant, an amphoteric surfactant, or mixtures thereof. Examples of anionic surfactants include those known in the art, such as DOWFAX® 2A1 (alkyldiphenyloxide disulfonate), ammonium lauryl sulfate, sodium lauryl sulfate, sodium laureth sulfate. Examples of non-ionic surfactants include those known in the art, such as polyoxyethylene glycol alkyl ethers, polyoxypropylene glycol alkyl ethers, glucoside alkyl ethers, polyoxyethylene glycol octylphenol ethers, polyoxyethylene glycol alkylphenol ethers, glycerol alkyl esters, polyoxyethylene glycol sorbitan alkyl esters, and sorbitan alkyl esters. Examples of amphoteric surfactants include those known in the art, such as Ammonyx® LO (lauramine oxide).
[0010] This composition does not disintegrate in a variety of media in which the ionic strength is very high caustic, household bleach, seawater, synthetic seawater). The term “disintegrate,” as used herein, means dissolve, disperse, or to be soluble. The media may be in the form of for example, a solution, a slurry, a dispersion, or a paste. The media may also be substantially free of substantial amounts of inorganic salts, but the media may include organic amine salts to provide the required ionic strength and alkalinity, Examples of such organic amine salts include mono-, di-, or -substituted alkylamine salts of carboxylic acid and fatty acid esters. High ionic strength media is media with a salt content of greater than about 3 percent, more preferably greater than about 7 percent. Upon exposure to low ionic strength aqueous media (e.g., deionized water, standard tap water, the wash liquid of a laundry machine) the e will break up within minutes, becoming dispersed within the low ionic strength media with gentle agitation. Low ionic strength media is media with a salt content of about 0 to about 2 percent (e.g., tap water, dionized water).
[0011] In marine applications, such as on boats or ships, the salinity of seawater provides the ionic strength required to prevent dissolution or disintegration of the composition, thus, the composition can be used as the basis of a coating, which once applied, can be removed after use via fresh water, i.e., low ionic strength, washing. In addition, the composition may be formulated in such a way that it contains an additive capable of acting as an anti-fouling agent,
[0012] Biofouling or biological fouling is the accumulation of microorganisms, plants, algae, or animals on wetted surfaces. Anti-fouling is the process of removing or preventing these accumulations. Examples of anti-fouling agents include, but are not limited to, biocides such as organotin compounds (e.g., the tributylitin moiety (TBT)) and copper compounds (e.g., copper oxide) and coatings based on organic polymers. Coatings based on organic polymers may be hydrophobic, such as those based on fluoropolymers and silicone, or hydrophilic, such as those based on highly hydrated zwitterions (e.g., glycine betaine and sulfobetaine).
[0013] The present composition could be used in any application where it is desirable to prevent growth or fouling, such as in water towers, on docks, on metal dam components, on oil rigs, and on ship hulls.
[0014] In particular embodiments, the composition may comprise an ethylene (meth)acrylic acid copolymer and an anti-fouling agent. At least a portion of the carboxylic acid groups in the (meth)acrylic acid component are neutralized with a base, resulting in a salt. For example, the carboxylic acid groups may be neutralized with a sodium cation to fort sodium salt. In another embodiment, the carboxylic acid groups may be neutralized with a potassium cation to form a potassium salt. The degree of neutralization may be between about 70 percent and about 100 percent, preferably between about 90 percent and about 100 percent, and more preferably between about 98 percent and about 100 percent. In other embodiments, the degree of neutralization may be between about 70 percent and about 95 percent, preferably between about 85 percent and about 95 percent, more preferably between about 90 percent and about 95 percent. A portion or all of the remaining (meth)acrylic acid may be ionically crosslinked. Increasing the degree of neutralization increases the dispersibility of the composition in low ionic strength media. Those skilled in the art recognize appropriate methods for determining degrees of neutralization. See, e.g., U.S. Pat. No. 3,472,825.
[0015] The composition may also comprise water, such that it forms a liquid composition, which may be applied to an article or may be dried to create, for example, a film or particles. In sonic embodiments, the composition may comprise about 60 to about 80 weight percent water. The ethylene (meth)acrylic acid copolymer may be present in a dispersion, which may be formed any number of methods known to those of skill in the art. The weight ratio of the ethylene to (meth)acrylic acid in the copolymer may be between about 50:50 and about 90:10, preferably between about 70:30 and about 90:10, and more preferably between about 75:25 and about 80:20.
[0016] The composition may be used to produce a coated article, for example, a coated ship, dock, or dam. The coated article may comprise the article, the composition comprising an ethylene (meth)acrylic acid copolymer, and the anti-fouling agent.
[0017] Also disclosed are methods of preventing growth or fouling. In such methods, the present composition is applied to an article and prevents the accumulation of microorganisms, plants, algae, or animals on the surface of the article.
EXAMPLES
Example 1
[0018] The functionalized polyolefin composition used for this example is a mixture of ethylene (meth)acrylic acid (80 weight percent ethylene and 20 weight percent (meth)acrylic acid) neutralized with potassium hydroxide. The degree of neutralization is 92 percent. The composition be prepared using procedures known in the art. See, e.g., U.S. Patent Application No. 2011/0319521; PCT Published Application No. WO2011034883; and PCT Published Application No. WO2012082624. The composition has a pH of 10 and a Brookfield viscosity of 500 (Brookfield RVT, #2 spindle, 20 RPM, 25° C.). and is hereinafter referred to as EAA-K.
[0019] To the composition of EAA-K (6.6 g, 23% active), 1.3 g of a suspension of copper oxide (46% in water) is added. The material is agitated via manual shaking of the vial to fully suspend the copper particles in the composition. A film is solution cast on glass using a 203 μm (8 mils) draw down bar, followed by drying in a 40 degrees Celsius oven for 1 hour. The film is removed from the glass and shown to be a freestanding film. Five samples of the film (approximately 2 cm×2 cm) are submerged in room temperature deionized water, tap water, synthetic seawater, saturated NaCl solution, and saturated KCl solution, respectively. The vial is inverted in order to achieve agitation.
[0020] In the high ionic strength systems (synthetic seawater, saturated NaCl solution, and saturated KCl solution) the films appear to remain intact, and no color change to the supernatant is observed. This suggests a low level of leaching of film components into the water during the experiment. In the low ionic strength media (deionized water and tap water), the films break apart within five minutes, and the supernatant is observed to have turned brown after allowing the solids to settle, This suggests high levels of leaching of the film during the experiment.
[0021] While the invention has been described above according to its preferred embodiments, it can be modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the invention using the general principles disclosed herein. Further, the application is intended to cover such departures from the present disclosure as come within the known or customary practice in the arm to which this invention pertains and which fall within the limits of the following claims.
|
A composition comprising an ethylene (meth)acrylic acid copolymer and an anti-fouling agent is provided. The composition selectively disintegrates in media of different ionic strengths. Also provided is a method of preventing fouling using the composition.
| 2
|
[0001] The present application claims priority from Korean Patent Application No. 10-2008-0097375 filed on Oct. 2, 2008, the entire subject matter of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Technical Field
[0003] The present invention generally relates to piezoelectric energy harvesters, and more particularly to a piezoelectric energy harvester having a high efficiency for energy transformation and a low natural frequency.
[0004] 2. Background Art
[0005] Piezoelectric energy harvesting is a process used to derive energy from ambient vibrations using piezoelectric materials. The ambient vibrations may be generated by a train, a vacuum pump, a mechanical motor, a car engine, a human's motion and so forth.
[0006] Recently, a ubiquitous sensor network has been researched and developed for improving the quality of human life. In order to build a ubiquitous sensor network, it is necessary to install a plurality of sensors on a large area. However the cost is high to connect an electric wire in each sensor for supplying power, charging a battery and recharging the battery. The piezoelectric energy harvesting technique, which can drive the sensors independently by using ambient energy, is certainly necessary to fabricate the ubiquitous sensor network. This is especially true since piezoelectric energy harvesting using vibration energy is time-independent and location-independent, and has a high efficiency for energy transformation.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 is schematic diagram showing a cantilever type piezoelectric energy harvester.
[0008] FIG. 2 is a schematic diagram showing an illustrative embodiment of a circular spiral spring type piezoelectric energy harvester.
[0009] FIG. 3 is a schematic diagram showing an illustrative embodiment of a beam of the piezoelectric energy harvester.
[0010] FIG. 4 is a schematic diagram showing an illustrative embodiment of a circular spiral spring type piezoelectric energy harvester.
[0011] FIG. 5 is a schematic diagram showing an illustrative embodiment of a tetragonal spiral spring type piezoelectric energy harvester.
DETAILED DESCRIPTION OF THE INVENTION
[0012] A detailed description may be provided with reference to the accompanying drawings. One of ordinary skill in the art may realize that the following description is illustrative only and is not in any way limiting. Other embodiments of the present invention may readily suggest themselves to such skilled persons having the benefit of this disclosure.
[0013] FIG. 1 is schematic diagram showing a cantilever type piezoelectric energy harvester. The cantilever type piezoelectric energy harvester 100 may include a substrate 101 , a piezoelectric element 102 and a proof mass 103 . The cantilever type piezoelectric energy harvester 100 may be fabricated to be small in size (micro) by using microelectromechanical systems (MEMS) for forming sensors, thin film rechargeable batteries and the piezoelectric energy harvesters on one chip. In this case, a natural frequency of the piezoelectric energy harvesting element may increase over hundreds of Hz. Because the frequency of an ambient vibration source is below 200 Hz, the cantilever type piezoelectric energy harvesting element may not resonate with the ambient vibration source through frequency tuning. An efficiency of energy transformation may be proportional to the piezoelectric constant. The piezoelectric energy harvester using a 31-mode (d 31 ) piezoelectric constant has a lower efficiency of energy transformation than the piezoelectric energy harvester using a 33-mode (d 33 ) piezoelectric constant. Generally, the piezoelectric constant has a relationship of 3d 31 ≈d 33 .
[0014] FIG. 2 is a schematic diagram showing an illustrative embodiment of a piezoelectric energy harvester. As illustrated in FIG. 2 , the piezoelectric energy harvester 200 may be fabricated to have a spiral spring structure. Reference numeral “ 210 ” in FIG. 2 represents a proof mass.
[0015] The spiral spring structure of the piezoelectric energy harvester 200 may be made by processing a beam of the piezoelectric energy harvester illustrated in FIG. 3 . Referring to FIG. 3 , the beam 300 of the piezoelectric energy harvester 200 may include an elastic substrate 301 , a first electrode 302 formed on the elastic substrate 301 , a piezoelectric film 303 formed on the first electrode 302 and a second electrode 304 formed on the piezoelectric film 303 . The first electrode 302 , a piezoelectric film 303 and a second electrode 304 may be formed by thin film techniques such as sputtering and evaporation or depending upon the material, by printing techniques.
[0016] When mechanical pressure is applied to the piezoelectric film 303 , polarization change may occur along a direction perpendicular to the first and second electrode 302 and 304 to thereby produce a voltage. In one embodiment, when the piezoelectric energy harvester 200 is fabricated using microelectromechanical systems (MEMS), the elastic substrate 301 may be formed by a silicon (Si) wafer or a silicon nitride (SiN) deposited on a silicon wafer. The elastic substrate 301 may further comprises a film formed by one of spring-steel, copper, brass, bronze, glass fiber and fiber reinforced plastic, but the materials are not limited thereto. The first and second electrode 302 and 304 may be formed using silver, platinum, gold, aluminum, nickel, copper-nickel alloy, but the materials are not limited thereto. The piezoelectric film 203 may be formed by a ceramic thick film or a thin film made one of gallium orthophosphate, lanthanum gallium silicate, barium titanate, lead titanate, potassium niobate, lithium niobate, lithium tantalate, sodium tungstate, lead zirconate titanate (PZT) series, but the material are not limited thereto.
[0017] When the piezoelectric energy harvester 200 resonates with an ambient vibration source, displacement of the piezoelectric energy harvester 200 may be maximized to thereby produce a maximum voltage. An energy transformation efficiency of mechanical to electrical energy may be maximized at resonance. For the resonance of the piezoelectric energy harvester 200 with the ambient vibration source, a natural frequency of the piezoelectric energy harvester 200 should be set identical to a frequency of the ambient vibration source. The natural frequency of the piezoelectric energy harvester 200 may be closely related with a dimension thereof. The ambient vibration source generally has a frequency of below 200 Hz. When the piezoelectric energy harvester is fabricated using the MEMS, in some embodiments the natural frequency may be above 200 Hz due to size. In order to lower the natural frequency, a proof mass 210 , which may be attached on an end of the beam of the piezoelectric energy harvester, can be used. Generally, the natural frequency of the piezoelectric energy harvester may be calculated using the following equation.
[0000]
f
natural
=
1
2
π
[
3
EI
L
3
(
M
+
0.24
M
b
)
]
1
/
2
(
1
)
[0018] wherein “f natural ” indicates the natural frequency of the piezoelectric energy harvester 200 , “E” indicates Young's modulus, “I” indicates a moment of Inertia, “M” indicates a weight of a proof mass 210 , “M b ” indicates a weight of a beam and “L” indicates a length of the beam 300 . As can be understood from equation (1), the natural frequency is inversely proportional to the length of the beam and the weights of the beam and the proof mass 210 .
[0019] When the piezoelectric energy harvester 200 is fabricated using the MEMS, a heavy proof mass 210 may not be used to lower the natural frequency because the piezoelectric energy harvester 200 may be damaged during the vibration of the piezoelectric energy harvester 200 . Accordingly, it may be difficult to lower the natural frequency of the piezoelectric energy harvester 200 using the proof mass 210 only. In one embodiment, the piezoelectric energy harvester 200 may be fabricated to have a circular spiral spring structure. However, the shape of the piezoelectric energy harvester may not be limited thereto. In another embodiment, the piezoelectric energy harvester may be fabricated to have various spiral spring structures such as a circular or polygonal spiral spring structure, etc., as illustrated in FIGS. 4-5 . The polygonal spiral spring structure may include spiral spring structures having the shape of a triangle, tetragon, hexagon, octagon and the like. In FIGS. 4-5 , numeral references “ 410 ” and “ 510 ” represent proof masses.
[0020] In one embodiment, since the piezoelectric energy harvester is fabricated to have the spiral spring structure, the length of the beam of the piezoelectric energy harvester can be extended within a limited size thereof. Thus, the natural frequency may be lowered to a frequency below 200 Hz. The electromechanical coupling factor of the piezoelectric energy harvester 200 , which indicates an energy transformation efficiency thereof, may be calculated using the following equation.
[0000]
k
2
=
d
2
s
·
K
33
=
d
·
g
s
=
d
2
Y
K
33
(
2
)
[0021] wherein “k” indicates an electro-mechanical coupling factor of the piezoelectric energy harvester 200 , “d” indicates a piezoelectric constant, “g” indicates a piezoelectric voltage constant, “Y” indicates the Young's modulus, “K” indicates a relative permittivity and “s” indicates an elastic compliance.
[0022] In one embodiment, a 15-mode (d 15 ) piezoelectric constant may be used when a shear stress is applied to the piezoelectric energy harvester 200 , instead of a 31 mode (d 31 ) piezoelectric constant which may be used when the displacement direction is perpendicular to an electric field. The piezoelectric constant d 31 is typically used in the conventional piezoelectric energy harvester 100 having a cantilever structure. Generally, the piezoelectric constant has a relationship of 3d 31 ≈d 33 <d 15 . Thus, the electromechanical coupling factor “k” representing the energy transformation efficiency of the piezoelectric energy harvester 200 may be greater than that of the piezoelectric energy harvester 100 having a cantilever structure.
[0023] In one embodiment, an inactive region of the piezoelectric energy harvester 200 , which represents an empty space necessary for vibration thereof, may be minimized compared to that of the piezoelectric energy harvester 100 having a cantilever structure, and an active region of the piezoelectric energy harvester 200 may be maximized. Further, it is possible to make a structure having a higher energy density by arraying a plurality of piezoelectric energy harvesters.
[0024] In one embodiment, the natural frequency of the piezoelectric energy harvesters 200 , 400 and 500 may be may be tuned according to the weight of the proof masses 210 , 410 and 510 . The natural frequency of the piezoelectric energy harvester 200 , 400 and 500 may be calculated using the following equation.
[0000]
f
n
=
f
0
α
m
+
1
(
4
)
[0025] wherein “f n ” indicates a natural frequency of the piezoelectric energy harvester having a proof mass, “f 0 ” indicates a natural frequency of the piezoelectric energy harvester without the proof mass, “m” indicates a weight of the proof mass, “a” indicates a constant associated with a type of the piezoelectric energy harvester. As can be understood from equation (4), the natural frequency of the piezoelectric energy harvester may be tuned by adjusting the weight of the proof masses 210 , 410 and 510 in the piezoelectric energy harvesters 200 , 400 and 500 .
[0026] Any reference in this specification to “one embodiment,” “an embodiment,” “example embodiment,” “illustrative embodiment,” etc. means that a particular feature, structure or characteristic described in connection with the embodiment may be included in at least one embodiment of the present invention. The appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment. Further, when a particular feature, structure or characteristic is described in connection with any embodiment, it is submitted that it is within the purview of one skilled in the art to affect such feature, structure or characteristic in connection with other embodiments.
[0027] Although embodiments have been described with reference to a number of illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure. More particularly, numerous variations and modifications are possible in the component parts and/or arrangements of the subject combination arrangement within the scope of the disclosure, the drawings and the appended claims. In addition to variations and modifications in the component parts and/or arrangements, alternative uses will also be apparent to those skilled in the art.
|
The present invention relates to a piezoelectric energy harvester having a high energy transformation efficiency and a low natural frequency. The piezoelectric energy harvester includes an elastic substrate having a spiral spring structure, a first electrode formed on the elastomeric substrate, a piezoelectric film formed on the first electrode and a second electrode formed on the piezoelectric film.
| 7
|
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a National Phase Entry of International Application No. PCT/FR2009/000459, filed on Apr. 17, 2009, which claims priority to French Application 08/52750, filed on Apr. 24, 2008, both of which are incorporated by reference herein.
TECHNICAL FIELD
The invention relates to the field of manipulator robots enabling the movement of a terminal end.
BACKGROUND
Manipulator robots are used for moving and positioning an object or a tool in space. They can have a serial, parallel or, less often, hybrid structure. In the case of serial structures, the various parts composing the robot are articulated with respect to each other, in series and the relative movements are obtained from actuators distributed along a kinematic chain. In the case of a parallel structure, several kinematic chains are closed and the elements constituting such chains are not necessarily all actuated.
The serial, hybrid or parallel manipulator robots have a certain number of degrees of robot flexibility making it possible to obtain degrees of freedom for the object to be handled. Most serial robots sold on an industrial scale are:
either of the SCARA type, with two mobile arms in a plane and a degree of robot flexibility in a direction perpendicular to such plane (possibly completed by rotation about such latter axis) making it possible to position and orient a solid in planes parallel to a base plane or of the anthropomorphic type, with a base, a shoulder and an arm supporting a wrist finally giving six degrees of robot flexibility (three for the position, three for the orientation).
A robot can be redundant if the number of degrees of robot flexibility (in relation with the number of actuators) is greater than the number of degrees of freedom obtained for the handled solid. Generally speaking, such robots are difficult to control but make it possible to avoid obstacles located in the working space or to work in hardly accessible spaces.
Standard ISO 9283 defines the performance criteria to be taken into account for an industrial robot, more particularly the reproducibility and the accuracy in the positioning. So far, the reproducibility of the positioning of the manipulator robots, whether serial or parallel, redundant or not, does not exceed a value close to one hundredth of a millimeter. As for the accuracy performances, they are even lower and today the best robots can guarantee only an exact positioning within 0.03 millimeters in the working space. In fields such as clock-making, where it is necessary to insert axes into holes 0.2 millimeters in diameter, or in the optoelectronic field, a reproducibility of less than 0.01 millimeters and accuracy in the positioning of the order of 0.01 millimeters are essential.
For some so-called singular configurations, the number of degrees of freedom of the terminal end of the robot is locally strictly lower than the number of degrees of robot flexibility. The Jacobean matrix is the matrix resulting from the differentiation of the geometric model of the robot; it is no longer revertible in singular positions. This raises a problem when, for example, the robot is controlled by a revertible differential model. Then, the terminal end of a robot is generally not positioned in areas close to the singular configurations because of the underlying control problems.
The document U.S. Pat. No. 4,523,100 is known in the prior art, which discloses a robot including an articulated arm supporting an articulated head for micro-movements. The articulated arm provides a rough positioning of the articulated head, and the accurate positioning is provided by linear verniers, composing the articulations of the head. Such robot has the drawback of requiring at least 6 articulations of a different nature. In so-called micro/macro devices used for accurately positioning an object in a three-dimensional space, the fine movements of the terminal ends are generally provided by an independent micrometric device fixed downstream of the kinematic chain; the assembly requires a minimum of three articulations of the supporting structure for positioning the micrometric device and the micrometric device itself includes three articulations, which means generally 6 articulations.
SUMMARY
The invention aims at remedying the drawbacks of the state of the art and more particularly at bringing an accurate positioning of the terminal end of redundant robots, which results in improved performances in accuracy (reproducibility and exact positioning) with respect to the prior art. In addition, the present invention makes it possible to work in areas close to the base or singular configurations of the robot structure. With respect to the macro/micro devices, the invention makes it possible to substantially reduce the number of articulations used for the fine positioning by providing an integrated architecture.
The invention relates to totally integrated and redundant robot structures for which a so-called “area of interest” exists, wherein the fine positioning of the terminal end of the robot can be obtained. The area of interest does not cover the whole working space accessible by the end of the robot, but a preferred volume of action within which the end of the robot may run along any path of motion, unlike the solution disclosed in U.S. Pat. No. 4,523,100. The invention relates to a robot including an articulated arm for the movement of an end in an N-dimensional space comprising at least N+1 motorized articulations, as well as a computer for controlling the movements of said motorized articulations, with said computer controlling a first step of prepositioning the terminal end of the articulated arm and a second step of fine positioning.
Said first step of prepositioning consists in engaging the end of an articulated arm in the area of interest, as close as possible to the centre of the optimum positioning area, with the centre being defined as a function of N secondary motorized articulations, with at least one of said secondary articulations being an axis of rotation. Said second step of fine positioning consists in blocking all the articulations except for said N secondary motorized articulations and in controlling the movement of the terminal end by elementary movements of at least one of the N secondary articulations.
In particular embodiments:
the articulated arm for a positioning in a three-dimensional space includes at least four motorized articulations, among which at least two axes of rotation, with the first step of prepositioning consisting in bringing the terminal end of the robot in the area of interest, with said area of interest being a sub-assembly of the working space, and in that the second step of fine positioning consists in blocking all the articulations except for three secondary motorized articulations, among which said two axes of rotation, and in carrying out the final positioning through elementary movements of at least one of said secondary articulations; the articulated arm for positioning in a three-dimensional space includes at least four motorized articulations, among which at least one axis of rotation, the first step of prepositioning consisting in bringing the terminal end of the robot to the area of interest, said area of interest being a sub-assembly of the working space and in that the second step of fine positioning consists in blocking all the articulations except for three secondary motorized articulations, among which said axis of rotation, and in executing the final positioning through elementary movements of said secondary articulations; the articulated structure includes at least three motorized articulations among which at least two so-called secondary parallel axes of rotation, and in that the first step of prepositioning consists in bringing the terminal end of the robot to the area of interest; a second step of fine positioning consisting in blocking all the motorized articulations except for said secondary motorized axes of rotation, and in carrying out the final positioning through elementary movements by the rotation of at least one of said secondary axes; the articulated arm for a positioning in a plane of a space includes at least three motorized articulations, among which at least one axis of rotation, with the first step of prepositioning consisting in bringing the terminal end of the robot to the area of interest, with said area of interest being a sub-assembly of the working space, and in that the second step of fine positioning consists in blocking all the articulations except for two secondary motorized articulations, among which said axis of rotation, and in executing the final positioning through elementary movements of at least one of said secondary articulations; the articulated arm for a positioning in a three-dimensional space includes at least four serial motorized articulations, among which at least 3 so-called secondary axes of rotation, with a first step of prepositioning consisting in bringing the terminal end of the robot to an area of interest, with said area of interest being a sub-assembly of the working space, wherein the lever arms with respect to the three secondary axes of rotation have a small length and in that the second step of fine positioning consists in blocking all the articulations except for said secondary motorized axes of rotation, and in proceeding to the final positioning through elementary movements by rotation of at least one of said secondary axes; the articulated arm includes at least three serial motorized articulations, among which at least two so-called secondary parallel axes of rotation, and in that the first step of prepositioning consists in bringing the terminal end of the robot to the area of interest, a fortiori to the optimum positioning area, with said optimum positioning area being a disc, the centre of which is the apex opposed to the hypotenuse of an isosceles right-angled triangle inscribed in a plane containing the terminal end of the handling arm and perpendicular to the secondary axes of rotation, with the hypotenuse having a first apex on the first secondary axis of rotation and a second apex on the second secondary axis of rotation; the diameter of said disc is approximately equal to the distance between the two secondary axes of rotation; the second step of fine positioning consisting in blocking all the motorized articulations except for said secondary motorized axes of rotation, and in carrying out the final positioning through elementary movements by rotation of at least one of said secondary axes; said robot includes at least one additional articulation located upstream of the kinematic chain and an opening step enabling the definition of an area of interest through the action of such additional articulation or articulations; the fine positioning is indirectly obtained through the reproduction of a portion of path of motion from a particular point called a point of harmonization to the target point, in order to solve the problems of dry frictions, with the harmonization point being a point located outside the dead zone linked to the target point; the fine positioning is obtained by the processing of position exteroceptive information making it possible to deduce the distance between the position of the terminal end of the robot and the target point, and to control the robot through elementary rotations about the secondary axes; both steps are computed prior to the execution in order to prepare a control law for a continuous movement; both steps are calculated prior to the execution, in order to prepare a control law and a periodical re-computation during the movement; the design of such a redundant robot for the fine positioning makes it possible to have a revertible geometric model at each step; the control of the redundant robot for the fine positioning uses a local calibration process for a better accuracy in the positioning upon completion of the prepositioning phase; a wrist is fixed at the end of the robot, which enables the control of the orientation of an object or a tool.
In other embodiments:
the secondary axes are selected as being those which have the smallest lever arm with respect to the target point; the distance between both secondary axes being smaller than the distance between a secondary and a third axis, as well as the distance between the third axis and the terminal point; the angular position sensors of the secondary articulations have a resolution which is greater than the resolution of the sensors of the other articulations; the design of the redundant robot for the fine positioning in two steps makes it possible to have an invertible geometric model at each step because of the redundancy of two consecutive parallel axes of rotation on the kinematic chain.
The robotic structure is composed of at least three articulated segments in serial, hybrid or parallel mode according to a redundant configuration, of proprioceptive sensors making it possible to obtain information on the actuators of the kinematic chain and a computer making it possible to control said kinematic chain. Two types of articulations are defined at the kinematic chain composing the robotic structure: the articulations for the positioning and the orientation called primary articulations (of the rotary, prismatic type or any type of articulation known to the persons skilled in the art), then among those, some rotary articulations used for a precise positioning of the terminal end of a robot so-called secondary articulations. The selection of the secondary rotary articulations in the kinematic chain depends on the configuration of the robotic structure, with some rotary articulations which can be configured as secondary articulations for a given configuration and only for primary articulations for another configuration. The selection of the secondary axes is based on the principle that the distances between the secondary axes of rotation and the terminal end of the robot are small with respect to the distances between the non secondary axes of rotation and the terminal end of the robot.
In alternate embodiments, some secondary motorized rotary articulations can be replaced by prismatic links in order to enable an accurate positioning in a plane or the three-dimensional space, provided that at least one motorized rotary articulation remains among the secondary articulations; thus, for a fine positioning in the three-dimensional space, the secondary articulations can result from the combination of two rotary articulations and a motorized prismatic articulation as illustrated in FIG. 10 or a rotary articulation and two motorized prismatic articulations; for a positioning in the plane, the secondary articulations can result from the combination of one motorized rotary articulation and one motorized prismatic articulation as illustrated in FIG. 8 - e.
The area of interest is a restricted area of the working space which intrinsically depends on the configuration of the robotic structure and for which the following properties are checked: the terminal end of the robot may be positioned in the area of interest; the space resolution of the position obtained by controlling the secondary axes of rotation is finer than in the remainder of the working space; the elementary vectorial movements induced by the elementary rotations about the secondary axes of rotation form a family generating vectors in space, ideally an orthogonal base. For a fine positioning in the three-dimensional space, three secondary articulations will be selected from the kinematic chain. For a fine positioning in a plane, two secondary articulations will be selected from the kinematic chain. For a fine positioning on a straight line, one secondary articulation will be selected in the kinematic chain. However, in such various cases, it may be necessary to choose more secondary articulations than previously defined, since the persons skilled in the art are capable of designing a control which can manage the local redundancy resulting from the elementary movements forming a family of vectors linked in the vectorial space of the requested movements, with the principles and the advantages of the invention remaining valid.
Within the area of interest, an optimum positioning area can be distinguished. The centre of the optimum positioning area is a particular point in the OPA located at the same distance from the secondary axes and for which the elementary vectorial movements induced by the elementary rotations about the secondary axes of rotation form an orthogonal base of vectors in space. Not all the redundant robotic structures have necessarily an area of interest, or a fortiori an OPA. For a given robotic structure, the area of interest and the OPA depend on the configuration of the kinematic chain. However, only a part of the working space may become an area of interest. The designer of the robotic structure must be careful and define the dimensions thereof so that the OPA can exist, have a sufficient volume and be accessible by movements and configurations according to the desired application. As for the user, he or she must select from all the possible configurations, the one that will enable him or her to make the area where the fine positioning is desired and the area of interest, or a fortiori the OPA coincide. The ideal is that the fine positioning is executed in a region close to the centre of the OPA.
When the final positioning is carried out at the centre of the OPA, the space control of the fine positioning is uncoupled with respect to the controls of the secondary axes. When getting further from the centre of the OPA while remaining in the area of interest, a partial coupling may appear. The invention relates to the fine positioning control which can be broken down into two independent steps: the first step, also called the prepositioning step, consists in bringing the terminal end of the handling arm to the area of interest, a fortiori to the OPA; the second step consists in finely positioning the terminal end of the handling arm only using one or several secondary articulations.
During the step of fine positioning, the secondary axes of rotation only are activated. Because of the present structure and with an equal resolution on the angular encoders, this enables a significant and computerized improvement of the reproducibility of the positioning estimated with respect to the secondary axes of rotation. On the other hand, at the centre of the OPA, the control between the Cartesian space and the secondary articulation space is uncoupled. This small value of the reproducibility in the positioning makes it possible to locally correct position errors by strictly limiting the non linearity intrinsic in the reproducibility “sphere”. For example, a “jump” ellipsoid control can be used.
During the step of fine positioning, the information from the exteroceptive position sensors (mechanical, digital, optical or other micrometers, microscopes, viewing devices) can be integrated in the control system. The information from such sensors makes it possible to obtain the relative deviations between the desired final position and the position reached by the terminal end. FIG. 1 relates to a fine assembly table illustrating such a principle. The device includes an assembling plate 10 , a first assembly formed of a North laser scanning micrometer 1 and a South laser scanning micrometer 2 associated to a laser beam 3 , and a second assembly formed by an East laser scanning micrometer 4 and a West laser scanning micrometer 5 associated to a laser beam 6 . The two (East-West, North-South) laser scanning micrometers make it possible to obtain the relative positions between a shaft 8 and a bore 9 . This deviation can then be used within a control system to obtain the final position desired.
FIG. 2 illustrates various methods which can be implemented to correct the deviation between the desired position 201 and the reached position. Because of dry frictions, small deviations in the position of the articulations are sometimes difficult to correct. As for the server control, a proportionate control does not exert a sufficient stress (torque or force) to overcome the stress of the dry friction in an area called a dead zone shown here by the sphere 202 wherein there is no movement generated; it is necessary to wait for the integral corrective action of the servo-control finally generating sufficient efforts to cause a movement with the risk of subsequently inducing passing phenomena related to the dynamics of the system; this is the case of the path of motion 205 which makes it possible to go from the point 203 located in the dead zone to the point 204 . Such passing may have secondary effects as regards safety and operation security. The final positioning 207 can be obtained by a direct control (for example a reverse differential control) if the origin of the path of motion 208 is outside the dead zone. If the reached position 209 is in the dead zone, it is possible obtain the fine positioning using the following process: a point of harmonization 210 is defined and located outside the dead zone obtained by the path of motion 211 . The principle then consists in reproducing a path of motion 213 starting from such a point of harmonization 210 by adjusting the final setting as a function of the deviation measured between the reached position 212 and the target 201 . The path of motion 214 is then used to go back to the point of harmonization 210 . The final setting is then slightly modified, taking into account the deviation between the point 212 and the target 201 . The path of motion 216 leads from the point of harmonization 210 to the point 215 which is the closest to the target 201 . This process can be resumed until the final point is close enough to the target 201 .
The accuracy of the position reached by the robot structure during the step of prepositioning remains that of a conventional manipulator robot. It can be significantly improved during the step of fine positioning in the area of interest by using a local calibration procedure. Such a procedure may, for example consist in accurately measuring the position of the terminal end with exteroceptive captors at a point of the area of interest and to deduce therefrom the variations in the position of the terminal end during the step of fine positioning by computerisation from the geometric (or differential) model, only based on the secondary axes. Other strategies can also be considered: several sensors distributed in the area of interest and coupled to various configurations making it possible to finally deduce the position of the terminal end in the area of interest while reducing the uncertainty relating to the non secondary articulations position sensors and to the errors in the geometric model on a part of the kinematics chain. Such local calibration must make it possible to reduce the importance of the errors in the geometric model related of the secondary axes by one order of magnitude.
It is possible to make the robot structure work as defined outside the area of interest, with the operation of the robot then being that of a conventional redundant robot without a fine positioning. The control of the articulations by the actuators is conventionally executed in closed loop using the proprioceptive information from the positions sensors (for example encoders) generally used on this type of robot. The orientation of an object or a tool fixed on the terminal end of the articulated arm can be conventionally controlled from the various articulations distributed on the kinematic chain. In an alternate embodiment, it can be considered to position a wrist on the terminal end of the robotised arm which makes it possible to control the orientation of an object or a tool fixed at the terminal end.
BRIEF DESCRIPTION OF THE FIGURES
Other characteristics and advantages of the invention will appear upon the reading the following description and referring to the appended figures briefly shown hereinunder:
FIG. 1 relates to a fine assembling table including two laser scanning micrometers making it possible to obtain the relative positions between a shaft and a bore;
FIG. 2 illustrates various paths of motion to correct the deviation between the desired position and the reached position;
FIG. 3 shows a perspective diagram of the kinematic chain of a generic embodiment for a fine positioning in the three-dimensional space;
FIGS. 4 - a (perspective view), 4 - b (top view) and 4 - c (side view) show the diagram of a kinematic chain of a first particular embodiment for a fine positioning in the three-dimensional space;
FIGS. 5 - a (side view) and 5 - b (top view) show a diagram of the kinematic chain of a second particular embodiment for a fine positioning in the three-dimensional space;
FIG. 6 - a (side view) and 6 - b (top view) show a diagram of the kinematic chain of a third particular embodiment for fine positioning in the three-dimensional space;
FIG. 7 shows a kinematic chain of a generic embodiment for the accurate positioning of the terminal end in one plane of space;
FIGS. 8 - a (perspective view) and 8 - b (top view) show diagrams of a kinematic chain of a first particular embodiment for the fine positioning in the two-dimensional space, FIG. 8 - c illustrates the improvement in the accuracy by a local calibration method; FIG. 8 - d is an alternative for which the additional degree of robot flexibility is inserted between the two secondary axes of rotation; FIG. 8 - e illustrates an alternate embodiment wherein a prismatic articulation is substituted for a secondary rotary articulation;
FIG. 9 (top view) shows a diagram of the kinematic chain of a second particular embodiment for a fine positioning in the two-dimensional space, making it possible to define the area of interest and to accurately position the terminal end of the robotized arm in this area;
FIG. 10 (top view) shows a diagram of the kinematic chain of a particular embodiment for a fine positioning in the three-dimensional space wherein one of the secondary articulations is prismatic; and
FIG. 11 (top view) shows a diagram of a kinematic chain of a particular embodiment corresponding to a hybrid robot structure for a fine positioning in a plane.
DETAILED DESCRIPTION OF THE EMBODIMENTS
Referring to FIG. 3 , in a general embodiment for a fine positioning in a three-dimensional space, the robot structure is composed of three rotary articulations 302 , 304 and 306 also called secondary articulations, in relation with, on the one hand the frame 300 through a kinematic chain 301 , and on the other hand together through the kinematic chains 303 and 305 and finally in relation with the terminal end 310 by a last kinematic chain. The global kinematic chain of the robot structure has at least one additional articulation (i.e. a fourth degree of robot flexibility) belonging to the so-called primary articulations and making it possible for the terminal end of the kinematic chain to run in a larger space than the working space related only to the secondary articulations. The fourth articulation may be inserted as desired into one of the kinematic chains 301 , 303 , 305 or between 306 and 310 , and here this concerns the rotary link 308 .
The robot structures concerned by the invention and enabling a fine positioning define, in the three-dimensional space, a so-called area of interest which corresponds to an assembly of points for which the distances with respect to the three so-called secondary axes 302 , 304 and 306 are small but not null, and the movements induced by elementary rotations about the axes of rotation 302 , 304 and 306 are executed along three not coplanar directions. For a particular configuration of the robot structure in this area of interest, a sub-assembly also called an optimal positioning area (OPA) is defined, the centre of which is defined as follows: this is the point of intersection 314 of three planes in space 311 , 312 and 313 containing the axes of rotation 302 , 304 and 306 . The distances between the point 314 and the axes of rotation 302 , 304 and 306 are substantially of the same order of magnitude; they are not null and small with respect to the other characteristic values of the kinematic chain defining the volume of the space which can be reached by 310 . When the terminal end 310 of the robot is at point 314 , the movements induced by the elementary rotations about the axes of rotation 302 , 304 and 306 are executed along three perpendicular directions in space. For this particular configuration, the OPA corresponds to a sphere having a centre 314 and the radius of which is approximately equal to half the minimum distance between the point 314 and the axes of rotation 302 , 304 and 306 .
The structure controlling method consists in placing the terminal end 310 in the OPA using the primary degrees of robot flexibility and in blocking all the articulations except for the secondary rotation articulations 302 , 304 and 306 which then make it possible to obtain a fine positioning in the OPA. The space resolution obtained at point 314 is then much finer than in the rest of the working space because of the small lever arms generated by the three secondary actions. In addition, the movements induced by the elementary rotations about the secondary axes are executed along three perpendicular directions in space and the control between the secondary articulation space and the Cartesian space is uncoupled. When getting further away from the centre of the OPA, the uncoupling tends to disappear but the advantages as regards the accuracy of the positioning remain within the OPA and more generally in the area called the area of interest.
The robot structure can also be used in a mode consisting in obtaining an accurate positioning in the three-dimensional space, whereas the three secondary axes do not exactly belong to three perpendicular planes intersecting at 314 as mentioned above, but that the previous principles of the invention are used: primary and secondary axes, small lever arms with respect to the secondary axes, movements induced by the non coplanar secondary axes. The robot structure can also be used in another embodiment consisting in obtaining a precise positioning in a plane of space using at least two axes among the secondary axes mentioned above. The robot structure can also be used in another embodiment consisting in obtaining a precise positioning on a straight line in space using at least one axis among the secondary axes mentioned above.
While referring to FIGS. 4 - a , 4 - b and 4 - c in a particular embodiment enabling the positioning of the terminal end in the three-dimensional space with a very high precision, the robot structure is composed of two parallel axes of rotation 402 and 404 and of two parallel axes of rotation 406 and 408 which are perpendicular to the axes of rotation 402 and 404 . The plane 413 contains the axis 406 and is perpendicular to the axis 402 . The point 410 is the intersection of the plane 413 with the axis 402 . The point 411 is the intersection of the plane 413 with the axis 404 . The distance between the axes 404 and 406 is equal to the distance between the axes 402 and 404 multiplied by the ratio 0.2. The distance between the axes 406 and 408 is equal to the distance between the terminal end 310 and the axis 408 from which 0.7 times the distance between the axes 402 and 404 is deducted, so that both distances remain within the same order of amplitude. We are looking for a “length of the arm 407 /length of the arm 403 ” ratio, which must be as high as possible. According to the industrial use of such a robot arm and according to the characteristics of the working space wherein the robot arm will be used, the persons skilled in the art have to optimise the above ratio. The persons skilled in the art can arbitrarily choose a length of the arm 407 and divide it by 10 to obtain the length of the arm 403 . The distance of the axis 402 to the base of the robot 400 is not an essential criterion and will be determined as a function of the constraints within the working space. 402 may be directly fixed on the base 400 without any intermediate arm 401 .
The method for controlling such a structure consists in driving the axes of rotation 402 , 406 and 408 in order to position the terminal end 310 in the area of interest close to the axes 402 , 404 and 406 . Ideally, the persons skilled in the art will try to position the terminal end 310 close to the centre 412 of the OPA. The centre of the OPA is an apex 412 of an isosceles right-angled triangle of the plane 413 , the hypotenuse of which is the segment connecting the point 410 and the point 411 . The distance between 412 and the axis of rotation 406 is equal to the distance between 412 and 410 . Depending on the configurations of the primary articulations, the point 412 may have various positions in space. For a given configuration, the OPA corresponds to a sphere with a centre 412 and the radius of which is substantially equal to half the distance between 410 and 412 . The positioning of the terminal end in the OPA aims at minimising the lengths of the lever arms associated with the axes of rotation 402 , 404 and 406 with respect to the terminal end 310 , but without cancelling these so that the end of the manipulator arm can be controlled in the three-dimensional space of the secondary axes. Once 310 is positioned within the OPA, the axis 408 is blocked. Then the axes 402 , 404 and 406 are activated so as to obtain a fine positioning in space. As regards the point 412 , the elementary movements induced by the rotations of the axes 402 , 404 and 406 are carried out in three perpendicular directions. In addition, with equal controls and resolutions on the angular sensors of the secondary axes, the position increments resulting from the elementary rotations of the secondary axes are identical in the three perpendicular directions. If the terminal end is further away from the point 412 while remaining within the OPA, the elementary movements are no longer necessarily orthogonal but remain linearly independent, and with equal control and resolutions on the angular sensors, the position increments can substantially vary. However, the advantages as regards the improvement in the accuracy of the positioning are not affected.
The space resolution is in relation with the digital control resolution, with the performances of the actuators control system characterized, among other things, by the covariance matrix and the proprioceptive sensors resolution and to the space configuration of the robot arm. On the modern systems, the resolution of the digital control can be considered as quasi-continuous thanks to the double precision processing by the computer. The robot structure shown makes it possible to obtain a much finer space resolution and a much better reproducibility within the OPA than in the remainder of the working space by controlling the axes 402 , 404 and 406 .
Because the axes 402 and 404 are parallel, the redundancy of the robot structure causes no particular problem for the control of the mechanism during both phases of the prepositioning and the fine positioning. As a matter of fact, driving a redundant robot is always difficult since this requires integrating additional criteria in the control process (optimising the energy criterion for example). Then, during the prepositioning phase, the axes 402 , 406 and 408 can be driven only with the only aim of bringing the terminal end in the OPA; during this phase the robot structure has a conventionally revertible geometric model. During the fine positioning phase, the axes 402 , 404 and 406 only are actuated and the geometric model is still conventionally locally revertible.
While referring to FIGS. 5 - a and 5 - b , in a particular embodiment, the robot structure for an accurate positioning of a terminal end of the robot in the three-dimensional space is composed in a reference configuration of three parallel axes 502 , 506 and 508 , and one axis 504 perpendicular to 502 , 506 and 508 . Except in the reference configuration, the axes 506 and 508 are always parallel but they are no longer necessarily parallel to the axis 502 . As for the dimensions of this structure, the persons skilled in the art will try to obtain a length of the arm 507 /length of the arm 505 ratio as high as possible while considering the constraints in the working space. The lengths of the arms 507 and 509 are substantially equal to each other within 10%. The length of the arm 507 is, for lack of constraints, at least 10 times longer than the distance between the axes 504 and 506 .
The control of such structure will be identical in every point to the previous structure, starting with the positioning of the terminal end 310 in the area of interest through the action of the axes of rotation 504 , 506 and 508 . Then, once the end 310 is positioned, the axis 508 is blocked and the accurate positioning occurs thanks to the simultaneous actuation of 502 , 504 and 506 .
While referring to FIGS. 6 - a and 6 - b , in a particular embodiment, the robot structure for an accurate positioning of a terminal end of the robot in a three-dimensional space is composed of three parallel axes 604 , 606 and 608 and one axis 602 perpendicular to 604 , 606 and 608 . To size this structure, the persons skilled in the art will try to obtain a length of the arm 607 /length of the arm 605 ratio as high as possible while considering the constraints in the working space. Lengths of the arms 607 and 609 are substantially within 10%. The length of the arm 607 is, for lack of constraints, at least 10 times greater than the length of the arm 605 .
The control of such structure will be identical in every point to the previous structures, starting with the positioning of the terminal end 310 of the arm in the area of interest through the action of the axis of rotation 602 , 606 and 608 (or the axes of rotation 602 , 604 and 608 ). And once the end 310 is positioned, the axis 608 is blocked and the accurate positioning occurs thanks to the joint actuation of 602 , 604 and 606 .
While referring to FIG. 7 , in a generic embodiment enabling the positioning of the terminal end 310 and the robot structure in one plane (P) in space, the structure is composed of three kinematic chains 701 , 703 and 705 and two axes of rotation 702 , 704 perpendicular to the plane (P). The kinematic chain 701 connects the rotary link 702 to the support 700 ; the kinematic chain 703 connects the two rotary connections 702 and 704 ; the kinematic chain 705 connects the rotary link 704 to the terminal end 310 . An additional degree of robot flexibility in the plane (in rotation or in translation) is then integrated in at least one of the kinematic chains 701 , 703 or 705 . This degree of robot flexibility aims at significantly widening the space which can be reached by the end 310 with respect to the space that can be reached by a robot structure of the SCARA type based on the articulations 702 and 704 .
The point 706 is the intersection between the plane (P) and the axis 702 . The point 708 is the intersection between the plane (P) and the axis 704 . The square of the plane (P) a diagonal of which connects the point 706 and 708 defines two new apexes 707 and 709 . In this general case and for a given configuration of the so-called secondary axes of rotation 702 and 704 , there are OPAs (indicated by OPA 1 and OPA 2 ) the centres of which are points 707 and 709 . OPAs are discs centred on 707 and 709 the radius of which is equal to half the distance between 706 and 709 .
The control of such structure is as follows: —Placing the end 310 in the OPA by actuating the primary articulations which include all the degrees of robot flexibility of the kinematic chains; —Blocking all the degrees of robot flexibility except for the secondary rotations along the axes 702 and 704 ; —Executing the fine positioning by actuating the axes 702 and 704 . Then, if the terminal end 310 is, for example, at 709 , the elementary movement induced by the rotations of the axes 702 and 704 are carried out along two perpendicular directions in the plane (P) from 709 to 706 and from 709 to 708 . In addition, with equal control and resolution on the angular sensors of the axes 702 and 704 , the position increments are identical in both perpendicular directions. If the terminal end 310 moves further away from the point 709 while remaining within the OPA 1 , the elementary movements are no longer necessarily perpendicular to each other but remain linearly independent and with an equal resolution on the angular sensors, the induced position increments may substantially vary. However, the advantages as regards the improvement in the accuracy of the positioning remain unaffected.
In a wider area than the OPA called the area of interest (ZI 1 and ZI 2 ), the short distance with the axes 702 and 704 makes it possible to obtain certain advantages during the fine positioning with performances which are indeed degraded with respect to the OPA but are often more interesting than in the remainder of the working space. Unless specific applications, the point 310 should not be positioned at the centre of the segment having ends 706 and 708 , since the elementary movements induced by the elementary rotations of the secondary axes 702 and 704 are then linearly dependent (local singularity) along the direction linking points 707 to 709 . The OPA depends on the configurations of the robot structure and also on the strategy of the positioning and moving the end of the arm and, if need be, the tool supported with respect to the part to be processed. In a previous step, it is still possible to select with some latitude the position of the centre of the OPA in the working space by acting on some primary degrees of robot flexibility. A motorized prismatic articulation along a parallel axis of articulation 702 can be added at the end of the kinematic chain 705 enabling a fine positioning in the three-dimensional space, with this principle being illustrated by the particular embodiment of FIG. 10 .
While referring to FIGS. 8 - a and 8 - b , in a particular embodiment making it possible to position the terminal end of the robot structure in a plane space, with the structure being composed of three rotary links 802 , 804 and 806 perpendicular to the plane 811 and thus parallel to each other. The rotary connection 802 is anchored on the one hand on a support integral with space 800 by one arm 801 and on the other hand it is in relation with the rotary 804 by one arm 803 . An arm 805 supports the rotary links 804 and 806 . The rotary link 806 controls the arm 807 . The terminal end to be positioned 310 is integral with the arm 807 . The lengths of the mars 805 and 807 are substantially equal to each other with a tolerance in the order of half the length of the arm 803 . The persons skilled in the art will try to obtain a length of 805 /length of 803 ratio as high as possible while considering the constraints in the working space. Without constraint, the persons skilled in the art will consider the length of the arm 803 as at least ten times smaller than that of the arm 805 . The length of the arm 805 is selected as a function of the size of the working space desired.
The plane 811 contains the point 310 and is perpendicular to the axes of rotation 802 , 804 and 806 . In this case, the centre of the OPA is the apex 810 of an isosceles right-angled triangle inscribed within the plane 811 , the ends of the hypotenuse of which are the point of intersection 808 of the plane 811 with the axis 802 and the point of intersection 809 of the plane 811 with the apex 804 . Depending on the configurations of the axes 802 and 804 , the point 810 may occupy various positions in space. For a given configuration, the area of interest corresponds to a disc with a centre 810 and the radius of which is substantially equal to half the distance between 810 and 808 .
The control of such structure is operated as follows: —Blocking the axis of rotation 802 ; —Placing the end 310 in the area of interest by actuating 804 and 806 ; —Blocking 806 ; —Carrying out the fine positioning by actuating 802 and 804 . Then, if the terminal end 310 is at point 810 , the elementary movements induced by the rotations of the axes 802 and 804 are carried out along two perpendicular directions in the plane 811 (from 810 to 808 and from 810 to 809 ). In addition, with equal control and resolutions on the angular sensors of the axes 802 and 804 , the position increments are identical in these two perpendicular directions. In a previous step, it is possible to select the position of the centre of the OPA by actuating axis 802 . If the terminal end 310 gets further away from the point 810 while remaining within the OPA, the elementary movements are no longer necessarily orthogonal, but remain linearly independent and with an equal resolution on the angular sensors, the induced position increments may substantially vary. However, the advantages as regards improvement and accuracy of the positioning remain unaffected.
While referring to FIG. 8 - c , the accuracy in the positioning may be significantly improved in the area of interest by using a local calibration process after the prepositioning phase. Two exteroceptive sensors 812 and 813 , for example digital micrometers, make it possible to know precisely the position of the terminal end 310 in the area of interest. During the step of fine positioning, with the articulation 806 blocked, the movements are carried out only from the axes 802 and 804 . The secondary geometric model connecting the angular movements of the secondary axes with the Cartesian movements in the plane can be rebuilt from the distances evaluated between 804 and 310 . Starting from the new reference in the local reference system thanks to this calibration operation, the movements on a path of motion 814 as from the position of 310 during the calibration are estimated by the secondary geometric model. Because of the small lengths of the lever arms with respect to the secondary axes, because the resolutions the sensors placed on the secondary axes are generally better than on the non secondary axes, because of the small distances between the secondary axes 802 and 804 , because of the calibration operation, the performances as regards the positioning accuracy within the area of interest are then much better than when the estimation of the position is computed from the geometric model taking into account all the primary articulations.
While referring to FIG. 8 - d , in a particular embodiment enabling the positioning of the terminal end of the robot structure in a plane of the space, the structure is composed of three rotary connections 802 , 804 and 806 with 802 and 806 being secondary axes of rotation and 804 being only a primary axis of rotation. The centre 810 of the OPA is defined as mentioned above with respect to the secondary axes 802 and 806 . The control method consists in blocking 804 when the prepositioning phase is completed and in activating the secondary axes 802 and 806 only during the fine positioning phase. Unlike the previous case, it is possible to modify the position of the centre 810 of the OPA with respect to the secondary axes of rotation by acting on the distance between the axes 802 and 806 , depending on the angular setting given for the axis 804 . This makes it possible during the fine positioning phase to reduce or to improve the sensitivity of the movements along both perpendicular directions. Another advantage is that such device can be integrated on existing SCARA robots, with the terminal part composed of the arm 807 and 310 which can be considered as a tool mounted on the end of the SCARA robot having a sufficient resolution on the axis 806 . The drawbacks are that the terminal end 310 cannot be placed at the centre of the OPA only for a particular value of the angular setting given for the axis 804 .
In an alternative solution of the previous structure, the axes of rotation 802 , 804 and 806 are not necessarily strictly parallel, however the movements of the terminal end during the fine positioning phase by actuating the secondary axes remain coplanar and the advantages of the structure as regards the performances in accuracy remain within an OPA which can be defined similarly to the previous case. While referring to FIG. 8 - e , in a particular embodiment making it possible to position the terminal end of the robot structure in a plane of the space, the secondary articulations are a vertical rotary link 802 and a horizontal prismatic link 816 ; the adjustment of the final position being provided by the small lever arm of the articulation 802 which gives an optimal resolution along a direction and by the prismatic articulation 816 in the perpendicular direction. Adding an additional vertical prismatic connection to provide a fine positioning in a three-dimensional space can be considered.
While referring to FIG. 9 , in a particular embodiment enabling the positioning of the terminal end of the robot structure in a plane of the space (P), with the possibility of defining more widely the OPA, the structure is composed of 5 rotary connections 902 , 904 , 802 , 804 , 806 which are all parallel to each other. In this structure, the kinematic chain 902 - 903 - 904 - 905 corresponds to a robot structure of the SCARA type, whereas the kinematic chain 802 - 804 - 805 - 806 - 807 - 310 can be compared to the previously disclosed structure for a precise positioning in a plane.
The control of such a structure starts with a step of defining the OPA in the plane space thanks to the rotary connections 902 and 904 . The centre 810 of the OPA can thus be positioned by the persons skilled in the art in an arbitrary area of the working space of a SCARA robot composed by the kinematic chain 902 - 903 - 904 - 905 .
The persons skilled in the art can then go on with the accurate positioning according to the previously disclosed method after selecting the centre of the OPA thanks to 902 and 904 . The selection of the dimensions must be made so that all the areas of interest desired by the persons skilled in the art belong to the space which can be reached by the SCARA robot corresponding to the kinematic chain 902 - 903 - 904 - 905 . The distribution of the lengths between 903 and 905 is estimated by the persons skilled in the art. Lacking constraints, both arms will have identical lengths. This structure advantageously enables to carry out a fine positioning in a wider area of the working space by reproducing, if necessary, the steps of positioning the centre of the OPA, the prepositioning and the fine positioning of the terminal end of the robot arm so as to position the centre of the OPA as close as possible to the desired target.
While referring to FIG. 10 , in one embodiment enabling the positioning of the terminal end of the robot structure in the three-dimensional space, the structure is composed of 3 rotary connections 802 , 804 , 806 , which are all parallel together and of a prismatic connection 850 along an also parallel axis, with the fine positioning being obtained by elementary movements of the secondary articulations 802 , 804 and 850 , with the articulation 806 being blocked after the prepositioning phase.
While referring to FIG. 11 , in one embodiment relating to a hybrid robot structure enabling the positioning of the terminal end in a plane, the structure is composed of three motorized rotary connections 802 , 804 and 806 , and three passive rotary connections 825 , 826 and 827 . The motorized rotary articulation 802 controls the angular position of the segment 822 and the rotary articulation 804 controls the angular position of the segment 824 . The segments 822 , 823 , 824 and the part of the segment 805 between the articulations 826 and 827 form a parallelogram, ideally a diamond. The centre 810 of the OPA is positioned on the segment 805 in a symmetrical position of the articulation 826 with respect to the articulation 827 . The control method consists in blocking 806 after the prepositioning phase and then in actuating the secondary axes 802 and 804 in the fine positioning phase only. Adding a motorized prismatic connection along an axis parallel to 802 at the end of the segment 807 so as to finely position the terminal end 310 in the three-dimensional space can be considered.
|
The disclosure relates to a robot that has an articulated arm for moving an end in an N-dimensional space including at least N+1 motorized articulations, and a computer for controlling the movements of the motorized articulations. The computer controls a first step of prepositioning the terminal end of the articulated arm and a second step for its fine positioning.
| 8
|
BACKGROUND OF THE INVENTION
This invention relates to methods and compositions for protecting materials from thermal extremes and from flame. It also relates to methods of making the compositions.
The situation in which it is desirable to protect materials from heat and flame include, for example, protecting static structures such as petroleum storage tanks, chemical production equipment, electrical cable trays, and structural steel from the spread of fire; protecting transportation equipment such as tank cars, aircraft cabins and seat cushions from the same risks; protecting the exterior surfaces of spacecraft and high performance aircraft from heat generated by atmospheric friction; and protecting the nozzles of rocket engines from the heat of propellant gases.
Numerous thermal protective coating materials and systems for applying them are known. Some of the materials are foamed passive insulative materials which protect merely by their low thermal conductivity and their thickness as applied. These include foamed cement or intumesced silicates. Other materials provide active thermal protection. Some intumesce when heated to form a thick closed cell protective layer over the substrate. These include silicate solutions or ammonium phosphate paints or materials such as those disclosed in Nielsen et al., U.S. Pat. No. 2,680,077 or Kaplan, U.S. Pat. No. 3,284,216. Other active thermal protective materials include constituents which sublime at a predetermined temperature, such as those disclosed in Feldman, U.S. Pat. No. 3,022,190. The active thermal protective materials disclosed in Feldman, U.S. Pat. No. 3,849,178 are particularly effective; when subjected to thermal extremes, these materials both undergo an endothermic phase change and expand to form a continuous porosity matrix.
Various methods and structures have also been used or proposed for applying these thermal protective coating materials. The most frequent approach is to apply the materials directly to the substrate, without additional structure. For many applications, however, a reinforcing material, such as fiberglass sheet or a wire mesh, has been embedded in the coating material to strengthen the material and prevent it from cracking or falling off the substrate under conditions of flame or thermal extreme. Examples of this approach are found in Feldman, U.S. Pat. No. 3,022,190, Billing et al, U.S. Pat. No. 3,913,290, Kaplan, U.S. Pat. No. 3,915,777, and Billing et al, U.S. Pat. No. 4,069,075. Sometimes the materials are first applied to a reinforcing structure such as a flexible tape or flexible wire mesh, and the combined structure is applied to the substrate. Examples of this approach are found in Feldman, U.S. Pat. Nos. 3,022,190, Pedlow, 4,018,962, Peterson et al, 4,064,359, Castle, 4,276,332, and Fryer et al,4,292,358. In these last-mentioned systems, the purpose of the reinforcing structure may be both to strengthen the resulting composite and to permit its application to a substrate without directly spraying, troweling or painting the uncured coating materials onto the substrate. In any of the foregoing methods and structures, multiple layers are frequently applied to the substrate to provide additional protection.
Presently known materials and methods, however, are not as efficient, in terms of length of protection for a given weight of protective material, as desirable. Efficiency is particularly important because in many applications weight or volume is critically limited. Moreover, heavily loading coating materials with fire retardants may seriously impair their physical characteristics and otherwise limit their suitability as coatings, for example by limiting their film-forming characteristics or their water-resisting characteristics. Presently known materials are thus frequently limited to certain types of applications.
SUMMARY OF THE INVENTION
One of the objects of this invention is to provide systems and compositions for providing more efficient protection against hyperthermal conditions than presently known compositions and systems.
Another object is to provide such systems and compositions which are adaptable to a wide variety of applications.
Another object is to provide such systems and compositions which provide particularly good protection when incorporated in coatings applied to substrates with or without reinforcement or additives.
Another object is to provide such systems and compositions which may be incorporated into the materials being protected or into structures applied to the materials being protected.
Another object of this invention is to provide such systems and compositions which may be tailored for use at different temperature ranges and different ambient conditions.
Other objects of this invention will be apparent to those skilled in the art in light of the following description and accompanying drawings.
In accordance with this invention, generally stated, compositions and systems for protection against hyperthermal heating are provided which incorporate a coordination complex which undergoes multiple endothermic transitions from solid to gaseous state over a substantial temperature range. A coordination complex is "a compound or ion that contains a central usu. metallic atom or ion combined by coordinate bonds with a definite number of surrounding ions, groups, or molecules, that retains its identity more or less even in solution, and that may be nonionic {as tri-ammine-trinitro-cobalt [Co(NH 3 ) 3 (NO 2 ) 3 ] 0 }, cationic {as hex-ammine-cobalt-(III) [Co(NH 3 ) 6 ] +++ }, or anionic {as hexachloroplatinate [PtCl 6 ] -- }." Webster's Third International dictionary (unabridged). Coordination complexes of transition metals are particularly useful, and the salts of such complexes with anions having thermal resistive qualities are particularly preferred. Preferably, the coordination complexes include a three dimensional (tricombic) complex including six ligands which are directly attached to a metal ion and are regarded as bonded to it. A ligand is "a group, ion, or molecule coordinated to the central atom in a coordination complex."
One preferred such salt for use in the present invention is hexamminenickel(II) difluoroborate. This salt includes an octahedrally coordinated complex of nickel(II) with six ammonia molecules oriented in such a way that one unshared pair of electrons from each ammonia is pointed directly at the metal ion to form the resultant complex cation [Ni(NH 3 ) 6 ] 2+ . Further reaction of this metal complex with two tetrafluoroborate (BF 4 ) -1 anions forms the desired complex salt.
Other exemplary salts of coordination complexes are hexamminezinc(II) difluoroborate, a similar salt of a perhaps tetrahedrally coordinated complex of zinc with six ammonia molecules and two tetrafluoroborate anions ([Zn(NH 3 ) 6 ](BF 4 ) 2 ) and diaquotetraamminezinc(II) difluoroborate ([Zn(NH 3 ) 4 (H 2 O) 2 ](BF 4 ) 2 ).
Many other coordination complexes are operative, although methods for the large-scale production of some of them have not yet been described. Other exemplary complexes include the following:
[Ag(NH 3 ) 2 ](BF 4 )
[Co(H 2 O) 6 ](BF 4 ) 2
[Co(NH 3 ) 6 ](BF 4 ) 2
[Fe(H 2 O) 6 ](BF 4 ) 2
[Fe(H 2 O) 5 F](BF 4 ) 2
[Ni(H 2 O) 6 ](BF 4 ) 2
[Cd(NH 3 ) 6 ](BF 4 ) 2
[Cu(NH 3 ) 4 ](BF 4 ) 2
[Ag(NH 3 ) 2 ](SnF 6 )
[Co(H 2 O) 6 ](SnF 6 ) 2
[Co(NH 3 ) 6 ](SnF 6 ) 2
[Fe(H 2 O) 6 ](SnF 6 ) 2
[Fe(H 2 O) 5 F](SnF 6 ) 2
[Ni(NH 3 ) 6 ](SnF 6 ) 2
[Ni(H 2 O) 6 ](SnF 6 ) 2
[Cd(NH 3 ) 6 ](SnF 6 ) 2
[Cu(NH 3 ) 4 ](SnF 6 ) 2
[Zn(NH 3 ) 4 (H 2 O) 2 ](SnF 6 ) 2
[Ag(NH 3 ) 2 ](SbF 6 )
[Co(H 2 O) 6 ](SbF 6 ) 2
[Co(NH 3 ) 6 ](SbF 6 ) 2
[Fe(H 2 O) 6 ](SbF 6 ) 2
[Fe(H 2 O) 5 F](SbF 6 ) 2
[Ni(NH 3 ) 6 ](SbF 6 ) 2
[Ni(H 2 O) 6 ](SbF 6 ) 2
[Cd(NH 3 ) 6 ](SbF 6 ) 2
[Cu(NH 3 ) 4 ](SbF 6 ) 2
[Zn(NH 3 ) 4 (H 2 O) 2 ](SbF 6 ) 2 .
Although the foregoing fluorine-containing salts are preferred for their heat resistant qualities, other salts may also be utilized. Halogen-containing anions are preferred. The complex may also be anionic or neutral, and salts in which both anion and cation are coordination complexes may be utilized. The metal ions of the preferred complexes form oxides in a fire atmosphere, and form thermally reflective components. Other endothermically decomposing complexes may also be used, including alkylamine complexes (methylamine through butylamines), such as salts of tetramethlyamminezinc(II) or dimethylamminenickel(II). A chelating ligand may be also be used instead of an ordinary ligand. A chelating ligand is one containing two or more functional groups so arranged that they can simultaneously occupy positions in the first coordination sphere of the metal ion. Familiar examples are lower alkyleneimines such as ethylenediamine and methylenediamine.
In prior compositions including subliming agents, sublimation takes place at a fixed temperature. In the present invention, gaseous evolution and active heat blockage may begin at a fixed temperature, but this indicates only the starting point of the heat blockage of the new material, which provides heat blockage continuously in a step-wise manner through a substantial temperature range. The present compositions give substantially increased rates of heat blockage, over substantially longer periods and higher temperature gradients.
The coordination complexes may be introduced into porous matrices, such as a porous metal or pyrolytic graphite, or placed under such matrices which are liable to exposure to flame or thermal extremes. The coordination complexes may also be blended with other materials in ratios ranging from about five percent to about ninety percent by weight, preferably about 20% to about 70% by weight. They are particularly useful in coatings. They can be incorporated in compositions which are formed by molding or extruding. In all applications, the material gives a continuous, controlled release of heat blocking material over a defined temperature range.
When the complex is added to a film-forming resin, it may form a superior intumescing agent. When properly matched to the resin, it will also provide protection in accordance with Feldman, U.S. Pat. No. 3,849,178. To provide an effective intumescing action, and to provide an open porosity matrix on application of excess heat, it is important that the carrier resin soften at a temperature near the temperature at which the active material undergoes a phase change, and to provide a heat exchange path for the gases produced by the active material. With previously known active materials, the temperature range of the phase change is small. Hence, the depth from the surface at which the matrix material softens and the active material undergoes a phase change is quite well defined at any given time in the course of exposure to a hyperthermal event such as a fire. The present materials, by contrast, undergo continuous endothermic phase changes over a wide temperature range. This provides a prolonged action of the gasses, and provides a long-term, controlled swelling, and much thicker char layers than previously obtainable, up to twenty times the original thickness of the coating. This provides a longer heat exchange path for the gasses to flow through, in the form of long, connected, open cells. The added retention time of the gasses in the matrix increases the thermal efficiency. Furthermore, the combination of a thick heat exchange matrix having a high temperature at its exposed face and a much lower temperature deeper in the coating, together with an active mechanism within the layer for absorbing and radiating heat, makes the coating an efficient radiator of heat.
For example, the complexes have been mixed with an epoxy-based matrix, with or without flexibilizers, reinforcing fibers, and the like. These complex-containing coatings have been found to give more efficient heat blocking per unit thickness of coating on a substrate.
Therefore, greater thermal protection can be given with the same thickness of material, without sacrificing physical properties of the material. Alternatively, the thickness and weight of the material may be decreased without sacrificing thermal protection, or the material may be formulated with a higher proportion of ingredients which improve the physical properties of the material, such as rheology-enhancing materials, film-formers, heat reflective agents, waterproofing agents, and the like.
The matrix may be strengthened with fibers, inorganic cloth, wire mesh, or otherwise. The fibers may constitute as little as one percent of the matrix or as much as seventy percent. The fibers may be long or a mixture of long and short fibers to provide for the maximum string capability in a particular environment, such as the wall of a tank car, or a structural steel beam, or the throat of a rocket engine. Fibers may be introduced as free fibers, or as a glass or graphite cloth, or as a three-dimensional fabric, for example.
Other materials, particularly those of polyanionic phosphorus-nitrogen compounds (such as ammonium polyphosphate) which have previously been demonstrated to be effective in thermally protective coatings, are believed to have a further synergistic effect with the transition metal complexes of the present invention. In fact, some of the materials of the present invention may be chemically combined with those polyanionic compounds or a precursor of those polyanionic compounds, in particular polyphosphoric acids, to provide a compound having superior heat blockage characteristics. Materials containing phosphorus and nitrogen are known to promote char formation. It is therefore believed that the combination of the present complexes containing nitrogen moieties into a compound containing phosphorus provides a long chain compound combining both endothermic phase change and char formation in one step. The materials combining tricombic transition metal complexes with polyphosphate may be formed from those compounds themselves, or they may be formed in situ during the formation of the complex or the polyphosphate. The complexes can also be blended with numerous polyanionic phosphorus-nitrogen containing compounds such as melamine pyrophosphate or monoammonium phosphate.
The complexes themselves can be blended to give a broader range of temperatures at which they perform their heat absorbing or blocking functions, and they can also be microencapsulated so as to increase the partial pressure of the complexes as they are exposed to heat and thereby raise the temperature at which they become active.
Other aspects of the invention will be better understood in the light of the following description of the preferred embodiments of materials in accordance with the present invention and examples of making and using them.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings, FIG. 1 is a graphical representation of differential scanning calorimetry thermograms for illustrative coordination complexes in accordance with the present invention.
FIG. 2 is a graphical representation of thermogravimetric analyses of illustrative coordination complexes in accordance with the present invention, selected prior art materials also being shown for comparison.
FIG. 3 is a graphical representation of differential scanning calorimetry thermograms for illustrative coating compositions in accordance with the present invention, as compared with prior art coating compositions.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following Examples are illustrative of the methods of making the complexes for use in the present invention, of the compositions and methods of the present invention, and of their performance in comparison with previously known compositions and methods.
EXAMPLE 1
Tricombic hexamminenickel(II) difluoroborate for use in the present invention was made by dissolving 0.01 mole of NiCl 2 . 6H 2 O (2.38 g) in 40 ml H 2 O, and adding 100 ml of concentrated NH 4 OH. The green color of the solution changed instantaneously to a characteristic blue as the nickel chloride reacted to form the hexamminenickel complex. Excess unreacted NiCl 2 . 6H 2 O was removed by filtration. To the clear blue solution was added 0.02 moles of NH 4 BF 4 (2.09 g) with stirring. After all the ammonium fluoroborate had been added, the mixture was stirred for fifteen more minutes, then allowed to stand at room temperature for thirty minutes. A light blue solid precipitate formed. The precipitate was filtered through a fast filter #41. Excess NH 4 BF 4 was removed by washing with 100 ml dilute (10%) NH 4 OH. The process produced about 93% of theoretical yield of hexamminenickel(II) difluoroborate, having a distinct blue color and a solubility of about 1.3% to 1.5 %.
The solubility of the material may be further reduced below 1% by washing with hot 10% NH 4 OH.
EXAMPLE 2
Tricombic diaquotetraamminezinc(II) and hexamminezinc(II) difluoroborate for use in the invention were made in a similar manner. 0.1 mole of ZnCl 2 (13.6 g) was dissolved in 40 ml deionized H 2 O, and 100 ml of concentrated NH 4 OH was added. The clear solution changes rapidly to a milky white color of diaquotetraamminezinc(II). Further addition of excess ammonia produces hexamminezinc complex. Separately, 0.2 moles of NH 4 BF 4 (20.9 g) is stirred into 25 ml of water, then added slowly to the desired zinc ammine complex. A gel-like material is formed which upon further mixing for 15 minutes is let to stand at room temperature for 30 minutes. The precipitate is collected, washed, filtered, and dried.
EXAMPLE 3
A conjugate of hexamminenickel(II) fluoroborate and a polyphosphate was formed by adding to 500 grams of polyphosphoric acid, H(PO 3 H) n OH, having a phosphoric acid equivalent of 115%, 500 grams of tetrafluoroboric acid, HBF 4 , having an acid equivalent of 50%, with mixing. This syrupy mixed "super"-acid was added in an ice bath to a 90% ammoniacal solution of nickel II complex (900 g. nickel complex in 100 g. ammonia) and mixed. There was an exothermic reaction of about 50° C., and the blue color of the hexamminenickel complex changed to a light green as the exotherm continued. The material was let stand and it solidified. The resulting solid was collected and pulverized, then washed once with water to remove unreacted materials and soluble by-products.
Fourier transform infrared (FTIR) analysis of this new complex revealed bond formation of phosphorus-nitrogen as expected in the 3300 cm -1 region.
Thermogravimetric analysis (TGA) of this complex indicated a more stable complex. Its thermograms had two distinct peaks at temperatures of T 1 =182° C., with 96% of the material still remaining, and at T 2 =281° C. with 81% of the material remaining. The mass loss at final temperature of 750° C. was 56%, i.e., 44% of the material remained as char. The complex has a solubility of 7.12% and a pH of 6.73.
Differential scanning calorimetric (DSC) analysis of this material indicated an endothermic decomposition at T 1 =210° C. to230° C. and a major endothermic peak starting at 300° C. to 450° C.
EXAMPLE 4
A conjugate of diaquotetraamminezinc(II) fluoroborate and a polyphosphate was similarly formed by mixing 500 grams of polyphosphoric acid having a phosphoric acid equivalent of 115% with 500 grams of tetrafluoroboric acid, having an acid equivalent of 50%. This syrupy mixed "super"-acid was added in an ice bath to a 90% ammoniacal solution of zinc II complex (900 g. zinc complex in 100 g. ammonia) and mixed. There was an exothermic reaction of about 65° C. without change in the color of the zinc complex. The material solidified and was pulverized. The material was 85% soluble and had a pH of 3.5.
TGA indicated 91% of the material remaining at T 1 =289° C. and 60% remaining at T 2 =396° C. The final mass (char) at 750° C. was 41% of the original material.
DSC of this complex also indicated an endothermic decomposition starting at T 1 =216° C. to 283° C. and a major endothermic peak starting at 372° C. to 445° C.
EXAMPLE 5
The materials of Examples 1-4 were tested in a differential scanning calorimeter (DSC). A DSC measures and records the energy necessary to maintain thermal equilibrium between a test sample and a reference. Indium is used as a calibration standard. Generally, a sample of known mass is heated at a constant temperature rate and the rate at which energy is absorbed (endothermic) or released (exothermic) is recorded against temperature. A phase change is represented as a peak. The area under the peak is proportional to the heat of fusion, sublimation or vaporization. In such devices, the rate of heat flux is a function to the fourth power of the temperature. Therefore, the rate of heat flux may be directly correlated with temperature.
As shown in FIG. 1, the DSC analysis shows that a simple endothermic material, illustratively ammonium fluoroborate (1), decomposes endothermically at 220° C. by losing its ammonia as gas; more importantly, this compound provides no additional endothermic mechanism until it reaches about 400° C.
By contrast, hexamminenickel(II) difluoroborate (2) and diaquotetraamminezinc tetrafluoroborate (3) begin to decompose endothermically below 200° C. and continue to decompose in a generally continuous and increasingly endothermic manner to a temperature well in excess of 400° C. for the nickel complex and 450° C. for the zinc complex. The total amount of energy absorbed, as represented by the area under the peaks, indicates that the materials are far better heat blockers than simple compounds like ammonium fluoroborate and that they will provide superior heat blockage when incorporated in substrates or in coatings applied to substrates. The indium calibration standard is shown as (4) in FIG. 1.
As shown in FIG. 2, a thermogravimetric analysis (TGA) of hexamminenickel(II) difluoroborate (5) and diaquotetraamminezinc tetrafluoroborate (6) confirms that the unconfined materials decompose to gaseous components at lower temperatures than pentaerythritol (7) or ammonium polyphosphate (8), and that they both leave a substantial solid residue. The TGA's of hexamminenickel(II) polyphosphoborate (9) of Example 3 and diaquotetraamminezinc(II) polyphosphoborate (10) of Example 4 are also shown in FIG. 2. The relatively low temperatures at which the tricombic complexes of the present invention volatilize provide early absorption of energy in a fire or other hyperthermal event. The TGA does not, of course, reflect recombinations which occur in a typical fire or other hyperthermal event.
EXAMPLE 6
The synergistic effects and heat absorbing effectiveness of different concentrations of diaquotetraamminezinc(II) fluoroborate and hexamminenickel(II) fluoroborate in epoxy formulations were studied by differential scanning calorimetry. Differing parts by weight of the coordination complexes were added to the following formulation (Table 1), and the DSC thermograms were charted as shown in FIG. 3. The formulations of Table 1 were made in two parts and mixed, in accordance with standard procedure. All figures are parts by weight.
TABLE 1______________________________________EXAMPLE A B C D E F G______________________________________MATERIALEpoxy 34.2 34.2 34.2 34.2 34.2 34.2 34.2(EEW = 182-192)Solvent 5.1 5.1 5.1 5.1 5.1 5.1 5.1Pentaerythritol 20.4 20.4 20.4 20.4 20.4 20.4 20.4Melamine 28.6 28.6 28.6 28.6 28.6 28.6 28.6Polysulfide resin 38.85 38.85 38.85 38.85 38.85 38.85 38.85Catalyst (amine) 5.25 5.25 5.25 5.25 5.25 5.25 5.25Solvent 31.35 31.35 31.35 31.35 31.35 31.35 31.35Ammonium 67.5 67.5 67.5 67.5 67.5 67.5 67.5PolyphosphateAqAmZnBF.sub.4 0 11.6 23.5 47.0 0 0 0(Example 2)AmNiBF.sub.4 0 0 0 0 11.6 23.5 47.0(Example 1)______________________________________
In FIG. 3, A is the standard epoxy coating material, B is 5% zinc complex, C is 10% zinc complex, D 20% zinc complex; E is 5% nickel complex; F is 10% nickel complex; and G is 20% nickel complex. The ordinate represents calories/second and the abscissa represents temperature (degrees C), so that the Figure shows the change in enthalpy of the system. The area under each curve is an indication of the material's effectiveness as a heat blocker. It will be seen that the behavior of all the materials falls into five phases: (1) up to about 180° C. the temperature within the material rises linearly (preheating phase); (2) from about 180° C. to about 230° C. the binder endothermically decomposes; (3) from about 230° to 325° C. the standard subliming agents undergo an endothermic phase change; (4) from about 325° C. to about 400° C. the material intumesces; and (5) above about 400° C. char is formed. Superimposed on this behavior, however, is a remarkable absorption of energy paralleling the results shown in FIG. 1 for the pure transition metal complexes.
As shown in FIG. 3, the compositions containing transition metal complexes in accordance with the present invention provide a remarkable effectiveness in hyperthermal heat blockage of a polyanionic-phosphorus-nitrogen system in an epoxy binder as compared with formulation A. Further, the time required for vitrification and the subsequent endothermic protection, and hence the contribution to a stable char formation in these systems happens at these formulations softens at a temperature just before endothermic decomposition of the complexes around 200° C.
EXAMPLE 7
To test the effectiveness of the materials of the present invention in presently standard intumescing coating materials, a basic fire-protective formulation having the solids content shown in the following Table 2 was made, solvent being added to each half to form the desired consistency:
TABLE 2______________________________________ Parts by weight______________________________________Epoxy resin (EEW = 182-192) 22Penaterythritol 8Melamine 10Titanium dioxide 6Glass fibers 4Polysulfide 22Curing agent 3Ammonium polyphosphate 23Glass fibers 2______________________________________
The formulation of Table 2 (identified as Example H) is a highly effective and efficient fire-protective formulation which operates in accordance with Feldman, U.S. Pat. No. 3,849,178, which when subjected to thermal extremes both undergoes an endothermic phase change and expands to form a continuous porosity matrix.
Improved formulations (Examples J-U) in accordance with the present invention were formed by adding to the basic fire-protective formulation of Table 2 (Example H) an additional 10, 30 and 50 parts by weight of materials in accordance with Examples 1-4 per 100 parts by weight of the basic fire-protective formulation, Example H.
These formulations were tested in a simulated fire environment to determine the rate of temperature rise of a protected substrate.
The protective formulations were sprayed onto a sample substrate. Following the guidelines of Department of Defense (Navy) test NADC-84170-60, the substrate is a 0.060" steel plate coated with 0.140" (140 mils) of protective material. The plate is protected on five sides by a ceramic pad. The exposed (coated) side of the plate is subjected to an air-vitiated liquid propane gas (LPG) flame having a temperature near its point of impingement on the sample of from 1800° to 2000° F. The rear (uncoated side) of the plate is provided with three thermocouples for measuring the temperature of the back of the plate, and the number of seconds required for the average thermocouple temperature to reach 500° F. is measured. The efficiency of each of the formulations was then calculated by dividing the number of seconds required for the average thermocouple temperature to reach 500° F. by the thickness in mils of the material (140).
TABLE 3______________________________________EX- THERMALAMPLE COORDINATION COMPLEX PARTS EFFICIENCY______________________________________H NONE -- 3.14 sec/milJ Hexamminenickel(II) 10 6.25 sec/mil difluoroborateK Hexamminenickel(II) 30 5.39 sec/mil difluoroborateL Hexamminenickel(II) 50 4.46 sec/mil difluoroborateM Diaquotetraamminezinc 10 6.39 sec/mil (II) fluoroborateN Diaquotetraamminezinc 30 5.18 sec/mil (II) fluoroborateO Diaquotetraamminezinc 50 5.07 sec/mil (II) fluoroborateP Hexamminenickel(II)- 10 6.39 sec/mil polyphosphateQ Hexamminenickel(II)- 30 4.36 sec/mil polyphosphateR Hexamminenickel(II)- 50 3.96 sec/mil polyphosphateS Diquotetraamminezinc(II)- 10 7.68 sec/mil polyphosphateT Diquotetraamminezinc(II)- 30 7.00 sec/mil polyphosphateU Diquotetraamminezinc(II)- 50 6.39 sec/mil polyphosphate______________________________________
From the foregoing, it will be seen that the compositions of the present invention provide a remarkable and synergistic improvement in protection from fire and other hyperthermal extremes, even as compared with highly effective and efficient materials. In each of these cases, addition of up to about 10% of the transition metal complex to the standard formulation increased char and strengthened the char formed.
EXAMPLE 8
To compare the effectiveness of the formulas containing tricombic transition metal complexes as compared with the prior art, thermal protective materials were made corresponding generally to that of Example 11 of Feldman, U.S. Pat. 3,849,178. These formulations were as follows:
TABLE 4______________________________________ Parts by weight______________________________________Heat blocking material 60Epoxy resin (EEW = 182-192) 15Polysulfide resin 15Tertiary amine curing agent 5Solvent (toluene) 5______________________________________
The heat blocking material (EXAMPLES V-Z) for each formulation was as shown in the following Table 5. Each material was tested in a simulated fire environment to determine the rate of temperature rise of a protected substrate in accordance with the same procedure as in the foregoing Example 7, and the results, expressed in thermal efficiency was determined as shown in Table 5.
TABLE 5______________________________________EX- THERMALAMPLE HEAT BLOCKING MATERIAL EFFICIENCY______________________________________V Molybdenum hexacarbonyl 2.00 sec/mil (Prior art)W Hexamminenickel(II) 3.64 sec/mil fluoroborate (Example 1)X Diaquotetraamminezine(II) 3.25 sec/mil fluoroborate (Example 2)Y Hexamminenickel(II)- 4.21 sec/mil polyphosphofluoroborate (Example 3)Z Diaquotetraamminezinc(II)- 3.36 sec/mil polyphosphofluoroborate (Ex. 4)______________________________________
EXAMPLE 9
The following compositions and tests were made to show the ability of compositions of the present invention to protect plastic materials from flame spread. A plastic material having the composition of the following Table 6 was formed:
TABLE 6______________________________________ Parts by weight______________________________________Epoxy resin (DER-331) 25Liquid polysulfide resin 25Catalyst (DMP-30) 4______________________________________
To this material were added the hexamminenickel(II) difluoroborate and diaquotetraamminezinc(II) difluoroborate transition metal complexes of Examples 1 and 2 in loadings of 15%, 25%, and 35%. The unmodified material and modified materials were tested in accordance with Underwriters'Laboratory test UL94HB, using a thin strip of the cured material, clamping one end of the strip to hold the strip horizontal, and exposing the free end of the strip to a flame. It was found that the unloaded plastic strip burned rapidly, and that each of the loaded samples greatly reduced flammability under the test conditions. All but the 15% loaded diaquotetraamminezinc(II) difluoroborate sample were selfextinguishing.
Numerous variations in the materials and methods of the present invention will be apparent to those skilled in the art in light of the foregoing disclosure. Merely by way of example, the materials of the invention may be applied to a mesh support, such as the support of Feldman, U.S. Pat. No. 4,493,945 or otherwise. The materials, either in the form of the pure coordination complexes or the complexes in a carrier, may be incorporated into matrices such as porous materials. For example, by using a water-soluble complex, rather than the insoluble complexes of the foregoing examples, the materials may be absorbed into a wooden substrate. Of the illustrative materials, the zinc complexes tend to be more soluble than the nickel complexes. The materials may also be used in a viscous carrier under a porous skin in aerospace applications, to give a boundary layer and transpirational cooling under supersonic heating conditions; this arrangement permits simple reloading of the protective material after each use (flight).
These variations are merely illustrative.
|
A product and process by which heat from hyperthermal sources is blocked by compositions including coordination complexes. The compositions provide a sustained, uniform, and controlled method of heat blockage in an artificial boundary layer or heat exchange matrix. When the compositions are incorporated in a coating composition, the rate of discharge of the coating medium is continuous, gradual, and controlled to the desired rate level for a given thermal environment.
| 8
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to an electrical switch device having at least one movable contact element, which can be moved by means of a switch activation member from a shut-off position to an operation position, and having a housing having at least one receptacle for an opposing contact element that can be contacted by the movable contact element when in its operation position.
2. Description of the Prior Art
In known switches having the above-mentioned characteristics, the movable contact element is formed as a bridge, the two end portions of which each contact one of the opposing contact elements when the switch is closed, which opposing contact elements are nondetachably secured in a suitable manner in the switch housing. These opposing contact elements are generally provided with a screw connection, plug connection or soldered connection. In mounting the apparatus in which the switch is installed, the switch housing must be connected to the apparatus, by means of screws or the like. In addition, the connection between the leads and the leads of the opposing contact elements must be established.
OBJECTS AND SUMMARY OF THE INVENTION
A primary object of the invention is to an electrical switch device, is more economical to connect with the associated apparatus than conventional switches.
Because switches of this type are generally not equipped or not completely equipped with the necessary opposing contact elements, at least the mounting costs for the missing opposing contact elements are eliminated. In switches having a movable contact element which on one side is in continuous contact with the associated electrical circuit and therefore only cooperates with a single stationary contact element, this single stationary contact element can be missing.
The switch according to the present invention is incapable of functioning until the missing stationary contact element or missing stationary contact elements have been placed into the associated receptacles. Preferably, this occurs during the mounting of the switch in the apparatus wherein each missing stationary contact element is introduced into its receptacle. To arrange the introduction of a stationary contact element of this type as simply as possible, in one preferred embodiment the receptacle has an insertion opening through the wall of the switch housing. This insertion opening is preferably formed as a guide channel for the contact element, so that it is assured that this contact element will come into the correct position in the switch as it is inserted.
For a correctly functioning arrangement of the subsequently introduced contact element it is also advantageous if the portion of the receptacle located inside the housing contains a support surface facing the movable contact element for the contact element to be introduced, which at least partially forms the opposing contact element.
In one preferred embodiment the switch housing is provided with one portion of a plug connection, whereby this plug connection is formed such that its plug direction coincides with the direction in which the opposing contact element must be introduced into the switch housing. In that way only a single plug process is required to correctly position the switch in the apparatus and to introduce the contact element or contact elements into the switch. Particularly advantageous is an arrangement of the portion of the plug connection provided on the wall of the housing coaxially to the insertion opening for the opposing contact element.
So as not to require more screws to secure the switch in its correct position, in one preferred embodiment, at least one detent connection is provided consisting of a resilient pawl and a notch, which detent connection engages at the end of the insertion process.
The shape of the opposing contact element can be freely selected within wide bounds. However, the shape of a rack or panel plug connector is very advantageous.
The switch according to the present invention can be completed by other means than by opposing contact elements securely arranged in the apparatus. When necessary, opposing contact elements can also be subsequently introduced that are provided with a plug connection, a screw connection or the like.
In one preferred embodiment, the opposing contact element is provided with at least one longitudinal slot extending to the end which comes to rest inside the housing. A wire can be clamped into such a longitudinal slot, thus simplifying the connection of the wire, which may, for example, belong to a lighting device. Such an arrangement may reduce the costs even further. Establishing wire contact in a longitudinal slot of this type is made especially easy by providing the wire in a channel crossing the longitudinal slot. The wire is secured in the longitudinal slot and supported by the wall of the channel.
To reduce costs even further, in one preferred embodiment, the two elements comprising the switch housing are joined by integral tabs which engage in corresponding openings as the housing elements are joined, and like the housing, have a shape that results in a detent connection.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention is described in greater detail below with the aid of an exemplary embodiment illustrated in the drawings, where:
FIG. 1 is an elevational view of a preferred embodiment of the invention, in section taken along line I--I of FIG. 4,
FIG. 2 is another sectional view taken along line II--II of FIG. 4,
FIG. 3 is another sectional view taken along line III--III of FIG. 4, and
FIG. 4 is a plan view in section of a preferred embodiment in the plane of the stationary contact elements.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings wherein like elements are shown by like reference numerals throughout the several views, the switch device illustrated in FIGS. 1 through 4 has an essentially block-like switch housing which is comprised of an upper housing element 1 and a lower housing element 2. As shown in FIGS. 3 and 4, upwardly directed connecting tabs 3 are located in the four corner areas of the lower housing element 2 to connect the upper and lower housing elements, each of which are made of plastic. Connecting tabs 3 taper toward their upper ends and form a plurality of flat annular rings. These connecting tabs 3, which can also have a cross-sectional shape that deviates from a circle, engage in correspondingly shaped channels in the upper housing element 1, thus producing an automatic detent connection when the two housing elements 1 and 2 are brought together.
A passageway or opening for receiving a pin-like switch activating member 4 is provided in the upper side of the upper housing element 1. As seen in FIGS. 1 and 2, switch activating member 4 is formed on a bearing member 5. Two bridge contacts 6, of the double pole switch comprise two parallel, moving contact elements. A prebiased return spring 7, which is formed as a helical compression spring, engages in a recess in the bearing member 5 which is open toward the lower housing element 2 and is aligned with the switch activating member 4. The other end of return spring 7 is supported on the base 8 of the lower housing element 2.
Upper housing 1 terminates with an elastic rubber collar which is secured on one end in an annular groove in the switch activating member 4, and on the other end in a circular recess provided in the upper housing element 1. An internal support bead 1' and an external, inwardly rolled boundary wall 1" seals the passage opening for the switch activating member 4. To close the switch, activating member 4 must be depressed against the force of the return spring 7.
At its lower end, the bearing member 5 has two diametrically opposite supports 10 for the two bridge contacts 6. Supports 10 project laterally to the direction of movement of bearing member 5. The two bridge contacts 6 are pressed against the lower supports 10 by respective helical compression springs 11. The other ends of the helical compression springs 11 are supported by two arms 12, which are integrally formed with the bearing member 5 at the upper end thereof. Arms 12 are located above the supports 10 and extend laterally in the same manner that supports 10 extend laterally from the bearing member 5, with respect to the direction of movement of bearing member. The central portion of bearing member 5 is provided with two guide ribs 13 (FIG. 3 and 4) which extend in the direction of movement of the bearing member 5 and are guided by a groove-like guide 14 in the housing portion, as shown in FIG. 4. At least one of the two arms 12 supports a shank spring 15 in the area of its free end, the shanks of which extend from the arm 12 toward the floor 8 and rest on respective sliding surfaces of a portion of material 16 of the lower housing element 2 which is spaced from the floor 8.
As shown in FIG. 1, two opposing sliding surfaces 17 are provided shaped as noses, which are engaged by the respective ends of the shank spring 15 when the bearing member 5 is in the closed position of the switch. By means of this forcible detent, a snap effect is achieved and reduces the force that must be exerted on the switch activating member 4 to hold it in the closed position after the switch is closed.
Respective stationary contact elements 19 (FIG. 4), which may include a screw connection, are associated with one end of the two bridge contacts 6, which are slotted in the longitudinal direction in their two end sections. Two contact elements 19 are located on the underside of each end section. These two stationary contact elements 19 are secured by the upper housing element 1 in the receptacle provided in the lower housing element 2. They each have a longitudinal bore 20 running laterally to the direction of movement of the bearing member 5 to receive the conductor to be connected thereto as well as a lateral bore 21 that is accessible from outside the housing, which contains a clamping screw (not shown). Of course, these two stationary contact elements 19 could also be provided with a plug connection or a solder connection.
On the side opposite the two stationary contact elements 19, the switch housing has two insertion openings 22 which are rectangular in cross-section, the longitudinal axes of which openings lie parallel to each other and to the axes of the longitudinal bores 20. The lower portion of the insertion openings 22 is limited by the lower housing element 2 and the upper portion thereof is limited by the upper housing element 1, enabling them to be produced without problem. As shown in FIGS. 1 and 4, truncated projections 23 are formed on the outside of the housing wall containing these insertion openings concentric to the two insertion openings 22, which form a portion of a plug connection and also lengthen the channel formed by the insertion openings 22.
The cross-section of the insertion openings 22 is adapted to the cross-section of type plug contact elements 24, which first pass through the insertion openings 22 into the interior of the housing as the switch is installed into the associated apparatus. As shown in FIG. 1, the lower housing element 2 includes an extension of the insertion opening 22, and a support surface 25 for the plug contact element 24 that extends to the material section 16. In addition, FIG. 1 shows that the insertion opening 22 and the support surface 25 are arranged such that the contact surface of plug contact element 24 facing the bridge contacts 6 lie in the same plane as the stationary contact surface of the contact element 19 secured in the switch housing.
The two plug contact elements 24 are formed by the end portions of respective bifurcated connectors which project beyond the surface 26 of the associated apparatus by the distance required for the support in the switch housing. Respective truncated recesses 27, concentric to the two bifurcated connectors, are provided in the surface 26, the shape of which corresponds to that of the projections 23. When the switch housing abuts the surface 26 a plug connection is therefore produced between it and the apparatus, which positions the switch and absorbs the forces that occur laterally to the insertion direction. A detent pawl 28 projects from the outside of the switch housing in the insertion direction and is formed integrally with the upper housing element 1; it engages behind a detent projection 29 on the apparatus when the switch abuts the surface 26, and thus secures the switch from becoming detached from the apparatus.
As shown in FIG. 4, the two bifurcated contact elements 24 are provided with a centrally located, longitudinal slot 30 that extends to the free end of the contact element 24. The two adjacent furcations thus formed are contacted by the respective contact elements 18 of the associated end section of the contact bridges 6 when the switch is closed. As shown in FIG. 1, the end sections of the bridge contacts 6 adjacent to a central section are curved toward the contact surfaces of the contact element 24. Thus, the contact elements 18 are pushed onto the contact elements 24 when the bridge contact 6 is pressed through into its extended position. This provides a self-cleaning effect for the contact surfaces.
Each longitudinal slot 30 of the two contact elements 24 is perpendicularly crossed by a channel 31 provided in the lower housing element 2 which extends into the upper housing element 1 for receiving the connecting wire 32 of an electrical component 33, e.g., a capacitor, to be electrically connected to the contact element 24. The diameter of the connecting wire 32 is somewhat larger than the width of the longitudinal slot 30. This achieves a good contact when the contact element 24 is introduced through the insertion opening 22 and the connecting wire 32 thereby enters into the conical longitudinal slot 30 and widens it somewhat.
To accommodate the component 33, the lower housing element 2 is provided with a downwardly open chamber formed by sidewalls each having retaining ledges 35 formed on the side walls. As shown in FIG. 2, ledges 35 hold the electrical component 33 in the chamber 34. Accordingly, the mounting of the electrical component 33 is extremely simple and economical.
Although only preferred embodiments are specifically illustrated and described herein, it will be appreciated that many modifications and variations of the present invention are possible in light of the above teachings and within the purview of the appended claims without departing from the spirit and intended scope of the invention.
|
A switch, particularly an apparatus switch having at least one movable contact element is described. The switch can be moved by an activating member from a shut-off position into an operational position, and includes a housing that has at least one receptacle for an opposing contact element that can be contacted by the movable contact element in its operational position. The receptacle is initially unequipped with a contact but is formed to subsequently receive a contact from the outside.
| 7
|
RELATED APPLICATIONS
[0001] This U.S. Patent Application claims priority under 35 U.S.C. §120 from U.S. Patent Application 61/414,322, filed on Nov. 16, 2010. The disclosure of this prior application is considered part of the disclosure of this application and is hereby incorporated herein by reference in its entirety.
TECHNICAL FIELD
[0002] This invention relates to knitting fabrics from yarns of differing stretch properties, such as from both elastomeric and non-elastomeric yarns, and the fabrics produced thereby.
BACKGROUND
[0003] Single-knit jersey fabrics are generally inexpensive and found in such things as underwear and T-shirts. Due to their interconnected loop structure, knit materials in general can be deformed or stretched by elongating individual stitches, even when the fabric is knit of yarns made of non-elastomeric fiber materials. To provide a greater degree of stretch and stretch recovery, elastomeric yarns may be knit into a fabric. One type of elastomeric yarn in common use is spandex. Spandex, sometimes sold under the trade name LYCRA®, is a manufactured fiber of a long-chain synthetic polymer containing at least 85 percent segmented polyurethane. The polyurethane is prepared from a polyether glycol, a mixture of diisocyanates, and a chain extender and then melt-spun, dry-spun or wet-spun to form the spandex fiber. Another type of elastomeric yarn is polybutylene-terephtalate (PBT) yarn, a highly elastic, friction-texturized polyester yarn available from Swicofil AG Textile Services of Emmenbruecke, Switzerland.
[0004] Knitting spandex yarns together with non-elastomeric yarns in a jersey knitting process is sometimes referred to as “plaiting” or “plating,” in which the non-elastomeric yarn and the bare spandex yarn are kept in a parallel, side-by-side relation throughout the knit, with the relation between the two yarns controlled such that the spandex material is always kept on one side of the non-elastomeric yarn. In plush or pile materials, the spandex yarn is generally kept away from the technical face of the fabric (i.e., the side opposite the raised pile), so as to present the typically more attractive and comfortable non-elastomeric yarn material at the technical face and to protect the spandex yarn fibers from snagging. Spandex yarns may also accept dye differently than other yarn materials, resulting in unacceptable color variations if exposed on the fabric surface. Stretchable pile fabrics may be made in a three end knitting process, meaning that three separate yarns are brought into the machine and knit together to form the fabric: a non-elastomeric ground yarn, an elastomeric ground yarn, and a pile yarn. As knit, the non-elastomeric and elastomeric ground yarns are generally limited to the ground of the fabric, and the pile yarns extend out of the fabric to form discrete loops, which in some cases are cut or shaved after processing to form a bed of fiber ends. The non-elastomeric and elastomeric ground yarns may be plated to keep the elastomeric yarns away from the technical fabric face while being knit into the fabric, or may be “laid in” or tucked into the knit structure using needle selection cams, to trap the elastomeric yarns between the non-elastomeric ground and pile yarns.
[0005] Some knit materials are formed as circular knit materials, meaning that they are initially knit as a tube on a machine in which the knitting needles are organized into a circular knitting bed. The needles are sequentially activated about the circular bed, such as by a cam surface acting against butt ends of the rotating set of needles, to lift and accept a yarn fed from a spool into a yarn carrier plate, to form a spiral row of stitches about the end of the tube. Such a process is also referred to as circular weft knitting. To circular knit a three end stretchable plush or pile fabric, the non-elastomeric ground yarn, the elastomeric ground yarn and the pile yarn are each fed separately to respective holes or slots in the carrier plate. In particular, the elastomeric yarn is kept separate from the non-elastomeric ground yarn until the point of introduction to the needles, so as to maintain the strict positional relation of non-elastomeric and elastomeric yarns, in order to keep the spandex material from being exposed, or “grinning through” the technical face of the fabric. In some cases, such as on some Orizio machines made by Orizio SRL, Brescia, Italy, the elastomeric yarn is run outside of the carrier plate, and guided into the needle before it closes by an outside guide roll. Circular knitting machines are also available from Vanguard Supreme, a division of the Monarch Knitting Machinery Corporation, in Monroe, N.C.
[0006] Improvements in stretchable laminate constructions and methods of making them will hopefully result in further advances in comfort and usefulness, as well as in reductions in costs.
SUMMARY
[0007] One aspect of the invention features a method of forming a circular knit fabric. The method includes feeding a multi-filament non-elastomeric yarn from a first spool into an aperture defined in a yarn carrier plate that guides the non-elastomeric yarn sequentially to a series of knitting needles spaced about a circular needle array, while feeding an elastomeric yarn from a second spool to the yarn carrier plate, such that a fabric is knit to have a ground comprising both the non-elastomeric yarn and the elastomeric yarn. The non-elastomeric yarn and the elastomeric yarn are fed together into the carrier plate aperture in an untwisted, unwrapped relation, such that the fabric ground is knit to have a technical face in which portions of the non-elastomeric yarn are exposed in some areas and portions of the elastomeric yarn are exposed in some areas.
[0008] In some embodiments, the method also includes feeding a pile yarn from a third spool into a pile yarn aperture defined in the carrier plate, such that the pile yarn is delivered to the knitting needles to form a pile extending from a technical back of the knit fabric.
[0009] In some examples the non-elastomeric yarn is a texturized yarn.
[0010] In some cases, the elastomeric yarn is a non-wrapped yarn.
[0011] Some examples of the method also include applying a stretchable binder to the knit fabric ground, and/or adhesively laminating the technical face of the knit ground of the fabric to a technical face of another fabric. The other fabric may also have a technical face at which elastomeric yarn is present.
[0012] Adhesively laminating the technical face of the knit ground may include applying a stretchable acrylic adhesive to the technical face of the knit ground. Preferably, the adhesive is applied to cover no more than about 70 percent of an area of the knit ground.
[0013] Another aspect of the invention features a circular knit fabric with a knit ground formed at least in part of an elastomeric yarn and a non-elastomeric yarn, with the elastomeric and non-elastomeric yarns following a common path through the ground. A pile is formed of at least one pile yarn knit with the ground and extends from a side of the fabric opposite a technical face. Both the elastomeric yarn and the non-elastomeric yarn of the knit ground are present on the technical face of the knit fabric, with the technical face including some areas of multiple adjacent stitches in which the elastomeric yarn covers the non-elastomeric yarn, and other areas of multiple adjacent stitches in which the non-elastomeric yarn covers the elastomeric yarn.
[0014] In some examples the non-elastomeric yarn is a texturized yarn, and/or the elastomeric yarn is non-wrapped yarn.
[0015] In some embodiments, the knit ground includes a binder, such as an elastomeric binder, disposed within the ground.
[0016] Another aspect of the invention features a stretchable fabric laminate of two of the circular knit fabrics described herein, adhesively laminated with their technical faces in face-to-face relation, with some of the areas of multiple adjacent stitches of one of the fabrics in which the elastomeric yarn covers the non-elastomeric yarn directly adhesively bonded to some of the areas of multiple adjacent stitches of the other of the fabrics in which the elastomeric yarn covers the non-elastomeric yarn, such that the elastomeric yarn of the knit ground of one of the fabrics is directly adhesively bonded to elastomeric yarn of the knit ground of the other of the fabrics.
[0017] In some examples of the laminate, one of the knit fabrics is relatively more hydrophilic than the other knit fabric.
[0018] Various examples of the proposed fabrics and methods described herein can provide particularly useful fabric properties, particularly in inexpensively providing a knit fabric with a technical face at which both elastomeric and non-elastomeric yarns are present. Lamination of such knit fabrics can be facilitated by having elastomeric as well as non-elastomeric yarns present on technical faces that are bonded together.
[0019] The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims.
DESCRIPTION OF DRAWINGS
[0020] FIG. 1 is a schematic illustration of a fabric laminate material, in side cross-sectional
[0021] FIG. 2 is an enlarged photograph of a fabric laminate material, in side view.
[0022] FIG. 3 is a schematic illustration of a knit ground structure.
[0023] FIG. 4 shows yarn paths through a three yarn knit material, with pile yarn included in every course and an elastomeric ground yarn included in every other course.
[0024] FIG. 5 illustrates a machine and process for forming a fabric laminate from two knit materials.
[0025] FIGS. 6 and 7 show a yarn feeder assembly in use in a circular knitting machine.
[0026] FIG. 8 shows a yarn feeder assembly as viewed from below.
[0027] FIG. 9 is a highly enlarged side view of a laminate, showing discrete amounts of adhesive bonding two knit fabrics together.
Like reference symbols in the various drawings indicate like elements.
DETAILED DESCRIPTION
[0028] Referring first to FIG. 1 , a flexible, breathable fabric laminate 10 includes a first stretchable fabric layer 12 in the form of a knit fabric 14 that has ground yarns and pile yarns forming hook-engageable fiber loops 16 exposed on an outer surface of the fabric laminate, and a second stretchable fabric layer 20 in the form of a second knit fabric 30 having a technical face 24 bonded directly to the technical face 18 of the first fabric layer 12 by an adhesive 22 . As will be discussed further below, elastomeric yarns are included in the ground yarns of both of the knit fabrics, so as to make each fabric elastically stretchable.
[0029] Both knit fabrics 14 , 30 may be jersey pile knits that are knit to have sections of pile fibers present on technical faces 18 , 24 along with at least some elastomeric ground yarns. Either or both fabrics may be circular knit fabrics. The adhesive 22 is arranged in discrete regions that together cover no more than about 70 percent of either fabric layer, leaving adhesive-free areas of the laminate 10 . Adhesive 22 is in contact with both portions of the pile yarns and portions of the elastomeric ground yarns of each fabric at their respective technical faces.
[0030] Referring also to FIG. 2 , the laminate 10 has an overall thickness, as measured in accordance with ASTM D1777 Section 7, Volume 7.01, with a thickness gauge modified for loop textiles with a two-inch (50 mm) diameter foot and a contact force of 31+/−3 grams, supplied by B C Ames Inc, of Melrose, Mass., USA, as Model no ABD-2600N DIG. IND, as per drawing number 07-0113, of about 0.095 inch (2.4 mm). Overall fabric thickness for many applications, measured in this manner, is preferably between about 0.07 and 0.15 inch (2 and 4 mm). Some loss of thickness can occur due to pressures applied in lamination or during winding. This may be more evident on lighter weight laminates with less crush resistance. The lamination of the two materials in the manner discussed herein provides a finished product with a relatively uniformly hook-engageable side 32 , and a comfortable cut-pile or broken loop side 34 . The technical faces of both materials are intimately bonded directly together by discrete, spaced-apart amounts of adhesive that flows into inter-fiber interstices of both fabrics without fouling either the loops 16 or the cut-loop fibers forming the skin contact surface. Furthermore, the hydrophobic-hydrophilic nature of the laminate tends to pull moisture away from surface 34 and toward surface 32 , where it evaporates. The nature of the fabric grounds, even with the inclusion of elastomeric yarns as discussed below, results in a very air-permeable product.
[0031] Referring back to FIG. 1 , first fabric layer 12 is a knit fabric 14 formed primarily of hydrophilic yarns that help pull moisture from inside the laminate, for evaporation from the exposed outer surface of the laminate. An example of such a fabric 14 is a circular knit loop material knitted from three yarns: a 40/13 texturized nylon ground yarn, a 70 denier monofilament spandex ground yarn having an elongation of at least 475 percent at break, and a 70/12 nylon pile yarn. (As used herein, an X/Y description of a yarn signifies a yarn with X total denier and Y filaments, such that the ratio X/Y denotes the denier per filament, or dpf.) The pile and ground yarns are introduced at every feed point, and the spandex ground yarn at every other feed point, with the spandex yarns fed through the same ground feed hole as the nylon ground yarn at every other carrier plate, such that every other row of stitches includes a spandex filament. The spandex yarns can be run into even fewer carriers, such as every third or fourth carrier plate, to produce fabrics of lower elasticity, or into every carrier plate if desired. Pile yarn can also be added every stitch, every other stitch, or as frequently as desired to provide a desired fabric weight and cost.
[0032] FIG. 3 illustrates a jersey knit ground structure in which every row of stitches contains both a spandex monofilament 40 and a multi-filament ground yarn 42 . The pile yarns are omitted from this illustration, for clarity. This figure illustrates an example of the relation of the non-elastomeric and elastomeric ground yarns as following the same path through the knit but not being plated so as to have the elastomeric yarn always lie on one side of the fabric or the other. Rather, as shown, the yarn positions will shift from front to back throughout the ground, due to movement of the yarns within the carrier plate ground feed hole. Using yarns of similar weights can exacerbate this effect. Heavier weight yarns will tend to migrate to the technical face if mixed with finer weight yarns.
[0033] FIG. 4 shows the path of each yarn through the knit structure of the fabric, and shows how the pile yarn 44 is knit alongside the spandex 40 and nylon 42 ground yarns, except that the pile yarn 44 is knit over sinkers to form a three-dimensional pile loop extending out of the plane of the ground. The material is knit to 32-34 wales per inch, as finished. Other wale counts can be obtained by changing the machine gauge or by stretching in finishing. As stabilized with an elastic acrylic binder as discussed below, first fabric layer 12 has a basis weight of about 6.9 osy (230 gsm). Although schematically illustrated in FIG. 1 as a flat surface, it can be seen from FIG. 2 that the outer surface of the knit fabric has the characteristic undulations of a knit structure from which the loop fibers extend. The fibers forming loops 16 should be of sufficient strength to function through repeated hook cycling, so that they are not easily broken when engaged with a hook, resulting in an objectionably worn (frayed) appearance. For a long-use (i.e., non-disposable) product the fiber denier should be selected to be much coarser than yarns and fibers used in second fabric layer 20 . There are numerous yarn and filament combinations possible, but as a practical matter commercial choices are normally limited to products that are currently available in volume. Yarns as large as 280/14 are commercially available, as well as yarns in then 200/10 range. Commercially available yarns as small as approximately 15/1 (i.e., monofilaments) can be used, and yarns as small as 20/5 are possible. Another particularly suitable pile yarn is a 140/24 nylon. Finer denier fibers can be used if the fibers are of sufficiently high tenacity. Fibers of approximately 4 grams/denier break strength are considered normal tenacity, while fibers of 8 grams/denier or more are considered high tenacity.
[0034] The nylon ground yarns are texturized with a false twist texturizing method, such as by heating and twisting the yarns between two surfaces during yarn manufacture. When relaxed, the yarn has substantial bulk and texture, and skein shrinkage of about 46 percent, as measured in accordance with ASTM D4031. Other texturizing methods include friction texturizing, nip twisting, air jet texturizing, knit-de-knit, edge crimping and gear crimping. Excessive texturizing can cause undesired kinking of the yarn. The nylon ground yarn is preferably texturized to skein shrinkage of between about 30 and 55 percent. During knitting, the tension on the texturized ground yarns is limited to maintain a desired level of texture or bulk. In this example the tension maintained on both the nylon and spandex ground yarns is 6 grams. A suitable texturized nylon ground yarn is available from Sapona Manufacturing Company, Inc. of Cedar Falls, N.C., as product code 08020.1. In some cases the pile yarn is also texturized, either to add randomization or density to the pile or to increase the stretchability of the fabric. Texturized pile yarns may require less or no napping for disorientation.
[0035] The knit nylon/spandex fabric tube is placed in a pressure vessel and heat set under pressure in the presence of an anionic liquid dye that reacts with amino groups of the nylon to form an ionic bond, the dye penetrating through the nylon to affect its molecular weight. Heat setting and dyeing may also be done at atmospheric pressures.
[0036] After heat-setting and dyeing, the knit tube is removed from the pressure vessel, slit open along its length, and treated with a commercial napping lubricant or fabric softener to facilitate napping. The slit fabric is then dried on a tenter frame or drum dryer (or other suitable dryer), and then napped to raise the loops of the pile for better hook engagement properties. Special precautions should be taken to prevent damage to the fabric when brushing or napping, due to the presence of elastomeric yarn. In a brushing or napping operation, if the spandex is contacted by the brush or napper wire, it can be cut or damaged. The knit fabric is then back-coated with a stretchable acrylic applied to the technical face of the product as a foam emulsion that breaks down to wick the acrylic into the ground of the fabric to serve as a binder to stabilize the pile loops for increased pull-out resistance and cycle life. In order to retain the stretch/recovery properties of the fabric, the back coating should be of a material and an application mode that does not significantly hinder stretching the final fabric. Using an elastomeric binder material can in some cases improve the resilience of the fabric even as compared to similarly constructed fabrics without a binder coat. A suitable elastomeric emulsion that can be applied as a foam is HyStretch® V-43, available from Lubrizol Advanced Materials, Inc. of Cleveland, Ohio. The V-43 material is mixed with water at a ratio of 1.6 liters V-43 to 1.0 liters of water in a mixer that foams the mixture by air injection at a volumetric blow ratio of 20 parts air to 1 part liquid. Other blow ratios as low as 3 to 1 are possible, depending on the density of foam desired. The amount of the dispersion applied can be controlled to increase or decrease the coat weight. Also, the mix ratio can be altered to achieve the desired results of binding and tie coating. In some cases where light coating is required, flow rates as low as 0.5 liter/min are applied at a fabric speed of 28 yards/min (25 meters/min). In other cases, flow rates of up to 5.0 liters/min are applied at similar line speeds. In some cases the back-coating is applied at a flow rate of 1.2 to 1.6 liters per minute, while a flow rate of 2.6 liters per minute can provide more bonding.
[0037] The binder should be selected to be compatible with the lamination adhesive in order to prevent poor lamination adhesion. Some common back-coating liquids, such as acrylic and urethane binders, can interfere with the bonding of co-polyamide or co-polyester hot melt adhesives. Back coating fabrics using co-polyamide or co-polyester powders may be done in a scatter coat application, resulting in a compatible binder coat that does not dramatically reduce air permeability. In other cases, these powders can be dispersed in a paste and applied in convention coating methods.
[0038] Back-coating powders may be dispersed in an acrylic or urethane binder to provide deeper penetration into the fabric than a hot melt. The dispersed powders, because of their larger particle size, tend to filter out and remain on the outside surface of the fabric. In some cases powders are dispersed as one part powder to ten parts binder, and have been found to give an improved bond over straight acrylic or urethanes. The weight percentage of the powder can be increased to 50 percent, or even higher, to improve tie coat results. In some cases powder level can be increased high enough to provide bonding to other surfaces or fabrics when reheated (such as for lamination by iron) without a secondary application of bonding hot melt. In one example, 10 percent co-polyester powder was blended into the acrylic binder and applied as a foam at a rate of 1.6 liters per minute at a line speed of 28 yards/min (25 meters/min). Further details of foam binder coating and fabric finishing can be found in U.S. Pat. No. 6,342,285, the contents of which are incorporated herein by reference. The final added weight percentage of the added binder in the finished fabric is between about 9 and 16 percent.
[0039] The binder is applied to the technical face of the fabric, either just before or while the fabric is stretched on a tenter frame and passed through an oven to dry and cross-link the binder before relaxing the fabric. The applied stretch during cross-linking of the acrylic binder is not excessive, and is primarily to hold the fabric taut during stabilization. In one example the fabric is stretched widthwise up to about 15 percent, while being overfed into the tenter as much as 15 to 20 percent in the lengthwise direction, to offset any residual longitudinal tension from prior processing and to prevent loss of elasticity. Tenter frame roll tension is also kept low. A greater amount of stretch during binder setting may increase breathability at some expense of elasticity. The fabric is then dried and heat set on the tenter frame, at a temperature of 320 degrees Fahrenheit (160 degrees C.) for about 35 seconds, then spooled.
[0040] This nylon/spandex example of knit fabric 14 has a fabric stretch of 20 to 34 percent, as tested per ASTM 6614-00 CRE method, with a recovery of about 97-98 percent.
[0041] Second fabric layer 20 is formed of hydrophobic, microdenier yarns and elastomeric yarns. By ‘microdenier yarns’ we mean yarns formed of microdenier fibers. In this example, each filament of the yarns is of about 1.0 denier. Fabric layer 20 is a circular knit material, of a basis weight of about 4.8 osy (160 gsm). It is preferable that the non-elastomeric yarn used in this fabric be of very fine fibers in the near-microdenier or microdenier range, making it soft against the skin to improve comfort. It has been discovered that if fibers in these yarns also have irregular cross-sections, such as dogbone or cloverleaf, or are hollow, tiny spaces between or inside the fibers promote capillary action, helping to remove moisture from the skin. Hydrophobic polyester yarns are desirable because of their low moisture content, but nylon fibers, in particular modified nylon or hydrophobic polypropylene fibers, can also be used. Additionally, these fibers may be produced with silver compounds included in the polymer, for anti-microbial properties. By adding these compounds into the fiber, or by topical addition to the finished fabric, bacterial growth can be controlled to reduce infection and prevent odor. In one example the yarns are supplied by Hyosung of Korea, available under the brand name of Aerosilver®. Several yarns and filament counts are available under this brand name. In one example a 70/72 yarn is selected for both the pile yarn and one ground yarn, the other ground yarn being the same 70 denier monofilament spandex yarn as in the example of first fabric layer 12 , described above. As in that example, the spandex yarn is fed into the same feed hole as the non-elastomeric ground yarn, in every other carrier plate, such that the spandex and non-elastomeric ground yarns follow the same path in the ground of the knit material but are both present on the technical face of the knit. The non-elastomeric polyester ground yarn is not texturized, but the non-circular Aerosilver® yarns are found to have some resiliency without post-texturization. Another suitable polyester yarn configuration is a 150/144 Aerosilver® or Aerocool® yarn, also available from Hyosung.
[0042] The knit polyester/spandex fabric tube is placed in a pressure vessel and heat set under pressure in the presence of a dispersed dye that penetrates into the polyester but forms only a weak hydrogen bond. A reducing agent helps to remove dye from the surface of the polyester, particularly in darker shades. After heat-setting and dying, the knit tube is removed from the pressure vessel, slit lengthwise, dried, and then napped to break the pile fibers to create a surface with a desired effective coefficient of friction to maintain position against skin, for example. No napping lubricant is needed as the intention of the napping is to break the pile. The broken-pile fabric is then pinned on a tenter frame, dried and heat set at a temperature of 320 degrees Fahrenheit (160 degrees C.) for about 35 seconds, and then spooled. In some cases it may also be advantageous to apply a stretch binder coat to the back of the polyester/spandex fabric. While such a coating is not needed to lock in the pile, it can improve the elastic recovery, and provide a cleaner cut edge to the laminate.
[0043] In the example described above, second fabric layer 20 is a circular knit fabric, but warp knit fabrics may also be employed. In some examples, first fabric layer 12 is a warp knit fabric and second fabric layer 20 is a circular knit.
[0044] Referring next to FIG. 5 , both knit fabrics 14 , 30 are laminated together to produce the finished laminate 10 . Hot melt adhesive 22 is applied to the technical face of knit fabric 14 by a gravure printing process. The adhesive is a heat-stabilized co-polyamide resin available from EMS as Griltex® D 1566A. It has a very high melting point, of about 240 to 257 degrees F. (applied at a temperature of 150 degrees C. for decreased viscosity), to enable the laminate to be stable through washing cycles. Alternatively, a co-PA/PET or co-PET resin may also be employed, as can moisture cure adhesives and adhesives other than hot melts. The adhesive is applied as discrete dots, in a pattern resulting in an average distribution of 28 gsm of adhesive, such that the adhesive comprises only about six percent of the final laminate weight. Higher adhesive application weights, such as 57 gsm, may be appropriate for some applications. This glue produces a good bond between two dissimilar surfaces. Other hot adhesives can be employed, such as polyamide, polyester or polypropylene. The technical face of fabric 14 contacts a rotating gravure roller 44 that leaves discrete dots of molten adhesive 22 on the technical face of the fabric, by known gravure printing methods. The technical faces of both fabrics may be heated, such as by infrared heaters 46 , just before entering a lamination nip 50 defined between pressure roller 48 and laminating roller 52 , where sufficient pressure is applied to form the laminate. Suitable lamination equipment may be obtained from Lacom Vertriebs GmbH Laminating Coating Machines of Lauchheim, Germany.
[0045] Gravure roller 44 has an outer surface that defines a pattern of offset or random cavities that each carries an associated, discrete volume of adhesive to the fabric surface. The pattern may comprise dots or lines, for example. With an offset or random dot pattern, adhesive dots are offset or random to distribute the bonding strength evenly. With a linear dot pattern the adhesive dots are arranged in lines, and in delaminating the products this can be felt as a bond-no bond force. The patterned adhesive application creates spaces between the adhesive dots for air to pass. Dot pattern, diameter, density, cavity depth, etc, all influence the percentage of coverage of adhesive on gravure roller 44 and in the final lamination 10 . This can also be influenced by the use of a negative or positive doctor blade position. Gravure rollers 44 are available to provide coverage of 10 to 70 percent, and custom patterns are available.
[0046] It is possible to improve the adhesive bond while still obtaining a good permeability by changing the depth of the gravure dot cavities. A deeper dot holds more volume of adhesive, and creates a taller mound of adhesive to bridge the spacer layer between the two fabrics being laminated. Cavity depths of 0.06 mm to 0.50 mm are available.
[0047] Line speed and temperature are important factors to control the laminate bond strength, particularly with gravure rollers 44 that deposit less adhesive, such as a CP 100 or CP 96 gravure roller. Slower line speeds of approximately 5.0 yds/min (4.5 meters/min) or less can improve the bond with these lower-adhesive rollers. Using gravure rollers 44 that deposit more adhesive, bond strength is increased at higher speeds. Preferably lamination occurs while the adhesive is still somewhat flowable. More gravure adhesive lamination details can be found in pending U.S. patent application Ser. No. 12/750,887, published as US-2010-0247846-A1, the entire contents of which are hereby incorporated by reference.
[0048] Following lamination, the laminate is then passed over a chilled roll 54 and the laminate edges may be trimmed in line as the laminate is being wound onto a roll. In some cases, the edge is trimmed in a separate process on suitable equipment designed for this purpose. It is preferred to trim outside edges that do not receive adhesive, and therefore are unbound. The laminate is then spooled for transportation or further processing.
[0049] The adhesive may be applied by other means. For example, a web adhesive or apertured film, such as available from DelStar Technologies, Inc. of Middletown, Del., USA can be used. These webs can be formed by a random spray pattern, embossed from a film, or formed on a laminating machine with a gravure roll to form an open web, which can then be fed between the two fabrics into a heated belt laminator. In other cases breathable laminates can be formed by ultrasonically bonding multiple layers of fabric using little or no adhesive in the laminate. Beckmann Converting Inc. of Amsterdam, N.Y., USA is capable of doing such ultrasonic lamination. Another means is scatter or powder coating, in which a hot-melt resin is sprinkled on a moving web as a powder, heated to melt the resin, and then nipped with the other fabric to bond the web and fabric together to form the laminate. In some cases, when adhesive is applied by any method, such as gravure, powder, spray, or web adhesive film, the two fabrics are compressed together with light pressure with heat on a belt laminator, so as to provide bonding without crushing surfaces of sensitive fabrics.
[0050] Mechanical methods of securing the two fabrics together, as an alternative to, or in addition to, adhesive, include needling or stitch-bonding the two fabrics together. Ultrasonic heat staking is another bonding means, which can create a quilted surface.
[0051] Laminate 10 , as formed, preferably has a basis weight of less than about 20 osy (675 gsm), or in a range of 10 to 20 osy (335 to 675 gsm). One example had a basis weight of 17.5 osy (590 gsm). Adhesive lamination bond strength can also be measured on an Instron tester in accordance with the ASTM D 2724-03 test method.
[0052] Laminate 10 , as formed, preferably has an air permeability, measured in accordance with ASTM D737-04, of at least 40 cfm per square foot (12 meters/min), more preferably at least 75 cfm per square foot (22 meters/min). Air permeability may be measured on a Frazier Air Permeability Instrument, model FAP-HP, supplied by Frazier Precision Instruments Co Inc. of Hagerstown, Md., USA.
[0053] Laminate 10 is fashioned to have significant in-plane resilience or stretchiness, in both machine and cross-machine directions, due in part to the inclusion of elastomeric fibers or yarns to both fabrics. Such fibers may be formed of a polyurethane polymer known as elastane or spandex. Spandex is extruded as a monofilament in round or shaped cross-section, and is available as a multifilament with a denier as low as 15. Increasing the denier of the spandex increases the “power” of elastic recovery. In some medical applications like elastic bandages, more power is desired to provide compression in the bandage.
[0054] Laminate 10 is also configured to provide particularly high friction coefficients at the skin contact surface, while at the same time providing a non-tacky, fibrous skin contact surface. In the case of medical textiles that are worn in direct contact with the skin, higher coefficients of friction help the material to stay in place as the wearer moves, while the material itself should be soft enough to prevent dermal abrasion. By “kinetic friction coefficient” and “static friction coefficient” I mean the friction coefficients as determined in accordance with ASTM D1894-01, with the laminate secured to a rigid surface such that the skin contact surface of the laminate is facing upward for direct contact with the 63 mm by 63 mm square underside of the 200 gram sled, which is of stainless steel and has an underside surface roughness of 15-18 micro-inch (0.40-0.45 μm). Using that method, one example of the laminate discussed above exhibited a static friction coefficient of about 0.42, and a kinetic friction coefficient (with the sled pulled across the laminate at a constant speed of 150 mm/min) of about 0.36. Preferably, the laminate has a static friction coefficient of at least 0.4, and a kinetic friction coefficient of at least 0.25, or in some cases at least 0.3.
[0055] In an example of a disposable, three-part laminate (not illustrated), an elastomeric core, such as a stretchable nonwoven or knit fabric or scrim or porous film, is laminated between a skin-friendly material of hydrophobic and antimicrobial properties, and a hook-engageable fabric. A lightweight, hook-engageable material is laminated to the opposite side of the stretchable core layer. As with the two-part laminate discussed above, sufficient adhesive may be applied to a given, discrete area to cause the adhesive to penetrate through the core and directly bond the outer fabric layers to one another.
[0056] The stretchable knit pile fabrics discussed above may be knit on a standard circular knitting machine equipped to feed the three distinct yarns from different spools. FIGS. 6 and 7 show one of a series of yarn carrier assemblies spaced about the rim of a circular knitting machine on which the fabric is formed. The carrier assembly 60 carries a yarn carrier plate 62 that receives the three yarns from their respective spools (not shown) via positive yarn storage feeders, and directs them sequentially to a series of needles 64 that are raised by a cam system with respect to the carrier plate. The ground yarns (elastomeric yarn 40 and texturized non-elastomeric yarn 42 ) are separately fed to a single ground yarn feed roller 66 , where they are joined and fed into a ground feed hole 68 in the top surface of the carrier plate. Pile yarn 44 is fed through a grommet 70 and into a pile yarn feed hole 72 in the side surface of the carrier plate. While the two ground yarns emerge together from ground feed hole 68 at the bottom of the foot of the carrier plate (see FIG. 8 ), the pile yarn 44 passes out the back side of the carrier plate and is knit into the material over a series of sinkers (not shown) to form the pile.
[0057] The elastomeric and non-elastomeric ground yarns are not normally joined in the carrier plate in typical stretch jersey knit materials. Rather, the elastomeric yarn is typically fed into a separate groove 74 that runs down the foot of the carrier plate (see FIG. 8 ) in this style of carrier plate, such that at the lower end of the carrier plate foot the two ground yarns exit always with a fixed relative positioning, with the result that the non-elastomeric yarn is consistently placed on the technical face of the fabric, while the elastomeric yarn will be generally trapped between the technical face yarn and the pile yarn. Because in this example the two ground yarns are fed through the same feed hole, they will tend to shift in their relative positioning during knitting, with the non-elastomeric yarn occasionally lying on the technical face, and the elastomeric yarn occasionally lying on the technical face. Because of this knitting method, both ground yarns will be present on the technical face, as illustrated in FIG. 3 .
[0058] By changing yarn position between hole and slot, the elastomeric yarn can be either positioned to be covered by the non-elastomeric yarn or positioned to be more exposed on the technical face of the knit fabric. By placing the elastomeric yarn in the slot, it will tend to be covered by the non-elastomeric yarn. If the elastomeric yarn is placed in the hole and the non-elastomeric yarn is placed in the slot, more of the elastomeric yarn will plait to the technical face. Carrier plates of Mayer knitting machines do not use a slot, but instead have 2 holes.
[0059] Feeding the elastomeric yarn through groove 74 will cause the elastomeric yarn to be exposed on the technical face in greater proportion than the non-elastomeric yarn. This may be particularly useful in laminating two such fabrics together with an adhesive that bonds two elastomeric surfaces together well. It may be that some urethane or acrylic adhesives will have better chemical affinity with a segmented polyurethane spandex surface, for example, than with a nylon or polyester surface, thereby efficiently and permanently bonding such spandex-backed materials together to form a laminate. Development of a strong chemical bond with the adhesive may help to reduce the bonding surface area required for reliable lamination, further increasing the obtainable air permeability of the laminate.
[0060] FIG. 9 shows how little adhesive may be necessary to effectively bond together two fabrics knit to have both elastomeric and non-elastomeric yarns exposed on their technical backs. In this enlarged side photograph, two discrete adhesive bonds are visible, corresponding to two discrete dots of adhesive applied by gravure printing during lamination, as discussed above. The adhesive shows up as lighter regions in the photograph, with one visible near the left of the photograph between the ground layers, and one near the right of the photograph. The adhesive is in intimate contact with, and encapsulates portions of, fibers of the technical faces of both fabrics.
[0061] While a number of examples have been described for illustration purposes, the foregoing description is not intended to limit the scope of the invention, which is defined by the scope of the appended claims. There are and will be other examples and modifications within the scope of the following claims.
|
A method of forming a circular knit fabric includes feeding a multi-filament non-elastomeric yarn from a first spool into an aperture defined in a yarn carrier plate that guides the non-elastomeric yarn sequentially to a series of knitting needles spaced about a circular needle array; while feeding an elastomeric yarn from a second spool to the yarn carrier plate, such that a fabric is knit to have a ground comprising both the non-elastomeric yarn and the elastomeric yarn. The non-elastomeric yarn and the elastomeric yarn are fed together into the carrier plate aperture in an untwisted, unwrapped relation, such that the fabric ground is knit to have a technical face in which potions of the non-elastomeric yarn are exposed in some areas and portions of the elastomeric yarn are exposed in some areas.
| 3
|
RELATED APPLICATIONS
This application is a divisional of application Ser. No. 10/671,996 filed Sep. 26, 2003 now U.S. Pat. No. 7,138,330, which is a continuation-in-part of application Ser. No. 10/331,186, filed Dec. 26, 2002 now abandoned, which is in turn claims the benefit of prior filed U.S. Provisional Application Ser. No. 60/414,289 filed Sep. 27, 2002. The entirety of each which are incorporated herein by reference.
This application related to U.S. patent application Ser. No. 10/038,276, filed 31 Dec. 2001, entitled “Sensor Substrate and Method of Fabricating Same,” the entirety of which is incorporated herein by reference.
BACKGROUND
1. Field of the Invention
Embodiments of the invention relate to semiconductor device fabrication, and, in particular, to the formation of multilayer wiring substrates on which integrated circuits or discrete devices are mounted.
2. Description of Related Art
A variety of mounting structures are known for electronic circuits. Multi-chip modules and hybrid circuits are typically mounted on ceramic substrates that include metallic conductors for interconnecting the components, and the components are typically sealed within a metal or ceramic casing. Complex hybrid circuits typically require equally complex interconnection structure. In such instances it is common to utilize a multilayer substrate comprised of multiple layers of conductors sandwiched between multiple layers of dielectric material. Multilayer substrates are conventionally fabricated by lamination techniques in which metal conductors are formed on individual dielectric layers, and the dielectric layers are then stacked and bonded together.
Various conventional lamination techniques are known, however each has limitations that restricts its usefulness for producing multilayer substrates. High temperature ceramic co-fire (HTCC) lamination techniques form conductors on “green sheets” of dielectric material that are bonded by firing at temperatures in excess of 1500 degrees C. in a reducing atmosphere. The high firing temperature precludes the use of noble metal conductors such as gold and platinum. As a result, substrates formed by high temperature processing are limited to the use of refractory metal conductors such as tungsten and molybdenum, which have very low resistance to corrosion in the presence of moisture and are therefore not appropriate for use in harsh environments.
Low temperature ceramic co-fire (LTCC) techniques also utilize green sheets of ceramic materials. Low-temperature techniques do not require the use of a reducing atmosphere during firing and therefore may employ noble metal conductors. However the dielectric materials used in low-temperature processes are generally provided with a high glass content and therefore have relatively poor resistance to environmental corrosion, as well as a relatively low dielectric constant and relatively poor thermal conductivity.
Thick film (TF) techniques form multilayer substrates by firing individual dielectric layers and then laminating the layers to form a multilayer stack. However, thick film techniques require the use of relatively thick dielectric layers and thus it is difficult to produce a thin multilayer substrate using thick film techniques. Thick film dielectrics also have relatively low dielectric constants, relatively poor thermal conductivity, and poor corrosion resistance.
In addition to the problems listed above, the conventional lamination techniques cannot use green sheets of less than 0.006 inches in thickness because thinner green sheets cannot reliably survive necessary processing such as drilling or punching of via holes. Also, because the designer has limited control over the thickness of individual green sheets, the number of layers of the multilayer substrate is often limited according to the maximum allowable substrate thickness for the intended application. Thus, where a thin multilayer substrate is desired, lamination techniques generally do not provide optimal results.
In addition, the firing required in the conventional lamination techniques can cause shrinkage in excess of 10% in both dielectric and conductor materials, which can produce distortions that result in misalignment of vias and conductors after firing. While shrinkage effects can be addressed to some extent during design for substrates having a modest interconnect density, the design process is made more time consuming and a significant reduction in yield may occur in applications with higher densities and tighter dimensional tolerances.
The conventional technology is therefore limited by several restrictions. All of the aforementioned techniques are limited with respect to the minimum substrate thicknesses that can be produced, and the various firing requirements of the aforementioned techniques prevent the use of materials that are desirable for circuit structures. All of the aforementioned techniques also suffer from shrinkage during firing that causes alignment problems.
SUMMARY OF THE INVENTION
In accordance with embodiments of the invention, a multilayer circuit substrate is comprised of a base substrate and one or more additional dielectric and conductive thin films formed over the base substrate by vacuum deposition methods. The vacuum deposited dielectric layers are significantly thinner than the dielectric layers used in conventional lamination techniques, allowing for the formation of multilayer circuit substrates that are significantly thinner than those formed by conventional lamination techniques. Because vacuum deposited dielectrics are deposited in an “as-fired” state that undergoes essentially no shrinkage during subsequent processing, yield reduction due to misalignment is significantly reduced or eliminated. In addition, vacuum deposition techniques do not impose limitations on the types of conductors or dielectric materials that may be employed, enabling the use of a wide variety of materials with highly tunable properties. Vacuum deposition techniques also produce hermetic layers that facilitate the production of highly reliable substrates.
In accordance with further embodiments of the invention, deposited dielectrics may be patterned through the use of sacrificial structures that may be removed using highly selective etch chemistry. The sacrificial structures are preferably formed using a high precision shadow mask that allow dielectric patterns to be precisely registered to underlying structures and thus enabling high interconnect densities and narrow dimensional tolerances not achievable by conventional lamination techniques.
In accordance with further embodiments of the invention, patterning techniques such as shadow masking, chemical etch and photoresist lift-off may be used for patterning conductive materials. Conductors may therefore be precisely aligned with underlying structures and formed with linewidths not achievable by conventional lamination techniques.
In accordance with further embodiments of the invention, hermetic vias may be formed in the dielectric base substrate by forming successive thin layers of a conductive material on the sidewalls of a via hole using a dilute conductive ink, followed by formation of a conductive plug using a concentrated conductive ink. The conductive material in the via is then sintered to form a unitary body, producing a hermetic via without shrinkage of the surrounding dielectric.
In accordance with one embodiment of the invention, a multilayer circuit substrate is characterized by a dielectric base substrate having conductors formed thereon, and at least one layer of a patterned vacuum deposited thin film dielectric overlying the conductors. In various implementations, multiple layers of conductors and deposited dielectrics may be used, multiple layers may be formed on both sides of the base substrate, and the base substrate may include hermetic vias. It is preferred that the deposited thin film dielectrics are patterned using sacrificial structures formed by shadow mask deposition.
In accordance with another embodiment of the invention, a multilayer circuit substrate for a multi-chip module or a hybrid circuit is produced. Initially a dielectric base substrate is provided. Conductors are then formed on the base substrate, preferably by patterning of a blanket layer of conductive thin film deposited by a vacuum deposition method. Sacrificial structures are then formed on the base substrate and conductors. The sacrificial structures define areas of the base substrate and conductors that are to be protected during subsequent dielectric deposition. The sacrificial structures are preferably formed by shadow mask deposition. A thin film dielectric layer is then vacuum deposited on the base substrate, the conductors and the sacrificial structures, and the sacrificial structures are removed to leave a patterned deposited thin film dielectric layer on the conductors and the base substrate. Further processing such as forming additional conductor layers and dielectric layers or mounting of an electronic component to the substrate may be performed.
DESCRIPTION OF THE DRAWINGS
FIGS. 1 a , 1 b , 1 c , 1 d , 1 e , 1 f , 1 g and 1 h show structures formed during fabrication of a hermetic via in accordance with a preferred embodiment;
FIGS. 2 a , 2 b , 2 c , 2 d , 2 e , 2 f , 2 g , 2 h , 2 i , 2 j and 2 k show structures formed during fabrication of a multilayer circuit substrate and circuit structure in accordance with the preferred embodiment; and
FIG. 3 shows a process flow encompassing the processing of FIGS. 2 a - 2 k and alternative processing.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
A preferred embodiment of a method for producing a multilayer circuit substrate is now described in the context of production of a hermetic blood glucose sensor circuit. It should be understood that the processing performed in the preferred embodiment represents one implementation of the invention and that the techniques of the invention have a variety of alternative applications, examples of which are provided after the description of the preferred embodiment.
FIGS. 1 a - 1 h show structures formed during processing in accordance with the preferred embodiment to form a hermetic via in a dielectric base substrate. While the processing of FIGS. 1 a - 1 h illustrates a single via, it will be appreciated that multiple vias may be produced simultaneously using the illustrated techniques.
FIG. 1 a shows a cross-sectional view of a portion of a dielectric base substrate 10 . The base substrate is preferably a sheet of 96% purity alumina (Al 2 O 3 ) that is pre-fired such that shrinkage will not occur during subsequent processing. The preferred embodiment utilizes a two inch by two inch substrate having a thickness of approximately 0.010 inches.
FIG. 1 b shows the base substrate of FIG. 1 a after laser drilling of a via hole 12 . Annealing is preferably performed after laser drilling to reduce imperfections caused during drilling. The use of laser drilling coupled with the techniques described below for precise registration of overlying materials enables the production of ultra-small vias with via densities up to the limits of laser processing. In accordance with the preferred embodiment, vias may be formed with diameters of 0.002 inches and a spacing of 0.006 inches, whereas conventional drilling and tape punch methods as well as shrinkage limit vias produced in HTCC and LTCC substrates to diameters of approximately 0.005 inches and spacings of approximately 0.015 inches.
FIG. 1 c shows the structure of FIG. 1 b after a dilute conductive ink 14 is introduced into the via hole 12 of the base substrate 10 . The conductive ink 14 typically comprises a slurry of a particulate noble metal such as gold or platinum suspended in an organic binder that is eliminated during later thermal processing. In accordance with the preferred embodiment, the ink applied to the substrate is diluted from its typical paste-like commercial consistency to a more flowable consistency through mixture with a solvent. The conductive ink 14 is preferably introduced to the via hole 12 by a screen printing technique using a metal screen having apertures corresponding to via holes 12 formed in the base substrate 10 . The metal screen is aligned with the base substrate, conductive ink is coated on a surface of the metal screen, and the ink is then forced through the apertures in the screen by dragging with a rubber blade.
FIG. 1 d shows the structure of FIG. 1 c after application of a vacuum to the via hole 12 . The application of the vacuum causes the conductive ink to form a thin conductive coating 16 that adheres to the sidewalls of the via hole 12 without bubbles or voids. Application of the vacuum is typically followed by low temperature firing in a range of 100-200 degrees C. to remove solvent from the conductive ink, and then by high temperature firing in a range of 850-950 degrees C. to burn out the organic binder from the conductive ink and to fuse the conductive particles.
FIG. 1 e shows the structure of FIG. 1 d after formation of multiple additional thin coats 16 of conductive material on the via hole 12 sidewalls through further applications of dilute conductive ink followed by application of vacuum and firing. As seen in FIG. 1 e , each successive layer of conductive material reduces the width of the opening between the sidewalls of the via hole 12 .
FIG. 1 f shows the structure of FIG. 1 e after formation of a plug 18 in the via using a conductive ink that is undiluted or substantially less dilute than the ink used for formation of the thin sidewall layers 16 . In some instances the formation of the plug may be followed by formation of one or more additional layers 20 of ink to fill any depressions at the ends of the via. The conductive ink is fired after each of these applications.
FIG. 1 g shows the structure of FIG. 1 f after removal of residual conductive material from the surface of the base substrate 10 . Residual conductive material is typically removed by a lapping process in which the base substrate 10 is held in a fixed position while an abrasive material is moved against its surface. Lapping may be followed by chemical etching to remove any remaining conductive material from the base substrate surface.
FIG. 1 h shows the structure of FIG. 1 g after sintering at a temperature of approximately 1000-1200 degrees C. to bond the individual conductive particles of the conductive ink layers into a monolithic via conductor 22 . After sintering, the via is subjected to helium leak testing to confirm the hermeticity of the via.
FIGS. 2 a through 2 k show structures formed during processing in accordance with the preferred embodiment for producing a blood glucose sensor using a base substrate having vias formed in accordance with the processing of FIGS. 1 a - 1 h . Each of FIGS. 2 a through 2 k provides a top plan view, a cross-section taken along line A-A′ of the top plan view, and a bottom plan view of a section of a substrate upon which processing is performed in accordance with the preferred embodiment.
FIG. 2 a shows a base substrate 30 having a plurality of hermetic vias 32 extending between its major surfaces. The base substrate 30 is preferably a substrate of the type used in the processing of FIGS. 1 a - 1 h , and the hermetic vias are preferably formed in accordance with the processing of FIGS. 1 a - 1 h.
FIG. 2 b shows the structure of FIG. 2 a after formation of welding pads 34 on the top surface of the substrate. The welding pads 34 provide connection points for external wires to the circuitry that will be mounted on the substrate. The welding pads of the preferred embodiment are formed by screen printing using a platinum conductive ink, however in alternative embodiments contacts may be formed by other techniques that are consistent with the requirements of the joining process.
FIG. 2 c shows the structure of FIG. 2 b after formation of patterned conductors 36 on the top surface of the base substrate 30 . The conductors 36 are preferably formed of consecutive layers of titanium, platinum and titanium that are patterned by a photoresist lift-off process. In the lift-off process, a photoresist layer is patterned to form a negative image of the conductors 36 using a conventional exposure and developing technique. A blanket metal thin film is formed over the substrate and the photoresist pattern such as by physical vapor deposition (sputtering), and a photoresist stripping chemistry is then used to remove the photoresist pattern. Metal deposited on the photoresist is lifted off as the underlying photoresist is dissolved, while metal deposited on the base substrate adheres to the base substrate and remains after lift-off. Accordingly, precise lithographically patterned thin film conductors are formed with precise alignment to the base substrate 30 and vias.
FIG. 2 d shows the structure of FIG. 2 c after formation of sacrificial structures 38 on the base substrate 20 and the conductors 36 . The sacrificial structures 38 are used to define areas of the base substrate 30 and conductors 36 that are to be protected during subsequent deposition of a dielectric material, in a manner analogous to the use of the photoresist mask in the lift-off technique for patterning the conductors 36 . The sacrificial structures 38 are preferably formed of a material that will survive subsequent vacuum deposition of dielectric and that is easily removed in later processing by a etchant that is highly selective of the sacrificial material with respect to other exposed materials. In the preferred embodiment, the sacrificial structures 38 are formed of aluminum that is deposited by a shadow mask process. In the shadow mask process, a shadow mask bearing a positive image of the sacrificial structures is placed in contact with or near the surface of the base substrate 30 and conductors 36 . Aluminum is blanket deposited over the shadow mask such as by a vacuum deposition process such as sputtering, and forms on the substrate in those areas that are exposed by apertures in the shadow mask. After deposition the shadow mask is removed, leaving patterned aluminum structures 38 as shown in FIG. 2 d . In the preferred embodiment it is preferable to form the sacrificial structures 38 to be substantially thicker than the subsequent dielectric layers that is to be patterned using the sacrificial structures 38 .
FIG. 2 e shows the structure of FIG. 2 d after vacuum deposition of a dielectric thin film 40 over the base substrate, the conductors and the sacrificial structures. In the preferred embodiment the dielectric material is alumina and is vacuum deposited by a method such as sputtering or evaporation, producing a highly hermetic dielectric material in an “as fired” form, that is, in a form that will not undergo significant structural changes such as shrinkage during subsequent processing. To enhance the density, adhesion and hermeticity of the dielectric thin film 40 , ion beam assisted deposition (IBAD) may be employed, wherein the deposited dielectric material is bombarded with low energy ions during deposition to provide improved adhesion and coating density. Formation of dielectric thin films by vacuum deposition can produce layers having thicknesses in the range of 100 angstroms to 20 microns (0.0000004-0.0008 inches), compared to the conventional minimum green sheet thickness of 0.006 inches or approximately 150 microns. Accordingly, the use of vacuum deposited dielectric thin films rather than conventional sheet dielectrics allows the production of significantly thinner multilayer substrates or the production of multilayer substrates having significantly more layers than those formed by conventional lamination methods. In addition, vacuum deposited layers are highly hermetic and provide significant protection of underlying materials against the outside environment.
FIG. 2 f shows the structure of FIG. 2 e after patterning of the deposited dielectric layer 40 by selective removal of the aluminum sacrificial structures. The aluminum sacrificial structures may be removed selectively with respect to the titanium conductors, alumina base substrate and gold vias using a ferric chloride solution or another mild etchant that is selective with respect to the aluminum sacrificial structures. The etchant reaches the aluminum sacrificial structures through pin-holes and other imperfections in the extremely thin layers of dielectric material that are deposited on the sidewalls of the sacrificial structures. By forming the sacrificial structures to be substantially taller than the dielectric layer, it is ensured that there will be sufficiently thin sidewall coverage and sufficient sidewall surface area to enable penetration of the etchant. As the aluminum sacrificial structures dissolve, the dielectric thin film overlying the sacrificial structures collapses and is rinsed away in subsequent cleaning, leaving a patterned dielectric thin film as shown in FIG. 2 f that protects the majority of the conductors 36 and base substrate 30 surface area while selectively exposing portions of the conductors 36 for connection to overlying conductors. Because the sacrificial structures 38 are precisely positioned relative to the base substrate 30 and conductors 36 using the shadow mask process described above, and because the deposited dielectric thin film 40 will not undergo significant structural changes during further processing, the openings in the deposited dielectric thin film 40 are precisely aligned with the underlying conductors 36 and base substrate 30 , enabling greater via and conductor densities and providing greater process yield.
FIG. 2 g shows the structure of FIG. 2 f after formation of additional welding pads 42 on the top surface of the base substrate 30 , followed by formation of sensor electrodes 44 on the bottom surface of the base substrate 30 . The sensor electrodes 44 are preferably formed of successive thin films of titanium, platinum and titanium that are patterned on the bottom surface of the base substrate 30 by a photoresist lift-off process.
FIG. 2 h shows the structure of FIG. 2 g after formation of caps 46 over portions of the sensor electrodes 44 that are in contact with vias 32 that extend through the dielectric base substrate 30 . The caps 46 prevent access of fluid contaminants to the vias 32 and portions of the base substrate 30 in the vicinities of the vias that may be somewhat amorphous as a result of laser drilling and therefore more susceptible to chemical degradation. In the preferred embodiment the caps 46 are highly pure alumina caps that are formed using a positive shadow mask process, thus allowing precise registration of the caps 46 to the vias 32 .
FIG. 2 i shows the structure of FIG. 2 h after formation of gold contact pads 48 on exposed portions of the conductors 36 . The gold contact pads 48 provide contact points for electrical connection of integrated circuits and discrete devices to the conductors 36 . A gold ring 50 is also formed at the perimeter of the deposited dielectric thin film 40 and defines an area within which circuit components will be mounted. The gold ring 50 is used in later processing for bonding a protective cap over the circuit components. The gold contact pads 48 and gold ring 50 are preferably formed by a photoresist lift-off process.
FIG. 2 j shows the structure of FIG. 2 i after mounting of an integrated circuit 52 and a discrete capacitor 54 to the multilayer substrate composed of the base substrate 30 , the conductors 36 and the deposited dielectric thin film 40 . The integrated circuit 52 is connected to the gold contact pads 48 by wire bonds. In the preferred embodiment, the integrated circuit is in electrical communication with the sensor electrodes 44 on the bottom of the base substrate 30 through the conductors 36 formed on the top surface of the base substrate 30 and the hermetic vias 32 formed through the base substrate 30 . The integrated circuit 52 makes oxygen and glucosine measurements using readings taken from the sensor electrodes 44 and provides a digital output representing those measurements. While the preferred embodiment connects the integrated circuit 52 using wire bonds, in alternative other connection structures such as flip chip and ball grid array structures may be used.
FIG. 2 k shows the structure of FIG. 2 j after bonding of a protective cap 56 to encase the circuit components. The cap 56 is preferably a gold cap that is bonded to the gold ring formed on the deposited dielectric thin film. In the resulting structure the protective cap 56 provides a hermetic seal against fluids at the top surface of the substrate, while the hermetic vias 32 and their associated caps 46 provide hermetic seals against fluids at the exposed bottom surface where the sensor electrodes 44 are located. The deposited dielectric thin film 40 that lies between the gold cap and the base substrate is also hermetically bonded to the base substrate 30 by virtue of its vacuum deposition, and as a result the circuit components are completely hermetically sealed against the outside environment.
While the processing shown in FIGS. 1 a - 1 h and 2 a - 2 k represents a preferred embodiment for producing a blood glucose monitor, the techniques used in this processing are generally applicable to a wide range of applications in which it is desired to produce thin multilayer substrates with a high degree of alignment precision, relatively little shrinkage, and a potentially high conductor and via density. Accordingly, many specific details of the preferred embodiment may be altered, adapted or eliminated to in accordance with various desired implementations.
In general terms the techniques of the preferred embodiment may be adapted to form multilayer substrates comprised of any desired number of dielectric and conductors layers. The substrate is formed of patterned dielectric and conductive thin films that are deposited on a base substrate. Deposited dielectric layers are preferably patterned using sacrificial structures to form openings in the dielectric layers for vias or for exposing larger contact areas of conductors.
The thin films use in accordance with embodiments of the invention are preferably vacuum deposited. For purposes of this disclosure, the term vacuum deposited refers deposition of a material at a low pressure in a controlled atmosphere. Such techniques include evaporation, sputtering (PVD) and chemical vapor deposition (CVD). Evaporation is preferably used where it is desired to form a relatively thick layer, e.g. 10 microns. However evaporation provides relatively poor adhesion and density. The adhesion and density of evaporated layers may be improved through the use of ion bombardment (ion-assisted evaporation). Sputtering (PVD) is preferred where adhesion is a priority. However the growth rate of layers formed by sputtering is approximately an order of magnitude slower than those formed by evaporation. CVD may be used as needed to form layers of materials that are not easily formed by evaporation or sputtering.
With regard to the base substrate, it is preferred in most embodiments to use a rigid sheet of an as-fired dielectric ceramic material. However, the base substrate may be composed of a wide variety of substrate materials since the deposition processes used to form forming dielectric and conductive thin films are performed at relatively low temperatures, and patterning of those thin films using sacrificial structures utilizes relatively mild etchants. While the preferred embodiment uses a substrate comprising 92-96% purity alumina, high purity berillia and aluminum nitride base substrates may also be used. Other types of dielectric substrates such as polyimide flex board and standard printed circuit board substrates comprised of epoxy resin impregnated glass fiber may also be used. In optical applications, substrates such as glass and sapphire may be used. For radiation hardened applications a gallium arsenide (GaAs) substrate may be used, and may be provided with a thin dielectric protective layer as required. In advanced applications, the substrate may be a semiconductor substrate such as silicon or GaAs that has an application specific integrated circuit (ASIC) formed therein by conventional lithographic techniques. Thin film dielectric and metal layers may then be formed on the semiconductor substrate in the manner of the present invention to protect the ASIC and to form sensor electrodes and metal patterns for connection of discrete components to the ASIC.
With regard to conductors, it is preferred to utilize thin film conductors that are patterned by shadow masking, photoresist lift-off patterning or chemical etching. However in alternative embodiments conductors may be formed by other methods such as screen printing. The thickness of the conductors may be selected in accordance with a type of joining operation that will be performed on the conductor. For example, conductors that will be resistance welded may be formed of a thick layer, while conductors that will be connected by a low power technique such as wire bonding may be formed of a thin film. Further, while the preferred embodiment provides conductors that are designed for wire bonding, in alternative embodiments the conductors may be patterned for use in other integrated circuit connection structures, such as flip chip and ball grid array structures. The types of conductor materials that may be used are not limited by processing conditions as in some conventional lamination methods, and may therefore be chosen in accordance with the particular application. Conductor materials may include metals such as platinum, gold, silver, copper, titanium, tungsten, and aluminum, as well as alloys, conductive compounds such as silicides, or any other conductor that is applicable in a particular implementation. While the conductors of the preferred embodiment are formed of successive layers of different conducting materials, single conducting materials may also be employed.
Embodiments of the invention also provide great freedom of choice with respect to the deposited dielectric material. As a general matter the dielectric layer should be capable of formation by a vacuum deposition technique that provides good adhesion to underlying materials and good process control for producing very thin layers. As a general matter any dielectric material that can be obtained in a substantially pure form may be evaporated and vacuum deposited as a thin film on a substrate. Accordingly, a variety of deposited dielectric materials may be used including alumina, aluminum nitride, silicon oxide, silicon nitride, silicon oxynitride, titanium nitride and the like. Vacuum deposited dielectric thin films provide a number of desirable properties, including highly controllable thickness, high hermeticity, dimensional stability, thermal and chemical stability, and tunable dielectric and thermal conductance properties. For purposes of this disclosure, the term “deposited dielectric” is therefore used not only to describe the processing by which the dielectric is formed, but also the resulting structural features of the deposited dielectric that distinguish it from conventional laminated dielectrics, including its conformality and hermeticity with respect to the materials on which it is formed, its high density and adhesion, and its dimensional, thermal and chemical stability.
Thin film dielectric layers are preferably patterned using sacrificial structures formed by shadow mask deposition. While the preferred embodiment utilized a single dielectric thin film having relatively large patterned openings, in alternative embodiments multiple layers of dielectric thin films may be employed, and the dielectric thin films may have very small patterning features such as vias for connecting conductors in adjacent layers. It is preferable to form the shadow mask apertures for small patterning features using laser drilling methods, thereby enabling the formation of vias with diameters as small as 0.002 inches and with spacings as small as 0.006 inches.
Accordingly, using conductive and dielectric thin films and patterning techniques in accordance with embodiments of the invention, the dimensions of multilayer substrate features may be significantly reduced compared to those produced through conventional lamination techniques. The following table compares the minimum dimensions and other characteristic features achievable through conventional lamination techniques and through embodiments of the present invention:
TABLE 1
Conventional
Preferred
Lamination
Embodiment
Minimum line width
0.005 inches
0.001 inches
Minimum dielectric thickness
0.006 inches
0.00004 inches
Minimum via diameter
0.005 inches
0.002 inches
Minimum via spacing
0.015 inches
0.006 inches
Shrinkage
in excess of 10%
none
While the multilayer substrate of the preferred embodiment is comprised solely of vias, conductors and dielectric layers, alternative embodiments may integrate or embed passive components such as capacitors, resistors and inductors into the multilayer substrate. For example, while the circuit of the preferred embodiment comprises a discrete capacitor, in alternative embodiments a capacitor may be integrally formed in the multilayer substrate from conductors separated by a deposited dielectric layer. Capacitors may be formed, for example, using a silicon oxide or silicon nitride dielectric layer between conductive plates. Interdigitated capacitors and trench may also be formed. The degree of material control and geometrical precision provided by vacuum deposition and patterning of the dielectric layers allows for precise patterning of the capacitor structure as well as tuning of the capacitor parameters through control of the thickness and dielectric constant of the deposited dielectric layer. Thin film inductors and thin film resistors may also be integrated into the multilayer substrate. Thin film resistors may be patterned from layers of materials such as tantalum nitride (TaN), polysilicon, titanium, cermet or nichrome. In other embodiments, substrate layers may be patterned to form micro-electro-mechanical systems (MEMS) that are integrated with the layers of the substrate. For example, the patterning techniques described above can be used to fabricate structures such as microfluidic structures, valves, reaction chambers, strain gages, micro-actuators, electro-mechanical sensors arrays and optical detectors. Additional properties of the multilayer substrate such as thermal management, power management, shielding and grounding can be precisely controlled through choices of layout and materials.
A wide variety of embodiments may therefore be implemented in accordance with the invention. In general terms, multilayer circuit substrates fabricated in accordance with embodiments of the invention are characterized by a dielectric base substrate having conductors formed thereon, and at least one layer of a patterned vacuum deposited dielectric thin film overlying the conductors. In various implementations, multiple layers of conductors and dielectric thin films may be used, conductors may be formed from thin films, multiple layers may be formed on both sides of the base substrate, and the base substrate may include hermetic vias. It is preferred that the deposited dielectric thin films are patterned using sacrificial structures formed by shadow mask deposition.
FIG. 3 shows a process flow for producing a multilayer circuit substrate that encompasses the preferred embodiment, the aforementioned alternative embodiments, and further alternatives. Initially a dielectric base substrate is provided ( 60 ). Conductors are then formed on the base substrate ( 62 ), preferably by patterning of a blanket layer of a conductive thin film deposited by a vacuum deposition method. Sacrificial structures are then formed on the base substrate and conductors ( 64 ). The sacrificial structures define areas of the base substrate and conductors that are to be protected during subsequent dielectric deposition. The sacrificial structures are preferably formed by shadow mask deposition. A dielectric thin film is then vacuum deposited on the base substrate, the conductors and the sacrificial structures ( 66 ), and the sacrificial structures are removed ( 68 ) to leave a patterned dielectric thin film on the conductors and the base substrate. Further processing such as forming additional conductor layers and dielectric layers or mounting of electronic components may be performed.
It will be apparent to those having ordinary skill in the art that the tasks described in the above processes are not necessarily exclusive of other tasks, but rather that further tasks may be incorporated into the above processes in accordance with the particular structures to be formed. For example, intermediate processing tasks such as formation and removal of passivation layers or protective layers between processing tasks, formation and removal of photoresist masks and other masking layers, application and removal of antireflective layers, doping, cleaning, planarization, annealing and other tasks, may be performed along with the tasks specifically described above. Further, the processes may be performed selectively on sections of a base substrate or at multiple locations on the base substrate simultaneously. Thus, while the embodiments illustrated in the figures and described above are presently preferred, it should be understood that these embodiments are offered by way of example only. The invention is not limited to a particular embodiment, but extends to various modifications, combinations, and permutations encompassed by the appended claims and their equivalents.
|
A multilayer circuit substrate for multi-chip modules or hybrid circuits includes a dielectric base substrate, conductors formed on the base substrate and a vacuum deposited dielectric thin film formed over the conductors and the base substrate. The vacuum deposited dielectric thin film is patterned using sacrificial structures formed by shadow mask techniques. Substrates formed in this manner enable significant increases in interconnect density and significant reduction of over-all substrate thickness.
| 7
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a novel heat-resistant polyester having a specific heat resistance and moldability or processability.
2. Description of the Related Art
Various proposals have been made for the production of polyesters from the starting material 9,9-bis(4-hydroxyphenyl)fluorene. For example, polyesters derived from 9,9-bis(4-hydroxyphenyl)fluorene and terephthalic acid or isophthalic acid are reported in Macromolecule 3,536 (1970), and polyesters derived from 9,9-bis(4-hydroxyphenyl)fluorene and a 3:7 to 7:3 mixture of terephthalic acid and isophthalic acid are reported in JP-A-No. 57-192432).
Furthermore, single polyesters derived from 9,9-bis(4-hydroxyphenyl)fluorene and isophthalic acid or a fatty acid are reported in U.S. Pat. No. 3546165. Although this patent describes the use of terephthalic acid/isophthalic acid (mole ratio=20/80) or terephthalic acid/sebacic acid (mole ratio=60/40), it does not describe the formation of a film.
The present inventors studied these reports, but found that the resultant polymers have disadvantages in that the polymerization degree of each resultant polymer is low, and only a white turbid solution is obtained because, when the polymer is dissolved in a solvent, a portion of the polymer is dissolved therein, and a film having a good appearance and good quality cannot be obtained by casting.
Furthermore, when injection, extrusion, compression, and other molding processes are applied to those polymers, molding is possible only when the processing is carried out at a higher temperature, which causes, for example, decomposition. In particular, the above-mentioned polymer is difficult to use in injection molding.
SUMMARY OF THE INVENTION
Accordingly, the objects of the present invention are to eliminate the above-mentioned disadvantages of the prior art and to provide a novel heat-resistant polyester having an excellent moldability or processability by including a diol and a mixture of phthalic acid and a fatty acid as components thereof.
Other objects and advantages of the present invention will be apparent from the following description.
In accordance with the present invention, there is provided a heat-resistant polyester having a structure represented by the formula (I):
--X--Y.sub.m (X--Z.sub.n -- (I)
wherein X represents the structure (A): ##STR3## wherein R represents hydrogen, methyl, or ethyl,
Y represents the structure (B): ##STR4##
Z represents the structure (C):
--OC(CH.sub.2).sub.l CO-- (C)
wherein l is an integer of 2 to 6, and
m and n are independent repeating numbers, the mole ratio of Y component and Z component in the formula (I) being 1/99 to 99/1 and said polyester having an inherent viscosity (η inh ) of at least 0.6 dl/g as determined at a temperature of 30° C. in a solution of 0.5 g of the polyester in 100 ml of a mixture of 60% by weight of phenol and 40% by weight of 1,1,2,2-tetrachloroethane.
BRIEF EXPLANATION OF THE DRAWING
The present invention will now be explained in detail with reference to the attached drawing of FIG. 1, which illustrates the correlation between a mole ratio of terephthalic acid/adipic acid and the glass transition temperature A or the decomposition initiating temperature B obtained from the thermal analysis of polyester obtained in the Example according to the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The polyesters according to the present invention contain a diol component and an acid mixture component composed of terephthalic acid and/or isophthalic acid and a fatty acids(s), wherein the mole ratio of the phthalic component to the fatty acid component is 1/99 to 99/1. Note, polyesters having a mole ratio of telephthalic acid to adipic acid of 1/99 to 60/40 exhibit the most desirable properties or characteristics for the present invention.
The polyesters according to the present invention have a glass transition temperature (Tg) of 170° C. to 320° C., an inherent viscosity of 0.6 dl/g or more, and a high degree of polymerization. In general, when the molded product is formed by heating, the necessary temperature difference between the decomposition temperature (Td) and the glass transition temperature is about 50° C. or more. The polyesters according to the present invention satisfy this requirement and, furthermore, since the Tg can be controlled by changing a mixing ratio of the carboxylic acids, the present polyesters can be preferably used as an injection molding material. In addition, since the present polyesters have excellent electric properties and the like, the polyesters can be preferably used in the fields of, for example, electrical connectors and electric parts of a microwave oven and the like. Furthermore, the present polyesters may be utilized as a heat-resistant adhesive. Note, the applications of the present polyesters are not limited to the above-mentioned fields.
The diols usable in the present invention are those having the formula: ##STR5## wherein R is H, CH3, or C 2 H 5 . Typical examples of such diols are 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene, 9,9-bis(3-ethyl-4-hydroxyphenyl)fluorene, and the like.
The carboxylic acids usable as the carboxylic acid component in the present invention may include aromatic carboxylic acids such as terephthalic acid and/or isophthalic acid and aliphatic carboxylic acids are those having the formula: HOOC(CH 2 ) l COOH, wherein l is 2 to 6, e.g., succinic acid, glutaric acid, adipic acid, pimeric acid, and suberic acid. Of these carboxylic acids, preferably adipic acid is used.
To maintain the decomposition temperature at as high a level as possible, and to control the glass transition temperature, preferably the above-mentioned aliphatic carboxylic acids are used. When the aliphatic chain of the aliphatic carboxylic acids is too long, the decomposition temperature is lowered, and when the aliphatic chain is too short, the glass transition temperature is not lowered to a desired level.
The mole ratio of the aromatic acid to the aliphatic acid in the present invention should be 1/99 to 99/1, for the following reasons. One object of the present invention is that the polyesters are moldable, e.g., injectable, extrudable, and compression moldable, by decreasing the Tg by including the specified amount of the aliphatic acids in the terephthalic acid and/or isophthalic acid. When the aliphatic acid component is included, the Tg is decreased but the Td is not decreased. Furthermore, when the aliphatic acid component is introduced, the flexibility is increased when a film is being formed, and the adhesion power and the handling properties are improved in the case of the adhesives. The present inventors found the difference between the above-mentioned tendency of Tg and Td, and effectively applied this finding to the production of the heat-resistant polyesters of this invention.
FIG. 1 illustrates one example of the thermal analysis data of the polyester (i.e., terephthalic acid-adipic acid), wherein the ratios of terephthalic acid-adipic acid are plotted on the abscissa axis and the temperatures are plotted on the ordinate axis, to show the glass transition temperature curve A and the decomposition initiation temperature curve B.
As shown in FIG. 1, when the mole ratio of terephthalic acid/adipic acid is increased, the glass transition temperature is linearly increased. Conversely, the decomposition initiating temperature is substantially constant at a mole ratio of the terephthalic acid/adipic acid of 80/20 to 10/90, but when the mole ratio is more than 80/20, the decomposition initiating temperature is rapidly raised.
Accordingly, when the mole ratio of terephthalic acid/adipic acid is more than about 60/40, the injection molding temperature is higher than the preferable temperature, i.e., the glass transition temperature +50° C., and therefore, the polyester is usually decomposed during injection molding. Consequently, polyesters having a mole ratio of terephthalic acid/adipic acid of 1/99 to 60/40, especially 1/99 to 40/60 or less are preferable as a molding material.
Furthermore, the polyesters according to the present invention are useful not only as the molding material, but also as a heat-resistant adhesive. Namely, depending upon the adhesion methods or the places or portions to be adhered, polyesters having varying ratios of the aromatic carboxylic acid to the aliphatic carboxylic acid may be used.
The production process of the present polyesters will now be explained.
The starting diols are dissolved in water by adding an alkali to form an aqueous solution. Although there are no limitations to the type of alkali, a hydroxide of alkali metals such as sodium hydroxide is preferably used. The advantageous concentration of the aqueous alkaline solution is 2% by weight or less, especially about 0.8% to 1.5% by weight. The diols are added to the aqueous alkaline solution to obtain the desired aqueous alkaline solution of the diols.
As the acid component, the chloride of each carboxylic acid is preferably used. The acid chlorides may be dissolved in organic halogen compounds such as 1,2-dichloroethane, chloroform, and trichloroethane to form the organic solvent solutions of the acid component.
Thereafter, the aqueous alkaline solution of the diols and the organic solvent solution of the acid component are subjected to interfacial polycondensation while stirring. Since the interfacial polycondensation reaction is carried out at the interface of the two solutions, the reaction is preferably accelerated when a surfactant is added to the aqueous alkaline solution of the diols in an amount such that the system is not emulsified.
Examples of such surfactants are those which do not react with the diols or the acid chlorides or the other acid components and which can withstand the alkali, because the surfactant is added to the aqueous alkaline solution. Preferable surfactants are cationic surfactants such as tetraalkyl (e.g., C 1 -C 6 alkyl) ammonium halide (e.g., chloride, bromide, iodide) and trialkyl (e.g., C 1 -C 6 alkyl) benzyl ammonium halide (e.g., chloride, bromide, iodide). Although the amount of the surfactant to be added is not critically limited and may be varied depending upon, for example, the type of surfactant, the amount usually used in the interfacial polymerization, is 5% by weight or less, more preferably 2% by weight or less, in the aqueous solution. The use of too large an amount of the surfactant unpreferably results in the formation of emulsification which makes the interfacial polymerization difficult.
Although there are no critical limitations to the polymerization conditions, the polymerization can be preferably effected at a temperature of 0° C. to 90° C., more preferably 20° C. to 30° C., for several hours to 24 hours.
After the reaction is completed, the resultant oil layer and the aqueous layer are separated and the above organic halogen compound added to the oil layer to lower the viscosity, followed by washing with water. The resultant product is then poured into, for example, methanol or acetone, the precipitated products are filtered and dried, and thus the desired polyesters are produced.
As explained above and in the following Examples, according to the present invention, heat-resistant polyesters having a glass transition temperature of 170° C. to 320° C., a tensile strength of 6 kg/mm 2 or more, and an inherent viscosity of 0.8 dl/g or more, which are capable of molding and processing can be unexpectedly provided, although it is known in the art that it is difficult to mold and process the polyester. Accordingly, molded products composed of polyesters having properties or characteristics comparable to or superior to those of products now on market as various mechanical parts, electric parts, and the like can be provided at a lower cost. Furthermore, the present polyesters can be used as a heat-resistant adhesive.
EXAMPLES
The present invention now will be further illustrated by, but is by no means limited to, the following Examples.
EXAMPLE 1
Adipic acid/terephthalic acid (mole ratio)=80/20
A 4.04 g amount of terephthalic acid chloride and 14.6 g of adipic acid chloride were dissolved in 300 ml of 1,2-dichloroethane. Further, 8 to 15 g of sodium hydroxide was dissolved in 1000 ml of water, followed by dissolving 35 g of 9,9-bis(4-hydroxyphenyl)fluorene and 15 g of tetraethyl ammonium chloride therein. The resultant solution was added all at once to the above-prepared organic solvent solution of the acid component while vigorously stirring, and the resultant mixture was allowed to react at room temperature for 10 to 15 hours. After completing the reaction, the aqueous phase was separated and 200 ml of 1,2-dichloroethane was added to the oily layer to lower the viscosity.
The resultant solution was washed three times with 500 ml of water and the solution was poured into acetone. The precipitate was then recovered by filtration, followed by drying, and thus the desired polyester was obtained.
The results of the physical property tests thereof are shown in Table 1.
EXAMPLE 2
A 100 millimole amount of a mixture of terephthalic acid chloride adipic acid chloride having a mole ratio of 1/99 to 99/1 was dissolved in 300 ml of 1,2-dichloroethane, followed by adding thereto an aqueous solution of 9,9-bis(4-hydroxyphenyl)fluorene used in Example 1, while vigorously stirring. The polyester was then produced in the same manner as in Example 1. The results are shown in Table 1.
EXAMPLE 3
The polyester was produced in the same manner as in Example 1, except that isophthalic acid chloride was used instead of the terephthalic acid chloride, and that the mole ratio of the adipic acid/isophthalic acid was 90/10.
The decomposition temperature was 360° C., the glass transition temperature was 200° C., and the inherent viscosity was 0.65 dl/g. The physical test results thereof are shown in Table 1.
EXAMPLE 4
The polyesters were produced in the same manner as in Example 1, except that an equal amount of succinic acid chloride, glutaric acid chloride, pimeric acid chloride, or suberic acid chloride was used instead of the adipic acid chloride. The decomposition temperature was 284° C., 259° C., 210° C. or 200° C., respectively, the decomposition temperature was 400° C., 400° C., 350° C., or 345° C., respectively, and the inherent viscosity was 0.73, 0.80, 0.65, and 0.66 dl/g, respectively.
The physical test results thereof are shown in Table 1.
The methods of determining the physical properties set forth in Table 1 are as follows:
1. Tensile strength . . . a film 10 mmW×100 mmL was used and the tensile strength thereof determined by an Autograph DSS 2000 manufactured by Shimazu Seisakusho, Japan.
2. Tensile modulus . . . Same as above
3. Tensile elongation at break . . . Same as above
4. Decomposition temperature . . . determined by using a Metler thermal analysis system TA 3000
5. Glass transition temperature . . . Same as above
6. Volume resistivity . . . determined by using a film having a tin foil adhered thereto as an electrode according to the method of Japanese Industrial Standard (JIS) C 2318.
7. Dielectric constant, dielectric dissipation factor . . . same as above
8. Dielectric breakdown strength . . . determined by holding a film between electrodes in the form of rods
9. Refractive index . . . determined by an Atago refractometer
10. Overall light transmission . . . determined according to the method of JIS K 7105
11. Yellowness . . . determined according to the method of JIS K 7103
12. Haze . . . determined according to the method of JIS K 7105
13. Water absorption . . . determined after drying at 120° C. for more than 10 hours, followed by dipping in ion-exchanged water at 23° C. for 24 hours
14. Solubility . . . determined by dissolving 1 g of polymer in 5 ml of a solvent
15. Inherent viscosity . . . the viscosity of a solution of 0.5 g of polyester in 100 ml of a mixture of 60% by weight of phenol and 40% by weight of 1,1,2,2-tetrachloroethane, at a temperature of 30° C., was determined.
TABLE 1__________________________________________________________________________ Example 1 Example 2*.sup.1 Example 3*.sup.2 Example__________________________________________________________________________ 4*.sup.3Mechanical PropertiesTensile Strength (23° C.) (kg/mm.sup.2) 5.93-6.0 5.8 5.6 4.9Tensile modulus (23° C.) (kg/mm.sup.2) 270 280 270 250Tensile elongation at break (23° C.) (%) 2.7 4.0 3.7 4.2Thermal PropertiesDecomposition temp. (°C.) 385 See FIG. 1 370 350Glass transition temp. (°C.) 220-225 " 180 160Electric PropertiesVolume resistivity (23° C., 100 V) (Q · cm) 1.5 × 10.sup.14 1.0 × 10.sup.14 2.3 × 10.sup.14 2.0 × 10.sup.14Volume resistivity (200° C., 100 V) (Ω · cm) 2.1 × 10.sup.13 -- -- --Dielectric constant (23° C., 1 MHZ) 3.27 3.27 3.22 3.04Dielectric dissipation factor (23° C., 1 MHZ) 0.022 0.023 0.021 0.024Dielectric breakdown strength (23° C.) (KV/mm) 107 110 98 96Optical PropertiesRefractive index 1.636 1.635 1.633 1.637Overall light transmittance (%) 91.6 90.5 91.0 90.5Yellowness 3.4 2.7 2.5 2.8Haze 0.9 0.6 0.9 0.8Chemical PropertiesWater absorption (23° C., 24 hr) 0.78 Same as Ex. 1 Same as Ex. Same as Ex. 1Solubility Dichloroethane " " " Chloroform " " " N--Methyl pyrrolidone " " " DMAC " " " DMF " " "Inherent viscosity (dl/g) 0.69 0.64 0.55 0.49__________________________________________________________________________ *.sup.1 Results obtained when ratio of adipic acid/terephthalic acid was 90/10 are shown. The results obtained in other mole ratios are similar except for the decomposition temperature and glass transition temperature *.sup.2 Results obtained when the mole ratio of adipic acid/isophthalic acid as 90/10 *.sup.3 Results obtained when the mole ratio of glutaric acid/terephthali acid was 80/20
|
A heat-resistant polyester having a structure represented by the formula (I):
--X--Y).sub.m X--Z).sub.n (I)
wherein X represents the structure (A): ##STR1## wherein R represents hydrogen, methyl, or ethyl, Y represents the structure (B): ##STR2## Z represents the structure (C):
--OC(CH.sub.2).sub.l CO-- (C)
wherein l is an integer of 2 to 6, and m and n are independent repeating numbers, the mole ratio of Y component and Z component in the formula (I) being 1/99 to 99/1 and said polyester having an inherent viscosity (η inh ) of at least 0.6 dl/g as determined at a temperature of 30° C. in a solution of 0.5 g of the polyester in 100 ml of a mixture of 60% by weight of phenol and 40% by weight of 1,1,2,2-tetrachloroethane.
| 2
|
BACKGROUND OF THE INVENTION
It is well-known that various simple carbides can be used to produce fuel gases such as acetylene, methane, allylene, etc., and that calcium carbide manufacture and conversion to acetylene has provided the basis for a major industry for many years. Nevertheless, carbide-acetylene has never had a measurable impact on the production of general purpose fuels. Rather, its applications have been restricted to providing high energy fuel for the welding gas industry plus major non-fuel or chemical applications, for example, as a chemical intermediate. Several factors have precluded more widespread use of calcium carbide derived acetylene for general fuel purposes; among these are: (1) High input power requirements resulting from the necessity of employing electric arc furnaces to reach the temperatures needed to manufacture calcium carbide (approximately 2000° C.); (2) The hazards of handling the derived acetylene, either under pressure or in mixtures with air, due to its endothermic nature; (3) The magnitude of the disposal problem for the spent lime that would arise if large amounts of carbide acetylene were used for general fuel purposes; (4) Transportation costs of raw materials and calcium carbide occasioned by high total tonnages per unit fuel value; and (5) Total system costs in comparison with alternative fuel systems.
Patents and a literature article bearing upon the state of the art of manufacture or reaction of carbides or generation of combustible volatiles of the type contemplated in the present invention includes the following:
U.S. Pat. No. 2,802,723--Aug. 13, 1957
U.S. Pat. No. 3,031,287--Apr. 24, 1962
U.S. Pat. No. 3,154,378--Oct. 27, 1964
U.S. Pat. No. 3,201,052--Aug. 17, 1965
U.S. Pat. No. 1,735,925--Nov. 19, 1929
U.S. Pat. No. 1,741,307--Dec. 31, 1929
U.S. Pat. No. 1,824,896--Sep. 29, 1931
U.S. Pat. No. 2,445,796--July 27, 1948
U.S. Pat. No. 2,942,959--June 28, 1960
U.S. Pat. No. 3,771,259--Nov. 13, 1973
U.S. Pat. No. 3,405,068--Oct. 8, 1968
U.S. Pat. No. 889,124--May 26, 1908
U.S. Pat. No. 1,445,644--Feb. 20, 1923
U.S. Pat. No. 260,954--July 11, 1882
U.S. Pat. No. 3,115,394--Dec. 24, 1963
U.S. Pat. No. 2,781,248--Feb. 12, 1957
U.S. Pat. No. 2,654,661--Oct. 6, 1953
U.S. Pat. No. 1,173,417--Feb. 29, 1916
U.S. Pat. No. 1,938,202--Dec. 5, 1933
U.S. Pat. No. 1,960,886--May 29, 1934
U.S. Pat. No. 3,188,179--June 8, 1965
U.S. Pat. No. 3,108,857--Oct. 29, 1963
U.S. Pat. No. 2,602,019--July 1, 1952.
Journal of Phys. Chem.-Vol. 65, pp. 2026-2028 (1961).
While the principal volatile products of conversion of carbide "fuel precursors" are hydrocarbons, they may be accompanied by various lesser amounts of hydrogen, carbon monoxide, carbon dioxide and compounds containing carbon, hydrogen and oxygen (and/or additional elements). In the succeeding discussion, the term "fuel" shall refer to all such volatiles, and "fuel precursor" shall designate a compound capable of generating all such volatiles where used for fuel or non-fuel purposes.
It is therefore a primary object of the present invention to provide a process for the economical production of fuel precursors and for the conversion of the fuel precursors to hydrocarbon gases or liquids for various fuel or non-fuel uses.
It is another object of the invention to provide a method of producing a fuel gas compound or mixture of greater intrinsic stability and safety than acetylene, for example, a fuel gas consisting primarily of methane or comparable compounds.
Another further object of the present invention is to provide a process for the manufacture of fuel precursors, which process uses substantially less power per unit derived fuel energy than the calcium carbide-acetylene system, which can be operated at substantially lower temperatures, and for which the mineral residue (oxide-hydroxide) generated from the fuel gas conversion stage can be readily and economically recycled to manufacture more fuel precursor.
Still another object of the present invention is to provide a fuel precursor which may be stored or stockpiled safely without undue fire hazard or deterioration due to air exposure or other factors, to provide an economical reserve capacity for accommodating short term or seasonal fluctuations in fuel demand or supply requirements during scheduled or unscheduled interruptions in manufacture of fuel precursor.
Yet another object of this invention is to provide a continuous process for the manufacture of fuel precursor and a conversion process for hydrocarbon generation which may be rapidly adjusted to meet utility demand loads.
A further object of the invention is to provide mineral carbide fuel precursors which are convertible to fuel gases or liquids.
Yet a further object of the present invention to provide fuel precursors from which sulfur and other noxious or undesirable impurities introduced by the coal or other raw materials during manufacture of the precursors can be substantially reduced or removed easily to provide environmentally clean gaseous or liquid fuels.
Even another object of the invention is to provide fuel precursors capable of generating high yields of unsaturated hydrocarbons, such as olefins and acetylenes, which are useful for manufacture of polymers and other valuable chemical products.
These together with other objects and advantages which will become subsequently apparent reside in the details of the process and operation of the invention as more fully hereinafter described and claimed, reference being had to the accompanying drawings forming a part hereof, wherein like numerals refer to like parts throughout.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic representation of a process for producing fuel precursors (solid).
FIG. 2 is a schematic representation of a process for converting the fuel precursors into useful fuel gases or liquids.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A recent review of metal carbides by Frad reports that of the 75 metallic and semi-metallic elements of atomic number 92 or lower, at least 48 form binary compounds with carbon (i.e. carbides) with another 7 elements having been reported as having formed carbides but whose existence requires further confirmation. Hundreds of carbides have been investigated in which two or more metallic elements are combined with carbon, both as true compounds with more or less fixed ratios of metallic elements, and as solid solutions between simple binary carbides. A problem in characterizing such complex systems, as well as binary carbides, is the tendency toward defect structures in which significant fractions of the lattice sites normally occupied by metal or carbon atoms may be vacant.
It is desirable to classify carbides in regard to chemical and physical properties or thermodynamic stabilities to identify those compounds useful as fuel precursors, refractories, abrasives or for cutting tool applications, and to indicate possible methods of preparation.
The classification of carbides into "salt-like" compounds and "metal-like" compounds is most useful in describing their general properties. Salt-like or ionic carbides are electrical insulators with thermophysical properties similar to oxides and usually showing little tendency toward defect structures. They are generally reactive toward water or dilute acids, are reducing agents at elevated temperatures and tend to dissolve in fused salt systems. These carbides are usually formed from the more basic metals such as alkali, alkaline earth, and aluminum family elements. On the other hand, metal-like carbides are electrical conductors with thermophysical properties similar to metals and usually showing an appreciable tendency toward defect structures. Most are substantially unreactive toward water or dilute acids at normal temperatures, do not behave as reducing agents except at extremely high temperatures and are generally chemically inert. Many are also extremely hard materials with high melting points. These metal-like carbides are usually formed from less basic elements such as transition metals or semi-metals; however, they also include lanthanide or actinide element carbides. Some exceptions to the above general trends may be noted in, for example, a number of carbides of the rare earth elements, thorium and uranium. Such carbides behave principally like ionic carbides but are electrical conductors, apparently due to lower than normal chemical valence and close metal-metal atomic distances in the crystal structure. In addition, some metallic carbides of first transition series elements such as vanadium, chromium, manganese, iron, cobalt and nickel behave in most characteristics like metallic or interstitial carbides, but are more reactive or corrodible by water or dilute acids, apparently resulting from atomic size defects in the crystal structure.
A classification of carbides on the basis of thermodynamic stability is useful in indicating possible methods of preparation, precautions in storage and handling and reactivity at various temperatures. It is convenient to use five categories which may be designated as highly stable, stable, metastable, marginally unstable, and highly unstable.
The highly stable carbides are limited to interstitial carbides of the transition elements which have negative heats of formation in excess of -(25)Kcal/mole° C. and which are extremely hard, refractory, and chemically inert. Examples include TiC, ZrC, TaC, NbC, and the like. Tungsten carbides, boron carbide and silicon carbide have lower heats of formation but have similar properties and should probably be included in this group.
The stable carbides include those carbides with negative free energies of formation at all temperatures from room temperature to 1200° C. or more except those carbides included in the first group. In this category are the carbides of the alkaline earth metals (except magnesium), aluminum, certain high carbides of chromium, manganese and the rare earth metals.
Metastable carbides are those compounds which are thermodynamically stable with respect to free metal and carbon at some elevated temperature but, even though unstable at ambient temperatures, can be quenched and preserved indefinitely at low or ambient temperatures. Examples include Mn 3 C, Mn 15 C 4 , UC 2 , MoC, etc.
The marginally unstable carbides include carbides of iron, cobalt and nickel which are slightly less stable than the corresponding metal and graphite but which are also storable for indefinite periods at room temperature.
The last class, highly unstable carbides, consists of the carbides that cannot be formed from the elements, but may only be prepared by lower temperature indirect processes from carbon compounds. These include the carbides of magnesium, zinc, copper, silver, etc. If their heats of formation are too positive, they may be subject to explosive decomposition.
For the purpose of evaluating carbides of potential utility in the generation of fuel gases or liquids, it is necessary to understand the chemical reactions of the various carbides, especially toward water or steam. Unfortunately, a large number of carbides which have previously been reported have either not been studied for hydrolytic behavior or such studies as have been made are unreliable due to poorly characterized starting materials or imprecise methods of analysis. This is evident from conflicting data from several investigators.
Based on the first classification system (properties) discussed, one may summarize hydrolysis studies as follows:
1. The salt-like or ionic carbides normally hydrolyze to yield a single hydrocarbon characteristic of the carbide and on that basis may be classified as acetylides, methanides or allylides corresponding to acetylene, methane or allylene as the hydrolytic reaction product.
2. The metal-like carbides are for the most part substantially chemically inert at low temperatures, but some may be hydrolyzed (corroded), yielding a mixture of hydrocarbons and various amounts of hydrogen, oxides of carbon, etc., depending on the conditions of hydrolysis.
3. In the metal-like carbides which are hydrolyzable, the excess metallic atoms are capable of reducing the water to form neutral hydrogen atoms which can then directly reduce carbon atoms or react with unsaturated hydrocarbons or chemical intermediates such as methylene groups (CH 2 ). The hydrolysis reactions of these compounds are consistent with treating them as solid solutions of ionic carbides in excess free metal alloys of metal and hydrolyzable carbide.
Most studies of hydrolytic behavior have been carried out in aqueous solution at moderate temperatures, but various studies with steam at elevated temperatures have been made. It has long been known in the prior art that even very inert carbides such as SiC are attacked slowly by prolonged exposure to steam at about 2000° F. It appears that carbides, especially the metal-like compounds, behave in many regards like the parent metal forming a superficial layer of oxide or hydroxide in the presence of water vapor and that further attack is inhibited unless some mechanism is present to accelerate diffusion or migration of additional water molecules through the surface layers.
Composition of Fuel Products
Of the ionic carbides, it is well-known from previous work that the hydrolysis product of carbides formed from metallic elements of small ionic radii such as aluminum and beryllium consists primarily of methane and the product formed from the lower carbide of magnesium, with Mg 2 C 3 forming allylene (methylacetylene). Most of the remaining ionic carbides yield acetylene upon hydrolysis.
For the metallic carbides, we may treat the mixture of carbide, excess metal and/or free carbon as a "pseudocompound" of composition M Z C, where the metal is represented by the symbol M. A fraction x of the carbon atoms yields hydrocarbons on hydrolysis, with a fraction 1-x appearing as free carbon. A nominal negative valence, v, is assigned to the x fraction of carbon (corresponding to V=-v hydrogen atoms combined per carbon atom). Then -V represents the valence of the carbon atom. Thus V=4 for pure methane formers, V=3 for ethane formers, V=2 for methylene or ethylene formers and V=1 for acetylene formers. We have found that the experimental results for transition metal carbides in the Mn 3 C, Fe 3 C, Ni 3 C series can be accommodated with a carbon valence of about v=-2.8 to -3.4. The rare earth dicarbides and sesquicarbides can be considered to have a carbon valence of about v=-1. The carbon content then contains Vx equivalents which are balanced by an equal number of metal ionic equivalents. The balance of the metal atoms can be considered as neutral metal.
The total number of metallic equivalents after hydrolysis is given by Z V where V is the average valence of lowest metallic states of constituent elements stable in the presence of water. The difference ZV-Vx represents the excess reducing power which appears as hydrogen in reaction products. We may thus write the over-all reaction as: ##EQU1##
The approximate value of fuel products heat of combustion per mole °C. is given by: ##EQU2##
Using the above formula we may determine the fuel gas heat of combustion for the following carbides:
______________________________________ For x = 1,Compound ΔH.sub.COM (Kcal/mole C) ΔH.sub.COM.sup.=______________________________________M.sub.3 C (V = 2, V = 3) ##STR1## 295.5M.sub.7 C.sub.3 (V = 2, V = 3) ##STR2## 249.9M.sub.3 C.sub.2 (V = 2, V = 3) ##STR3## 193M'C.sub.2 (V = 3, V = 1) ##STR4## 172.1M.sub.2 'C.sub.3 (V = 3, V = 1) ##STR5## 189.2M.sub.2 'C.sub. 3 (V = 3, V = 2) x(174) + (1 - x) 68.3 174M'C.sub.2 (V = 2.5, V = 1) ##STR6## 163.5M.sub.2 'C.sub.3 (V = 2.5, V = 1) ##STR7## 177.8______________________________________
The specific heating value of the fuel gas depends on the distribution of carbon atoms between methane and higher hydrocarbons with 2, 3 or more carbon atoms per molecule.
Thus for V=3, CH 3 may be derived from CH 3 =1/2CH 4 +1/4C 2 H 4 (m=1.33) or CH 3 =1/2C 2 H 6 (m=2), where m is the average number of carbon atoms per hydrocarbon molecule. The heat of combustion per mole of carbon is nearly the same for both systems, but the heat of combustion per unit volume (gas mole) is 50% greater in the second case. As an example, for Mn 3 C the average number of carbon atoms per hydrocarbon molecule obtained on hydrolysis equals 1.45.
Energy Balance for Synthetic Fuels
All of the existing or proposed processes for producing hydrocarbons and/or carbon monoxide and hydrogen from carbonaceous sources may be considered as a sum of individual chemical reactions in which all reactants other than carbon and oxygen enter in a cyclic manner, emerging in the same compounds as they enter. For a given quantity of carbon, the potential heating value upon complete combustion is equal to 94.05 Kcal/gram mole (169.29 KBTU/lb mole) which may be taken as the theoretical input energy unless other forms of energy are also consumed. For every mole of carbon consumed a fraction f will be recovered as useful fuel gases and the fraction 1-f will be burned or otherwise lost to supply process heat. The fraction f may be divided into two parts, f=f hc +f o where f hc is the fraction appearing in hydrocarbons and f o is the fraction appearing as carbon monoxide. The useful output heat is then given by:
ΔH.sub.out =f.sub.hc ΔH.sub.hc +f.sub.o ΔH.sub.co +f.sub.H.sbsb.2 ΔH.sub.H.sbsb.2
where ΔH a is the average heat of combustion of a per mole (with hydrocarbons C m H n rewritten as CH n/m ) and f H .sbsb.2 is the fractional number of moles of hydrogen produced per mole of carbon consumed.
In the formation of fuel gas directly from carbon, the water gas (or synthesis gas) reaction is of importance:
C+H.sub.2 O=CO+H.sub.2 ΔH=+41.9 Kcal/mole °C.
Since the reaction is endothermic, the heat necessary is usually supplied by burning extra carbon. By noting that the heat of combustion of carbon to carbon dioxide is 94.05 Kcal/mole, it may be readily calculated that 0.445 additional moles of carbon must be burned to provide the theoretical amount of heat necessary to produce one mole of carbon monoxide by the above equation. Restated in terms of the previous discussion, the fraction f=0.692 of the original carbon is converted to CO while the fraction 1-f=0.308 is burned to CO 2 to supply process heat. The output heat ΔH out =0.692(67.65)+0.692(68.3)=94.05 Kcal which is just equal to the theoretical input energy. All real processes will operate at less than 100% thermal efficiency due to thermal, frictional and other losses.
For processes that use metallic carbides as chemical intermediates, two other thermal figures of merit are useful, namely, net and gross heat ratios, where the net heat ratio is the ratio of heat of combustion of fuel gases produced to the heat of combustion of the carbide, and the gross heat ratio is the ratio of the sum of the heat of fuel gas combustion plus heat of conversion (hydrolysis) to the heat of combustion of the carbide. In these calculations, the oxidation of the metallic component is considered to be carried to the valence state normally found after hydrolysis. Table I shows heats of combustion and net heat ratios for various carbides.
TABLE I______________________________________Thermochemistry of Carbides Net Heat of Heat of Fuel Gas Heat HeatCompound Formation Combustion of Combustion Ratio______________________________________CaC.sub.2 -15 325 310.61 .956Al.sub.4 C.sub.3 -48.6 1031.55 638 .618Mn.sub.3 C -3 367.05 333 .907BeC.sub.2 -5 316.5 310.6 .981Be.sub.2 C -22.2 363.85 212.8 .585MgC.sub.2 +21 352.9 310.6 .88Mg.sub.2 C.sub.3 +19 588.75 463.1 .787Fe.sub.3 C +5 290.15 269 .927ThC.sub.2 -45 435.1UC.sub.2 -42 416.1 360 .865LaC.sub.2 (-30 est) (372 est) (323-355 est)La.sub.2 C.sub.3 (-50 est) (660 est) (505-568 est)CeC.sub.2 (-30 est) (375.5 est) 355Ce.sub.2 C.sub.3 (-50 est) (667 est) (505-568 est)______________________________________
In Table I heats of formation or combustion are expressed in kilocalories per mole.
The net heat ratios are generally above 0.8-0.9, except for the ionic carbides which yield methane on hydrolysis. Thus, Al 4 C 3 has a net heat ratio of 0.618 while Be 2 C has a value of 0.585, which are both too low for efficient synthetic fuel processes.
If we wish to formulate a carbide fuel process which is economical and produces a fuel with lower handling hazards than acetylene, we may eliminate from consideration all the simple ionic carbide. The remaining carbides are members of the alloy or metal-like carbide class. There are two principal types of metal-like carbides which may be considered as candidates for a synthetic fuel process: (1) Interstitial alloy carbides such as Mn 3 C, Fe 3 C and related carbides of higher carbon content; (2) Rare earth or actinide carbides such as cerium, thorium, or uranium carbides.
The first class (interstitial alloy carbides) contains metals whose oxides are easily reducible, but their heating values per unit weight are low and their reactivity toward water or steam is low in some cases. In addition, they are difficult to prepare free of excess metal, which usually requires an acidic medium to effect hydrolysis.
The second class (rare earth or actinide carbides) is more reactive, but the metallic elements are difficult to reduce.
We have discovered that by modifying the composition of each class we can achieve practical advantages in realizing a practical synthetic fuel process.
It has been previously established that Fe 3 C and Mn 3 C form a continuous series of solid solutions. As the iron content increases, the energy efficiency of the fuel process increases, but the reactivity toward water or steam is lowered. To hydrolyze pure iron carbide requires either dilute acids or very high temperature steam. We have found that by incorporating small amounts of a reactive or corrodible metal such as calcium, magnesium, zinc, and/or aluminum to the alloy which is reacted with carbon to form the carbide, a limited amount of the reactive metal is incorporated in the carbide solid solution and an additional amount remains in the alloy phase. Alternatively, ternary phases such as Al Fe 3 C may be formed with the various mixed carbides.
In the usual methods of forming the transition metal carbides from molten metal and carbon, it is often difficult to prepare the carbides completely free from an excess metal-rich phase. This phase can be more resistant to action of water or steam. By incorporating sufficient reactive metal (Ca, Mg, Al, Zn) to reach a level of 2 to 30 atom percent of metal in the alloy phase, the corrodibility is enhanced allowing easier hydrolysis. It also tends to lower the melting point of the alloy, permitting synthesis at a lower temperature.
Slightly higher energy values per pound of fuel precursor can be achieved by hydrolyzing carbides of higher carbon content, such as Mn 7 C 3 , Cr 7 C 3 , or Cr 3 C 2 . These carbides, especially the chromium compounds, are quite resistant to hydrolysis. We have found that by alloying again with reactive metals such as Mg, Al, Zn, or Ca, we can produce a more easily corrodible carbide.
While chromium or vanadium do not form trichromium or trivanadium carbides, compounds may be formed by substituting one aluminum atom, as Cr 2 AlC or V 2 AlC which have a high potential energy value per pound. These compounds can also form solid solutions with the (Fe, Mn) 3 C system.
Among the Rare Earth carbides, cerium or lanthanum dicarbides or sesquicarbides REC 2 or RE 2 C 3 have the best potential as a fuel precursor of previously reported carbides, where RE represents a rare earth metal. Similar compounds formed from Misch-metal or unseparated Rare Earth metals and carbonhave a lower system cost for fuel generation.
We have discovered that by alloying the Rare Earth metal with bi- or trivalent metals of more easily reducible metals, especially of large ionic radius, the energy of formation may be lowered. On size grounds, calcium, strontium, barium, bismuth, lead, and tin are candidates, but the alkaline earth metals do not offer appreciable savings in energy. We have found that the solubility of smaller ions such as zinc or iron or manganese can be enhanced by co-dissolving a larger than normal ion such as barium.
While the substitution of divalent metal ions for Rare Earth ions can lower the molecular weight and reduction energy of the fuel precursor, it also lowers the fuel value of gases since the reducing capacity is lower for divalent than trivalent metals.
Preparation
It is well-known in the art that the following carbides may be prepared by one or more of the following procedures:
1. Direct combination of metallic element(s) and carbon:
A. Solid state diffusion
B. Melting+congruent solidification
C. Peritectic freezing
D. Eutectic freezing
E. Eutectoid or peritectoid decomposition.
2. Reduction of oxide with excess carbon:
A. Solid state
B. From melt.
3. Reduction of sulfides with added carbon and optionally hydrogen.
4. Reduction of chlorides with added carbon and optionally hydrogen.
5. Metathesis with other carbides.
Of these methods only the first and second are applicable to a cyclic process for fuels generation. Calcium carbide is made commercially by reduction of an oxide with excess carbon from a melt (method 2B), but this requires exceptionally high temperatures and a massive input of heat, usually furnished by electric sources.
In contrast, the processes in the first group are exothermic, supplying their own reaction heat, but require prior reduction of metal oxides to metals. The most applicable method within the first group is governed by the phase diagram of the system involved; however, methods based on solid state transformations (1A and 1E) are generally too slow to be useful for large scale synthesis.
Most systems of interest cannot be readily produced by method 1B, congruent solidification, so we are generally left with methods 1C or 1D. Method 1C could yield pure carbide in principle, but for practical configurations, the desired product will be mixed with a metal rich phase. This condition will also be found for method 1D.
We have found that for most of the modified compositions discussed earlier, a peritectic freezing process is the most favorable method of synthesizing the desired carbide.
For the modified (Fe, Mn)C system, the following constraints are present:
1. Pure Mn 3 C can only be made by solid state reaction since it is unstable above 1050° C.
2. Pure Fe 3 C is marginally unstable but may be produced by peritectic freezing at temperatures above 1050° C.
3. Fe-Mn alloys up to about 80% Mn may form carbides by peritectic freezing at temperatures which drop as the Mn content increases.
I have discovered that a molten (Fe-Mn) alloy with dissolved carbon may be modified by additions of metallic calcium, aluminum, magnesium or zinc with the following results:
1. Melting point is lowered.
2. Peritectic freezing yields a trimetal carbide M 3 C whose metallic atoms consist predominantly of Fe and Mn, but with lesser amounts of low melting point metals.
3. In partial freezing, a slushy mixture of M 3 C and liquid metal results which upon further cooling yields a multiphase solid mixture which may be readily hydrolyzed with water or steam to yield a mixture of hydrogen and hydrocarbons.
It will be understood by those familiar with the art that some departure from specified metal/carbon ratios may commonly occur in these alloy carbide systems without changing the general behavior or advantageous properties of such systems.
One may form higher carbides within this system by solid state reaction of trimetal carbides with excess carbon to yield carbides of nominal composition M 7 C 3 (also M 5 C 2 ). These may conveniently be formed by partial peritectic freezing of M 3 C with equilibrium metal rich phases, then adding additional powered carbon and completing solidification followed by aging or curing at temperatures of 400°-700° C.
A similar procedure may be used to form M 3 C 2 carbides with high chromium content.
For the modified RE 2 C 3 system (where RE represents a rare earth element), the following constraints are present:
1. Pure La 2 C 3 or Ce 2 C 3 may be produced by peritectic freezing at temperatures above 800° C.
2. Misch-metal alloy with dissolved carbon can yield RE 2 C 3 by peritectic freezing above 750° C.
I have discovered that molten lanthanum, cerium or misch-metal with dissolved carbon modified by additions of barium, zinc, lead, and/or bismuth give an alloy with the following results:
1. Melting point is lowered.
2. Peritectic freezing yields a sesquicarbide containing appreciable quantities of non-lanthanide metal atoms.
3. The carbides formed upon partial or total freezing plus the interstitial metal rich phase retain the reactivity toward water or steam shown by the pure lanthanide carbides or metals.
4. The energy of reduction of the metallic alloy is lower than for the pure lanthanide system equivalent to a given amount of carbon.
The higher rare earth carbides REC 2 may be formed congruently from the melt at extremely high temperatures, peritectically at intermediate temperature or by solid state transformation.
I have found that the dicarbides REC 2 may be conveniently prepared by first forming the modified sesquicarbides, RE 2 C 3 as previously described. By mixing excess (powdered) carbon with a partially frozen peritectic mixture consisting of a liquid metal-rich phase in equilibrium with crystalline carbide, and then cooling, a 3 phase solid mass is obtained which will slowly convert to a structure containing predominantly dicarbide if maintained at elevated temperatures (400°-700° C.).
As a practical matter in forming carbides by peritectic freezing, by mixing a controlled amount of powdered carbon with a partially frozen peritectic mixture of carbide and metal-rich liquid, removing additional heat to complete solidification and aging or curing to promote more complete transformation to carbide, one may produce carbides more easily than by employing separation techniques on partially frozen mixtures.
Hydrolysis
The results of hydrolysis experiments on metal-like carbides have been reported on numerous occasions, often with conflicting results. An examination of previous work along with my own studies has led to several generalizations in this field:
1. The metal-like carbides can be considered to be an "alloy" between excess metal and an ionic carbide where the ionic carbide would contain metal ions in a normal valence state and carbon has a nominal valence of -4 for most carbides whose structure leads to large C-C bond distances and a valence of -1 for acetylides where C-C distances below 1.3 A are found between isolated pairs of carbon atoms.
2. Upon hydrolysis, the excess metal reduces the water to hydrogen while the ionic carbides yield methane or acetylene.
3. Some of the hydrogen tends to react with acetylene or unsaturated carbon or hydrocarbon fragments which may evolve by other processes.
4. Metastable carbides such as Fe 3 C or Mn 3 C tend to partially revert to metal and carbon which gives a higher than expected H 2 content on hydrolysis. From 10 to 15% or more of the total carbon content may revert to free carbon.
5. The rare earth carbides on hydrolysis behave as acetylides with excess reducing agents; they may be viewed as alloys between excess rare earth and hypothetical REC 3 . The hydrogen evolved by the excess metal partially reduces the acetylene and partially appears as H 2 .
6. The metal-like carbides generally produce lesser amounts of various other hydrocarbon molecules as a result of secondary reactions of intermediate or primary hydrolysis products.
Of prime importance in thermal efficiency of cyclic processes is the final state of the metal atoms following hydrolysis. By reacting the carbides with steam or water and allowing the reactants to increase in temperature, the metallic constituents may be largely recovered as oxides rather than hydroxides. As is well-known in the chemical arts, the alkali metal hydroxides cannot be dehydrated at atmospheric pressure below their boiling points, but alkaline earth metal hydroxides can be dehydrated at temperatures in the 200°-600° C. range and other metal hydroxides are more easily dehydrated. As a general rule, the hydroxides with very low water solubility are easily dehydrated.
By recovering metals in oxide form, the energy of dehydration is saved in processing the material for reduction to metal.
Description of Complete Process
The following describes the complete process for forming fuel gases or liquids from carbonaceous sources using metallic carbide synthesis and hydrolysis as intermediate steps. The process will be described in terms of preferred embodiments, it being understood that certain variations in operating conditions may be useful as operating experience is gained on larger scale installations.
A. Forming the Fuel Precursors
1. Carbonizing or pyrolyzing raw carbonaceous material to remove volatile matter and forming coke or char.
2. Mixing spent metal oxide-hydroxide residue with sufficient carbonized coke or char to reduce said metal compounds to free metal and saturate said metal with carbon and applying heat to cause such reduction.
3. Mixing said carbon-saturated molten metal with excess finely divided coke or char and maintaining such mixture at temperatures above the freezing point of the molten metal until a major fraction of the mixture has been converted to carbide compounds.
4. Removing the carbide material formed in step 3, along with various amounts of molten metal-rich solution and optionally some unconverted carbon in fine particulate form and holding said mixture at some lower temperature at which the remaining molten material solidifies, or alternatively becomes to viscous that migration of carbon or carbide particles is inhibited, until further conversion processes to form carbides are essentially complete.
5. Dividing and consolidating carbide product into agglomerates of useful size for storage or handling and cooling sufficiently to permit storage or shipment.
B. Conversion of Precursors to Fuel Products
6. Introducing said carbide agglomerates (fuel precursors) along with steam or water into a gas tight reaction chamber to effect hydrolysis to form metal oxides and/or hydroxides plus volatile fuel products consisting of fuels and optionally hydrogen plus small amounts of impurities.
7. Removing spent metal oxides/hydroxides which are returned to step 2 and recovering the heat of hydrolytic reaction.
8. Purifying generated gases and molten metals by filtering, scrubbing or slagging operations.
9. Removal and recovery of volatile fuel products.
Formation or Manufacture of Fuel Precursors
Referring now to the drawings for a more detailed explanation of the process of the invention, it can be seen that FIG. 1 is a schematic representation or flow diagram of a process for producing solid metallic carbides which can be converted, by chemical reaction, to fuel gases or liquids. Raw materials for the process are raw carbonaceous materials, and one or more metal oxides or hydroxides which may be largely supplied as recycled material from the gas generation stage of the process.
The raw carbonaceous material is reduced in particle size in crusher 16, to dimensions which will at least pass a 10 mesh screen. All of the entering carbonaceous material is pyrolyzed to remove a large portion of its constituent volatiles, although conditions in pyrolyzer 18 need not be controlled to achieve complete coking or devolatization. Thus, pyrolysis is advantageously accomplished below normal coking temperatures of about 2000° F. Rather, the raw, crushed carbonaceous materials are subjected only to a pyrolyzing temperature of about 750°-1250° F., preferably 900°-1100° F. for a time sufficient to remove from 80 to 95% by weight of the volatiles therein. The time required will be limited by heat transfer considerations and will vary from flash heating systems to 12 hours or more depending on process apparatus employed. Partial vacuum (for example, at pressures in the range pf 2 to 8 psia) may be used if desired. It is important that the pyrolyzing temperature be sufficiently high that the partial pressure of water be kept sufficiently low to convert to oxides the major proportion of dehydratable starting material hydroxides in subsequent steps of the process. Water driven off in pyrolyzer 18 can be reintroduced into the process as steam. Volatile gases with fuel value may be used to supply over-all process heat by combustion in the plant, mixed with hydrolytic process gas to augment output, or marketed as a separate fuel gas. A portion of the pyrolyzed carbonaceous material continues on to the mixer 20 for admixture with the metallic oxide/hydroxide materials. The balance of the pyrolyzed carbonaceous material is directed to synthesizer 26 where it is used to form the solid mixed metallic carbide hydrocarbon gas precursor elements.
The metallic oxide/hydroxide raw materials are passed directly to one or more crushers 12, 14 where they are reduced in particle size for ease of handling and to enhance subsequent processing, and then to mixer 20. Although the particle size of the crushed metal compounds is by no means critical, it is preferred that they pass a 20 mesh screen. In mixer 20, the ambient temperature metal oxide/hydroxide materials are thoroughly mixed, as by tumbling, with the relatively hot (800°-900° F.) pyrolyzed carbonaceous material. If spent fuel precursors from which the fuel gas has already been generated are recycled, they would be crushed, if necessary, and then metered from supply 15 in appropriate proportions directly into mixer 20.
The thoroughly admixed constituents of mixer 20 are conveyed through metering device 21 into reactor 22 where they are reduced to liquid metal at the reactor temperature of about 1400°-2400° F. A considerable quantity of heat must be supplied either by radiant energy or chamber walls heated by indirect combustion or by concurrent combustion of excess carbon inside the chamber as in a blast furnace. The time of reaction will depend on heat transfer limitations but may be expected to require several hours for commercial size reduction chambers. In the reactor, the metal oxides/hydroxides are reduced to free metal according to the reactions:
M.sub.x O+C→xM+CO
M.sub.x (OH).sub.2 +2C→xM+2CO+H.sub.2
M.sub.x (OH).sub.2 +C→xM+CO+H.sub.2 O
where M represents the metal element.
Any by-product carbon monoxide gas generated in reactor 22 from the reduction of the metallic compounds or from the residual volatiles in the carbonaceous material is directed to a scrubber (not shown) and then marketed as a fuel gas or used to supply process heat. The composition exiting from reactor 22 is molten and consists primarily of liquid metal with dissolved carbon and an insoluble slag or impurity layer which may be separately drained and disposed. The metallic layer then enters a heated blender/reservoir 24 which has the capability to store the molten composition and via meter 25 to control the quantity of composition which passes directly to synthesizer 26. The balance of the molten composition is directed to a converter 28 which is maintained at approximately 1000° F. minimum temperature. In the converter the composition is modified as necessary, with additional quantities of carbon from supply 29 or liquid metal from supply 27. By virtue of meters 21 and 25 and the transformation capability in converter 28, the material flow to synthesizer 26 can be controlled and stabilized in order that the composition of the mixed metallic carbides produced in the process can be held at selected levels.
Three separate materials flow streams enter synthesizer 26--the pyrolyzed carbonaceous material from the pyrolyzer 18, the molten composition exiting the blender/reservoir 24, and the residual molten material from converter 28. Temperatures within synthesizer 26 are maintained in the range of 1600°-2400° F. so that a portion of the materials therein readily react to form mixtures of ternary metallic carbides. Dwell time in the synthesizer is about 4 to 7 hours and, nominally, about 5 hours to obtain the peritectic mixture initially required to allow further processing to yield hydrocarbon precursor compositions. By controlling the input to the synthesizer as hereinbefore described and by continuously monitoring and sampling the product composition from the synthesizer, the desired mixture of modified metallic carbides can be controlled.
The partially converted material exiting from the synthesizer is conveyed through line 31 to converter 28 where additional conversion occurs. In converter 28 additional carbon is added from supply 29 to react with molten metal-rich phase or alternatively to react with intermediate carbides to form carbides of higher carbon content either through solid state diffusion processes or by transmittal through a liquid metal film acting as a solvent.
The bulk of the output from converter 28 consisting of the desired mixed metallic carbides is drained into a compactor 30 where the product is compressed or otherwise formed into pellets, bricks or briquettes, preferably spherical or at least non-angular in configuration, of a size which can readily be handled and transported. Typical briquette sizes are in the range 1 to 9 inches in major dimension, although the size of the compacted fuel precursor is not critical. The shaped fuel precursors cool rapidly to ambient temperature and may be stored in bin 32, packed for shipment or immediately used to generate fuels.
Conversion of Precursors to Fuels Products
The mixed metallic carbide fuel precursors can be converted to fuels by the process which is schematically depicted in FIG. 2. The input supply 38 to the conversion process is the fuel precursors hereinbefore produced in the process of FIG. 1, which precursors are metered from compactor 30 or bin 32 via hopper/feeder device 40 at a predetermined rate into conversion chamber 42. In chamber 42, the mixed metallic carbide fuel precursors are sprayed or otherwise contacted with water or steam to form the volatile fuel gases and the spent mixed metallic oxides or hydroxides exiting the converter are recycled to the fuel precursor production process. If desired, additives, such as odorizers, may be added to the fuel gas in the conversion chamber 42. The conversion chamber is maintained at a temperature in the range 250°-600° F., preferably 300°-450° F. In this temperature range, temperatures are high enough that most metal hydroxides will be dehydrated and low enough that unwanted vapors, such as sulfur dioxide, hydrogen sulfide, etc., can be readily removed. The reaction which forms the volatile fuels is exothermic, generating substantial quantities of reaction heat and necessitating a heat exchange system 44 in the chamber 42 to capture this heat of reaction. Preferably, coolant water is caused to flow through heat exchanger 44 to absorb and withdraw the excess reaction heat and to control the converter temperature to the desired range. The coolant water may be converted to steam which can be transported through line 47 for use elsewhere.
The fuel precursors are moved through chamber 42 by a screw conveyor 45 and are sprayed from above with the water by sprayers 46. The water is advantageously distilled water condensed from the steam line to avoid introducing dissolved minerals into the reduction stage during recycling.
The gas exiting chamber 42 through line 54 is a mixture of fuel gases or volatile fuels and water vapor which can be separated by conventional techniques in scrubbers 48. For ease and continuity of operation, a series of scrubber towers is preferably provided with appropriate conventional valving means (not shown) to permit gas flow through selected scrubber towers. In this manner, the towers can be taken off line and repacked with fresh adsorbants when necessary.
Inasmuch as there is considerable vapor production in the conversion chamber 42 creating a pressure in the range 2 to 8 psig therein, fuel precursor feed into and spent fuel precursor removal therefrom must pass through gas sealing mechanisms. The spent fuel precursor, consisting now predominantly of mixed metallic oxides, is passed into a storage pit 52 where any additionally generated volatiles can be collected prior to recycling the spent carbides to mixer 20 (see FIG. 1) as fuel precursor production input. The fuels pass from the chamber 42 and from the spent fuel storage pit 52 through scrubbers 48 into a compressor stage 50 wherein the gas pressure is raised to a level suitable for distribution, for example, in gas mains. Liquid fuels may be removed at this stage if desired. The compressor 50 also serves as a mixer unit wherein the fuel gas can be admixed with an inert (e.g., nitrogen, carbon dioxide) or active (e.g., carbon monoxide) diluent gas prior to distribution through mains or otherwise.
Impurities present in the raw feed material may be removed at special points in the process by one or more of the following methods:
1. Silica, phosphorus, sulfur or other acidic impurities arising primarily from the carbonaceous input may be removed as a dross or slag in the reactor 22 being generally immiscible and floating on liquid metal layer. Additions of lime or magnesia in amount sufficient to combine with the acidic impurities may aid in separation of said impurities. Basic impurities such as alumina would usually combine with acidic impurities normally present in excess, but if necessary controlled additions of silica can be made to effect removal.
2. Impurities introduced into the synthesizer 26 would normally be carried over into the fuel precursor product. With the exception of sulfur, they would pass through the conversion chamber 42 largely unchanged and would be removed in the reactor 22 upon recycling. Sulfur which may be released as H 2 S or SO 2 in hydrolysis can be removed by mild oxidation or absorption by basic materials (lime, soda, ash or alkaline liquids) in scrubbers 48.
EXAMPLE 1
As an example of preferred compositions in the modified (Fe, Mn)C system we list the following data.
The pyrolyzer output yields approximately 70 lb coke or char per 100 lb raw coal for medium volatile coking coals and proportionately more or less for coals of greater or lesser volatiles content.
Mixer 20 is charged with approximately 497 lb of mixed metal oxides (FeO and MnO) containing 10-65% FeO by weight, preferably about 50% with approximately 84 lb of carbon (about 90 lb coke) plus sufficient excess carbon to saturate the reduced liquid metals (about 4-5%). If the furnace is to be internally fired, additional carbon must be added and burned to CO to provide process heat. The synthesizer is charged with approximately 385 lb of liquid metal from the reactor 22 with about 36 lb of carbon (total of dissolved and added C) to permit ultimate conversion of M 7 C 3 , where M represents the metal, and sufficient soft metal to provide an interstitial liquid metal film to retain fluidity to the reacting mixture and promote diffusion of the metallic atoms. The soft metal is preferably magnesium or magnesium zinc alloy and is present in the synthesizer chamber 26 in an amount equal to 5 to 20% by weight of the Fe, Mn content. Most of the soft metal content is retained in the synthesizer and converter chambers. In the hydrolytic conversion chamber 42, approximately 421 lb of mixed metallic carbides are reacted with about 126 lb of water or steam to provide approximately 45 lb of fuels of average composition C n H 3n and about 5 lb of hydrogen.
EXAMPLE 2
For the modified rare earth carbide system we have the following preferred compositions.
Operation of the pyrolyzer would be essentially the same as for the Fe, Mn carbide system described in Example 1.
Mixer 20 is charged with approximately 328 lb of mixed rare earth oxides or La/Ce oxides with about 36 lb of carbon plus sufficient excess carbon to saturate the reduced liquid metals (about 2-3% by weight). Reduction of the rare earth oxides requires more drastic conditions than for Fe or Mn such as higher temperatures or reduction of partial pressures of CO as by vacuum or inert gas purge. Synthesizer 26 is charged with approximately 280 lb of liquid metal from the reactor 22 with about 48 lb of carbon (total dissolved plus added carbon) to permit ultimate conversion to REC 2 and sufficient soft metal to provide an interstitial liquid metal film to retain fluidity to the reacting mixture and promote diffusion of the metallic atoms. The soft metal is preferably magnesium or magnesium-lead-barium and/or zinc alloy and is present in the synthesizer chamber 26 in an amount equal to 5 to 40% by weight of the rare earth metal content. A majority of the soft metal is retained in synthesizer 26 and converter 28. In the hydrolytic conversion chamber 42, approximately 328 lb of mixed metallic carbides are reacted with about 54 lb of water or steam to provide approximately 54 lb of combined fuels plus hydrogen.
The foregoing is considered as illustrative only of the principles of the invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention.
Throughout the specification and claims, unless otherwise specified, parts and proportions are expressed in weight percent, pressures in pounds per square inch absolute, temperatures in degrees Centigrade or Celsius, and heats of formation, combustion, or the like in kilocalories per mole.
|
The present invention relates to a method for producing gaseous or liquid fuels or hydrocarbons from solid mineral sources and, more particularly, to a process for producing solid compounds, hereinafter designated fuel precursors, capable of releasing or generating flammable gases or liquids by chemical and/or physical conversion phenomena and to the process and methods to accomplish said fuel generation. The fuel precursors consist primarily of carbides formed from two or more metallic elements combined with carbon. The precursors additionally may contain minor amounts of free metal, unreacted carbon or other impurities.
| 2
|
[0001] This application claims priority to French Application FR 00 08586 filed Jul. 3, 2000.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to a system for assembly of an apparatus activating a mobile closure on a fixed support, and more particularly of a system for driving a window regulator, of the cable drum type, on the door panel of a vehicle.
[0003] At the present time, the motor and drum cover parts, of a window regulator, are assembled together before being secured on the vehicle. The motor and the drum cover thus form a single element, which may be easily manipulated by an operator. However, in the event of breakdown of the motor, the latter cannot be changed easily. In effect, dismantling of the motor will lead to dismantling of the drum and therefore of the cables which are wound therearound. One of the drawbacks of this solution is that the system cannot be easily repaired in the event of breakdown of the motor for example.
[0004] Another embodiment described in Patent Application DE-19619087A1 to Brose solves this problem. However, the system constituted by the motor and the drum cover is not readily adaptable to all types of doors, as an order of assembly on the door must be respected: the cover then the motor (or vice versa).
[0005] Another drawback of that Patent is that the drum and the cover are independent before being secured on the door panel, which may raise problems during transport of the window regulator.
[0006] DE 44 47 151 discloses a electric window regulator for an automobile vehicle, incorporating cables, whose drum is housed in a cavity made between a cover body and a cap. The cover body is capable of being secured on a fixed support by first securing means and the cap is secured on the cover body. The principal body of the motor which contains the transmission shaft and the reduction gear forms one piece with the cover body. In the event of breakdown of the motor, it is necessary to dismantle the cover body by removing the first securing means, which brings about dismantling of the drum and of the cables wound therearound.
[0007] Now, it may sometimes be useful to manipulate the motorized window regulator as an assembly, in order to facilitate transport thereof, while retaining the possibility of dismantling the motor in the event of malfunction. In that case, it should be possible to assemble the window regulator as an assembly constituted by the cover and the motor.
[0008] It is an object of the present invention to overcome the drawbacks set forth hereinabove.
SUMMARY OF THE INVENTION
[0009] This invention therefore relates to a system for assembly of an apparatus activating a mobile closure on a fixed support, this activation apparatus comprising a drum housed in a drum cover, and a motor assembly for driving the drum in rotation, the drum cover comprising a cover body capable of being secured on the fixed support by first securing means and a cap secured on said cover body, said cover body comprising lugs which, in cooperation with the cap, block the drum in its housing.
[0010] According to the invention, this system is characterized in that the motor assembly comprises a principal body capable of being secured on the cover body by second securing means and in such a manner that said motor assembly can be assembled on said cover body before or after the assembly of said cover body on the fixed support.
[0011] The cover and motor elements may be assembled on the door panel in two different ways:
[0012] Either the cover is secured on the door panel then the motor is secured on the cover.
[0013] Or the motor is secured on the cover then the assembly is secured on the door panel.
[0014] Assembly of the different elements is therefore more variable, and transport of these elements is facilitated.
[0015] In addition, the assembly formed by the drum and its cover is connected so that, even if the cover is not mounted on the door panel, or if the cover of the drum and the motor are not assembled, the drum is still secured in its cover, hence an easier manipulation of the independent elements without risk of the cable escaping from the grooves of the drum.
[0016] The following advantageous arrangements are also preferably adopted:
[0017] The cap is secured on the cover body by clips.
[0018] The motor assembly further comprises a shaft driving a wheel which itself drives the drum with the aid of teeth.
[0019] A first O-ring is interposed between the motor assembly and the cover body.
[0020] The second securing means are screws.
[0021] The motor assembly comprises a manual system driven by a crank.
[0022] The manual system comprises a so-called brake jacket system of which the principal body is secured on the cover body by clips or fold-down tabs which are housed in notches.
[0023] The system comprises a second O-ring between the manual system and the drum.
[0024] A third O-ring is interposed between the cover body and the fixed support.
[0025] The third O-ring is moulded or stuck on the cover body and comprises a hook-shaped part which is clipped on the fixed support.
[0026] The hook-shaped part is discontinuous over the perimeter of a hole in the fixed support.
[0027] The third O-ring is stuck on the fixed support and comprises a hook-shaped part which is clipped on the cover body.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] The invention will be more readily understood on reading the following description with reference to the accompanying drawings, in which:
[0029] [0029]FIG. 1 shows a view of the prior art.
[0030] [0030]FIG. 2 shows a window regulator system according to the invention in section.
[0031] [0031]FIG. 3 shows another embodiment of the invention.
[0032] [0032]FIG. 4 shows an enlarged view of part of the invention (detail IV of FIG. 2).
DESCRIPTION OF PREFERRED EMBODIMENT
[0033] Referring now to the drawings, and firstly to FIG. 1, the drum 11 is housed in the cover 2 which is secured on the motor 3 by securing elements 19 , for example screws. It will be noted that, if the motor is not assembled, the drum 11 is free to emerge from its housing.
[0034] The door panel 1 represents the support of the system, constituted by the drum and its cover 2 , and of the motor 3 . This door panel may be a stamped metal sheet or a plate of moulded plastics material or any other material which may be preformed and used as door panel. In the following description, a sheet metal plate will be taken as example.
[0035] In FIG. 2, the sheet metal plate 1 is constituted by a stamped metal sheet pierced with a hole 4 allowing the different elements to pass through, its shape being defined so that it delimits the dry side 5 and the wet side 6 , the motor being located on the dry side and the cable and drum on the wet side.
[0036] Tightness is ensured with the aid of seals: a first O-ring 7 for the seal between the plate and the cover, and a second O-ring 8 for the seal between the cover and the motor.
[0037] The motor 3 is constituted by a shaft 9 which drives the wheel 10 , which itself drives the drum 11 thanks to teeth 12 . The other elements of the motor are known and will not be described.
[0038] The cover of the drum 2 is constituted by a first part 13 constituting the body of the cover, and by a second part 14 constituting a cap which is secured on the body 13 , thanks to clips 15 for example, at the same time as the the drum 11 is positioned in the cover; cables (not shown) are also positioned around the drum.
[0039] The cap 14 and the lugs 16 block the drum, which allows the cover/drum assembly to be easily transported.
[0040] The assembly thus constituted may then be mounted on the sheet metal 1 and secured for example by screws 17 regularly distributed on the periphery.
[0041] The motor 3 assembly further comprises a principal body 18 which is secured on the cover for example by regularly distributed screws 19 .
[0042] It may also be imagined that the assemblies 2 and 3 are firstly joined and secured together by screws 19 , before securing the assembly thus obtained on the sheet metal 1 with the aid of screws 17 .
[0043] The system can then be mounted in different ways, which facilitates assembly and allows several possibilities as to the order of assembly of the different elements.
[0044] It will be noted that the screw heads are all on the dry side of the sheet metal, i.e. they are easily accessible to the person assembling and dismantling the system.
[0045] The securing means 18 and 19 may easily be constituted by clips which must be dismountable. Such securing means offer less rigidity, but are more profitable as to the assembly time.
[0046] Another possibility concerning the cover of the drum would be to make the opening to introduce the drum on the motor side. The cap 14 would in that case be on the motor side, the lugs 16 would be made by a particular shape of the cap 14 . This system would make it possible, after dismantling of the motor, to have access to the drum after the cap 14 has been unclipped, and this without dismantling the screws 17 . There would thus be access to all the parts from the same side, which facilitates repairs in the event of breakdown of one of the mobile elements.
[0047] Another advantage is that the take-up bearing 24 , which was on the part 14 and was more or less rigid, is now on the part 13 which is more rigid, this improving the mechanical strength of the bearing and the precision of alignment of the shafts.
[0048] [0048]FIG. 3 shows the invention in the case of a manual window regulator.
[0049] The system envisaged is a motorized window regulator but this principle may very well be adapted to a manual one. In that case, the shaft 9 becomes the rotation shaft driven by the user's crank. The motor is in that case replaced by a manual system 22 which may comprise a so-called brake jacket system which is secured beneath the body 13 thanks to clips or fold-down tabs 21 housed in the notches 20 .
[0050] The notches 20 of this configuration will advantageously be placed inside the so-called wet zone of the motorized configuration defined by the inner perimeter of the motor seal 8 .
[0051] The tightness which is ensured by O-rings 8 in the motorized case is ensured by the tabs 21 which are housed in the notches 10 , this obstructing them and preventing water from penetrating inside the dry zone in the manual case. It may also be envisaged having an O-ring 25 positioned between the manual system 22 and the drum.
[0052] One sole component 13 may therefore be envisaged for the manual or electric systems, this allowing savings to be made by rationalizing production of the different types of window regulators.
[0053] [0053]FIG. 4 shows another embodiment of the invention.
[0054] When the cover 2 is secured on the plate 1 by the securing means 17 , it is necessary for the operator to hold the cover 2 , but, in the case of assembly in a door, where the dimensions are reduced, it is sometimes difficult to hold the cover and secure the securing means 17 at the same time. A means is therefore necessary which ensures sufficient hold of the cover 2 on the plate 1 to allow the operator to secure the cover 2 on the plate 1 by the securing means 17 without having to hold the cover during this operation.
[0055] This role of hold may be performed by the seal 7 which, by the addition of a special shape, may be anchored in the plate 1 . The shape of the seal 7 includes, in addition to part 40 which provides tightness, a part 41 in the form of a hook, which, by clipping on the plate 1 , makes it possible to hold the cover 2 .
[0056] The hook-shaped part 41 may be continuous all along the seal or a plurality of hook-shaped parts may be distributed along the seal, in which case the hook-shaped part 41 is discontinuous over the perimeter of the hole 4 in the fixed support 1 .
[0057] These shapes ensure not only the hold of the cover 2 on the plate 1 , but they also improve tightness and make it possible to position the cover 2 with respect to its housing in the plate 1 .
[0058] The seal may be moulded or stuck on the cover in conventional manner. The seal may also be stuck on the plate 1 and, in that case, the shapes 41 clip on the cover.
[0059] A preferred embodiment of this invention has been disclosed. However, a worker of ordinary skill in this art would recognize that certain modifications would come within the scope of this invention. For that reason, the following claims should be studied to determine the true scope and content of this invention.
|
This invention relates to a system for assembling two components of a device activating a window regulator on a fixed support. According to the invention, one of the components is secured to the other component by a securing means and at least one of the components is secured to the fixed support by another securing means.
| 4
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is directed to a method for computed tomography (CT), of the type wherein, for scanning a subject with a conical ray beam emanating from a focus and with a matrix-like detector array for detecting the ray beam, the focus is moved on a spiral path around a system axis relative to the subject, with the detector array supplying output data corresponding to the received radiation, and wherein images having an inclined image plane relative to the system axis are reconstructed from output data supplied during the motion of the focus on a spiral segment. The invention also is directed to a computed tomography apparatus of the type having a radiation source having a focus from which a conical ray beam emanates, a matrix-like detector array for detecting the ray beam, the detector array supplying output data corresponding to the received radiation, an arrangement for generating a relative motion between radiation source and detector array, and a subject, and an image computer to which the output data are supplied, the means for generating a relative motion for scanning the subject with the ray beam and the two-dimensional detector array causing a relative motion of the focus with respect to the system, such that the focus moves on a helical spiral path relative to the system, axis having a central axis corresponding to the system axis, and whereby the image computer reconstructs images with an image plane inclined relative to the system axis from output data supplied during the motion of the focus on a spiral segment.
2. Description of the Prior Art
Various CT methods using conical x-ray beams are known particularly in conjunction with detector arrays having a number of lines of detector elements. The cone angle that thereby occurs as a consequence of the conical shape of the x-ray beam is taken into consideration in various ways.
In the simplest case (see, for example, K. Taguchi, H. Aradate, “Algorithm for image reconstruction in multi-slice helical CT”, Med. Phys. 25, pp. 550-561, 1998; H. Hu, “Multi-slice helical CT: Scan and reconstruction”, Med. Phys. 26, pp. 5-18, 1999), the cone angle is left out of consideration, with the disadvantage that artifacts occur in a large number of lines, and thus a large cone angle.
Further, an algorithm referred to as the MFR Algorithm (S. Schaller, T. Flohr, P. Steffen, “New, efficient Fourier-reconstruction method for approximate image reconstruction in spiral cone-beam CT at small cone-angles”, SPIE Medical Imaging Conf., Proc. Vol. 3032, pp. 213-224, 1997) is known, the disadvantage thereof being that a complicated Fourier reconstruction was necessary and the image quality leaves much to be desired.
Exact algorithms (for example, S. Schaller, F. Noo, F. Sauer, K. C. Tam, G. Lauritsch, T. Flohr, “Exact Radon rebinning algorithm for the long object problem in helical cone-beam CT, in Proc. of the 1999 Int. Meeting on Fully 3D Image Reconstruction, pp. 11-14, 1999 or H. Kudo, F. Noo and M. Defrise,:Cone-beam filtered back-projection algorithm for truncated helical data”, in Phs. Med. Biol., 43, pp. 2885-2909, 1998) have also been described, which have the common disadvantage of extremely complicated reconstruction.
A method and CT apparatus of the type initially described are disclosed in U.S. Pat. No. 5,802,134. In accord therewith, in contrast, images are reconstructed for image planes that are inclined by an inclination angle γ around the x-axis relative to the system axis z. As a result, the (at least theoretical) advantage is achieved that the images contain fewer artifacts when the inclination angle γ is selected such that a good and optimum adaptation of the image plane to the spiral path is established, insofar as possible according to a suitable error criterion, for example minimum square average of the distance measured in z-direction of all points of the spiral segment from the image plane.
In U.S. Pat. No. 5,802,134, fan data, i.e. data registered in the known fan geometry are employed for the reconstruction, the data having been acquired with the motion of the focus along a spiral segment having the length 180° plus the fan angle, for example 240°. The optimum inclination angle γ is dependent on the slope of the spiral, and thus on the pitch p.
Fundamentally, the method disclosed in U.S. Pat. No. 5,802,134 can be employed for arbitrary values of the pitch p. However, an optimum utilization of the detector area available, and thus of the radiation dose applied to the patient for image acquisition (dose utilization) is not possible below the maximum pitch P max . This is because even though a given transverse slice, i.e. a slice of the subject residing at a right angle relative to the system axis z, is scanned via a spiral segment that is longer then 180° plus fan angle, only a spiral segment having the length 180° plus the cone angle can be utilized for values of the pitch p below the maximum pitch P max since the utilization of a longer spiral segment would make it impossible to adapt the image plane to the spiral path well enough.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a method and a CT apparatus of the type initially described wherein the cone angle is taken into consideration and wherein the preconditions for an optimum detector utilization and thus an optimum dose utilization are also established for values of the pitch p below the maximum pitch P max .
This object is achieved in accordance with the invention in a method for producing a computed tomography image wherein a subject is scanned with a conical x-ray beam emanating from a focus which is detected, after attenuation by the subject, using a matrix-like detector array while the focus moves along a spiral path around the subject relative to a system axis. The detector array generates output data dependent on the radiation from the x-ray beam that is incident thereon, and the output data, for a segment of the spiral path having a length that is adequate for reconstructing a CT image, are divided into a number of datasets respectively for a number of sub-segments of the aforementioned segment. Each of these sub-segments has a length that is shorter than the length that is adequate for reconstructing a CT image. For each of the sub-segments, a number of segment images is reconstructed, the segment images being in respective planes that are inclined relative to the system axis. For each sub-segment, the segment images associated therewith are combined to form a partial image with respect to a target image plane. These partial images that arise for the respective sub-segments are then combined to form a resulting CT image with respect to the target plane.
Since in the inventive method, the spiral segment whose length suffices for the reconstruction of a CT image is divided into sub-segments whose lengths are each less then the length required for the reconstruction of a CT image, the deviations of the image planes of the segment images reconstructed with respect to the sub-segments from the spiral path along the sub-segments are very small. The segment images thus contain only very slight errors caused by deviations of the image planes of the segment images from the spiral path along the sub-segments, so that the image quality in the generation of the resulting CT image is high.
The maximum inclination of the image planes of the segment images is defined from the condition that rays for the image plane of the respective segment image must be present at both ends of the sub-segment within the measurement field.
The segment images that are not useable by themselves because the length of the sub-segments is shorter then the length required for the reconstruction of a CT image are calculated in a known way, i.e. the rays most beneficial for the image plane of the respective segment image are selected from the projections for the respective sub-segment present in parallel or fan geometry according to a suitable error criterion, and are filtered and back-projected or reconstructed with other standard methods.
The combining of the segment images belonging to a sub-segment, i.e. their reformatting onto a target image plane, leads to a sub-image that is likewise not useable by itself because of the excessively short length of the sub-segment. It is only when the sub-images of all sub-images belonging to the respective spiral segment for the desired target image plane are combined to form a resulting CT image does a useable image arise, since the overall length of the spiral segment derived from the sub-segments suffices for the reconstruction of a CT image.
The image quality of this image is especially high when the segment images are reconstructed for image planes that are inclined around a first axis intersecting the system axis at a right angle by an inclination angle χ as well as around a second axis intersecting each of the first and the system axis at a right angle by a tilt angle δ with respect to the system axis because the adaptation of the image planes of the segment to the spiral path of the respective sub-segment is then better again.
In an embodiment of the invention, the neighboring sub-segments overlap, so the output data belonging to the overlap regions are respectively weighted such that the weights of output data corresponding to one another in the overlapping sub-segments produce a value of one.
The advantage of overlapping sub-segments is that artifacts that would otherwise occur at the adjoining edges of the sub-segments are avoided.
In an embodiment, segment images for a number n ima of inclined image planes are reconstructed for each sub-segment, whereby the image planes have different z-positions z ima . Due to the reconstruction of a number of segment images having differently inclined image plane for different z-positions, it is possible—by a suitable selection of the inclination angle γ and of the tilt angle Δ—to optimally adapt the image plane of the respective segment image for each of these z-positions to the sub-segment and to thus utilize the detector array as well as the dose completely in theoretical terms and to the greatest extent in practice. In a preferred embodiment of the invention, the number of inclined image planes intersect in a straight line that proceeds tangentially relative to the sub-segment.
In order to obtain an optimally complete detector utilization and dose utilization, the following applies according to a version of the invention for the extreme values +δ max and −δ max of the tilt angle δ of the inclined image planes belonging to a sub-segment: ± δ max = arctan ( WM 2 + Sp α 1 2 π ± RFOV cos α 1 tan γ 0 - R f cos γ 0 - ( ± RFOV ) sin α 1 cos γ 0 )
wherein γ 0 is the value of the inclination angle γ determined for the tilt angle δ=0 according to γ 0 = tan ( - Sp α ⋒ 2 π R f sin α )
For a high image quality, in another version of the invention the optimum value γ min of the inclination angle belonging to a given amount |δ max | of the maximum value of the tilt angle δ is determined such that an error criterion is met, for example minimum average of the squares the respective spacings of all points of the sub-segment from the image plane measured in the z-direction, is met.
If the rotational axis, around which the focus rotates around the system axis, is not identical with the system axis but intersects the system axis at an angle referred to as a gantry angle ρ, then the following applies to the inclination angle γ′ to be selected: γ ′ = arctan Sp · cos ρ 4 π 2 · R f + S 2 P 2 + 4 π · R f cos α sin ρ · Sp
Here, as well, there is the possibility of determining the appertaining optimum value of the inclination angle γ′ for a given magnitude of the maximum value of the tilt angle |δ max | such that an error criterion, for example minimum average of the squares of the respective spacings of all points of the sub-segment from the image plane measured in the z-direction.
In order to obtain an optimally complete detector and dose utilization, the following is also valid according to a version of the invention for the number n ima of the inclined image planes, for which segment images with inclined plane are generated for each sub-segment: n ima = floor [ sM p ]
wherein s is the length of the sub-segments.
Likewise for an optimally complete detector and dose utilization, the tilt angles δ of the inclined image planes are determined in a version of the invention according to δ ( i ) = δ max 2 i - ( n ima - 1 ) n ima - 1
given the condition of detector lines of equal width.
In order to create the conditions for obtaining transverse tomograms to which the users of CT apparatus are accustomed, a reformatting is provided according to one version of the invention, i.e. a sub-image is generated in a further method wherein a number of segment images are combined. In an embodiment of the invention, it may occur that a number of segment images are combined to form a sub-image by interpolation or by, in particular, weighted averaging.
The reconstruction slice thickness of the sub-images, and thus of the resulting CT image is set according to a preferred embodiment of the invention by weighting the segment images according to the desired reconstruction slice thickness of the sub-image in the combining to form a sub-image.
In the combination of a number of segment images to form a sub-image, there is the possibility according to a preferred version of the invention of selecting the number of segment images that are combined for generating a sub-image according to the desired reconstruction slice thickness of the sub-image. For an optimally high image quality, there is the possibility of reconstructing the segment images with the least possible slice thickness.
A desired reconstruction slice thickness of a sub-image can be set according to another preferred version of the invention by selecting the number of segment images for generating a sub-image according to the following equation:
N M =2·max( z*,sup φΔ zR )/ W·N S
The combining of the sub-images into the resulting CT image preferably ensues by addition, also preferably for a target image plane that intersects the system axis at a right angle. The target image plane, however, also can be inclined relative to the system axis.
In order to keep the amount of data arising in the generation of the segment images within limits, in a version of the invention the data corresponding to the segment images are compressed.
In a preferred embodiment of the invention the compressed data corresponding to the segment images exhibit a non-uniform pixel matrix such that the resolution in a first direction, proceeding essentially in the direction of the reference projection direction belonging to the respective sub-segment, is higher then in a second direction that proceeds essentially orthogonally relative to the reference projection direction. Such a procedure is possible because the information density and the segment images orthogonally to the reference projection direction belonging to the respective sub-segment is significantly greater than in the reference projection direction belonging to the respective sub-segment.
In a version of the invention, the realization of a non-uniform pixel matrix is especially simple when the compressed data corresponding to the segment images are pixels having an oblong shape, particularly rectangular pixels, with the longest extent of each pixel proceeding essentially in the direction of the reference projection direction belonging to the respective sub-segment.
Because it is time-saving, it is especially advantageous, according to another preferred embodiment of the invention, to reconstruct the segment images in the non-uniform pixel matrix, since significantly fewer pixels need to be reconstructed than in the case of a uniform pixel matrix that has the same resolution in the reference projection direction belonging to the respective sub-segment. The back-projection has an especially simple form when the back-projection direction essentially corresponds to the direction of the reference projection direction belonging to the respective sub-segment.
Since the resulting CT image exhibits a uniform pixel matrix in the usual way, the compression—if it is based on the employment of a non-uniform pixel matrix—must be reversed according to a version of the invention no later than during the combining of the sub-images to form the resulting CT image.
The above object also is achieved in a computed tomography apparatus operating according to the inventive CT method described above. The comments and discussion above relating to the inventive CT method apply equally to the inventive CT apparatus.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view with a block circuit diagram of a CT apparatus having multiple of lines of detector elements constructed and operating in accordance with the invention.
FIG. 2 is a longitudinal section through the apparatus of FIG. 1 in a first operating mode.
FIG. 3 illustrates the spiral path described by the focus of the x-rays in a spiral scan in the CT apparatus according to FIGS. 1 and 2.
FIG. 4 illustrates the image planes of the segment images belonging to a sub-segment in accordance with the invention.
FIG. 5 illustrates an example of a segment image in accordance with the invention.
FIG. 6 illustrates the non-uniform pixel matrix of a segment image and the uniform pixel matrix of the appertaining sub-image in accordance with the invention.
FIG. 7 shows another operating mode of the CT apparatus according to FIGS. 1 and 2 in an illustration analogous to FIG. 2 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIGS. 1 and 2 show a CT apparatus of the third generation suitable for the implementation of the inventive method. The measurement arrangement 1 thereof has an x-ray source 2 with a source-proximate radiation diaphragm 3 (FIG. 2) preceding it and a detector system 5 fashioned as a planar array of a number of rows and columns of detector elements, one of which is referenced 4 in FIG. 1 . The detector system 5 has a detector-proximate radiation diaphragm 6 (FIG. 2) preceding it. For clarity, only eight lines of detector elements 4 are shown in FIG. 1; as indicated dot-dashed in FIG. 2, however, the detector system 5 has (or can have) more lines of detector elements.
The x-ray source 2 with the radiation diaphragm 3 , and the detector system 5 with the radiation diaphragm 6 , are opposite one another on a rotary frame 7 as shown in FIG. 3 such that a pyramidal x-ray beam (whose edge rays are referenced 8 ), that emanates from the x-ray source 2 during operation of the CT apparatus and is gated by the adjustable radiation diaphragm 3 , strikes the detector system 5 . The radiation diaphragm 6 is set corresponding to the cross-section of the x-ray beam that is set with the radiation diaphragm 3 so that only that region of the detector system 5 is activated that can be directly struck by the x-ray beam. In the operating mode shown in FIGS. 1 and 2, these enabled or activated lines are eight lines of detector elements 4 , which are referred to as active lines below. The further lines indicated by dots are covered by the radiation diaphragm 6 and therefore are not active. Each line of detector elements 4 has a K detector element, respectively designated by a channel index k=1 through K. The active lines L n of detector elements 4 are referenced in FIG. 2 as L 1 through L N , respectively indicated by a line index n=1 through N.
The x-ray beam exhibits the cone angle β shown in FIG. 2 which is the aperture angle of the x-ray beam in a plane containing the system axis Z and the focus F. The fan angle (φ of the x-ray beam also is shown in FIGS. 1 and 2, this being the aperture angle of the x-ray beam in a plane that is oriented at a right angle relative to the system axis Z and containing the focus F.
The rotary frame 7 can be placed into rotation around the system axis Z by a drive 22 . The system axis Z proceeds parallel to the z-axis of a spatial rectangular coordinate system shown in FIG. 1 .
The columns of the detector system 5 likewise proceed in the direction of the z-axis, whereby the lines (rows), whose width W is measured in the direction of the z-axis and amounts, for example, to 1 mm, proceeding transversely relative to the system axis Z and the z-axis.
In order to be able to introduce an examination subject, for example a patient, into the beam path of the x-ray beam, a support mechanism 9 is displaceable parallel to the system axis Z, i.e. in the direction of the z-axis, with a synchronization between the rotational motion of the rotary frame 7 and the translational motion of the support mechanism 9 that causes the ratio of translational to rotational velocity to be constant. This ratio can be set by selecting a value for the feed h of the support mechanism 9 per revolution of the rotary frame 7 .
A volume of an examination object situated on the support mechanism 9 thus can be examined during the course of a volume scan. The volume scan can be undertaken in the form of a spiral scan in the sense that, given simultaneous rotation of the measurement unit 1 and translation of the support mechanism 9 , a number of projections from different projection directions is registered with the measurement unit per revolution of the measurement unit 1 . In the spiral scan, the focus F of the x-ray source moves on a spiral path (referenced S in FIG. 1) relative to the support mechanism 9 .
The measured data corresponding to the individual projections and read out in parallel during the spiral scan from the detector elements of every active line of the detector system 5 are subjected to a digital-to-analog conversion in a data editing unit 10 , and are serialized and transmitted to an image computer 11 .
After a pre-processing of the measured data in a pre-processing unit 12 of the image computer 11 , the resulting data stream proceeds to a reconstruction unit 13 that reconstructs CT images of desired slices of the examination subject from the measured data, either according to methods that are known themselves (for example, 180 LI or 360 LI interpolation) or, in an operating mode corresponding to the invention, according to a method that is explained in greater detail.
The CT images are composed of pixels arranged in a matrix, with the pixels being allocated to the respective image plane. A CT number in Hounsfield units (HU) is allocated to each pixel, and the individual pixels, corresponding to a CT number/gray scale value—are presented in a gray value corresponding to the respective CT number.
The images reconstructed by the tomogram reconstruction unit 13 and the x-ray shadowgram reconstruction unit are displayed at a display unit 16 , for example a monitor, connected to the image computer 11 .
The x-ray source 2 , for example an x-ray tube, is supplied with the necessary voltages and currents, for example the tube current U, by a generator unit 17 . In order to be able to set these parameters to the necessary values, the generator unit 17 has a control unit 18 with a keyboard 19 which allows the necessary settings.
The rest of the operation and control of the CT apparatus ensues with the control unit 18 and the keyboard 19 , this being illustrated by the connection of the control unit to the image computer 11 .
Among other things, the number N of active lines of detector elements 4 , and thus the position of the radiation diaphragms 3 and 6 , can be set, for which purpose the control unit 18 is connected to adjustment units 20 and 21 allocated to the radiation diaphragms 3 and 6 . Further, the rotation time τ can be set, which is time the rotary frame 7 requires for a complete revolution. This is illustrated by the connection of the drive unit 22 for the rotary frame 7 to the control unit 18 .
When an operating mode in accordance with the invention is selected, the calculation of the corresponding CT images ensues using the inventive method explained in greater detail below.
To that end, a spiral scan is implemented over a length that suffices at least for the reconstruction of a CT image. In the example illustrated in FIG. 3, this is a spiral scan of the length 6π. Measured data corresponding to a number of overlapping sub-segments are obtained from the measured data thereby acquired, with the length of each sub-segment being less than the length required for the reconstruction of a CT image. The number and length, for example π/4 or π/8, of the sub-segments are selected such that they produce at least one spiral segment overall having length, for example π+φ, that suffices for the reconstruction of a CT image, i.e. it is at least equal to the length required for the reconstruction of a CT image. A number of N tilt of segment images, whose pixels relate to different image planes inclined relative to the middle plane, is calculated for each of the sub-segments from the corresponding measured data.
It can be seen from FIG. 3 that 12 overlapping sub-segments are present per full revolution in the described exemplary embodiment, i.e. N α =12. The sub-segments of the first of the three full revolutions shown in FIG. 3 are referenced US 1 through US 12 in FIG. 3 .
In the exemplary embodiment, five segment images are calculated per sub-segment, as can be seen from FIG. 4 with reference to the example of the sub-segment US 4 , i.e. N tilt =5, this being illustrated by the image planes Pl 1 through Pl 5 of the segment images.
For a full revolution, thus, a total of N α *N tilt =60 segment images are calculated from the measured data of the full revolution, with the segment images belonging to a sub-segment being combined later to form a sub-image.
The image planes Pl 1 through Pl 5 of the segment images all intersect in a straight line according to FIG. 4 . In the illustrated exemplary embodiment, this line is the tangent T at the middle M of the sub-segment in question, i.e. that point of the portion of the focal path belonging to the sub-segment that lies at half the arc length of this portion of the focal path.
Those measured values that correspond to the line integrals required for a reconstruction of the respective segment image are selected for each of these image planes Pl 1 through Pl 5 from the measured data that are supplied by the various detector lines L 1 through L 8 . The selection ensues such that the beams utilized for reconstruction of the respective segment image satisfy a suitable error criterion with respect to their distance from the inclined image plane of the respective segment image. In the exemplary embodiment, this is the minimum average of the squares of the distances measured in the z-direction, of all rays utilized for the reconstruction of the respective segment image, from the respective, inclined image plane Pl 1 through Pl 5 .
The maximum inclination of an image plane of a segment image thus is defined by the requirement that measured values must be available for all required line integrals whose rays lie adequately close to the inclined image plane according to the error criterion.
The segment image belonging to each image plane Pl 1 through Pl 5 is then calculated from these line integrals compiled for each image plane Pl 1 through Pl 5 from different measured values, for example by means of the standard reconstruction method of convolution and back-projection. The pixels of these segment images belong to the respective, inclined image plane Pl 1 through Pl 5 . In the described exemplary embodiment, thus, a stack of five segment images is calculated for each sub-segment.
The N tilt segment images obtained in this way per sub-segment are combined in a following reformatting step to form a sub-image with respect to a desired target image plane IP that is different from the image planes Pl 1 , through Pl 5 and intersects the system axis Z, preferably at a right angle as shown in FIG. 2, dependent on selectable combining modes (explained below) either by weighting or by interpolation. Independently of the combining mode, the image noise is reduced during the course of the combining, and the desired reconstruction slice thickness is set, with the setting of the segment images ensuing by means of the weighting and/or the number of the segment images involved in the reformatting. This number preferably equals to the number of segment images reconstructed per sub-segment.
The Nα sub-images obtained in this way are combined with respect to the target image plane to form a resulting CT image in a final reformatting step, by addition.
The combining of segment images to form a sub-image ensues in a first combining mode by weighting, by either of two selectable weighting modes. Independently of the selected weighting mode, the pixels of the segment images respectively contribute as source pixels to a corresponding target pixel of the resulting CT image, and the magnitude of a source pixel relative to a target pixel is weighted dependent on a geometric reference quantity. In other words: the CT number belonging to a target pixel is determined from the CT numbers of the corresponding source pixels taking the geometrical reference quantity into consideration.
In the first weighting mode, the distance of the respective source pixel from the corresponding target pixel is taken into consideration as the geometrical reference quantity.
In the second weighting mode, a weighting dependent on the distance of the source pixel from the middle of the sub-segment in question additionally ensues in order to avoid artifacts.
In a second combining mode, the combining of the segment images to from a sub-image ensues by interpolation, i.e. the target pixels—the pixels of the resulting CT image—are determined by interpolation, for example linear interpolation, from the corresponding source pixels, i.e. from the corresponding pixels of the segment images.
The conditions underlying the reconstruction of segment images shall be explained as an example below on the basis of a sub-segment that is centered with respect to a reference projection angle α r =0. Since the image planes of the n ima segment images are inclined relative to the x-axis by the inclination angle γ as well as relative to the y-axis by the tilt angle δ, a normal vector of an image plane is established by: n → ( γ , δ = ( sin δ - cos δ sin γ cos δ cos γ ) ( 1 )
The distance d(α, δ, γ) that an arbitrary point (X f , Y f , Z f ) on the spiral path, or the sub-segment under consideration, has from the image plane inclined by the inclination angle γ and the tilt angle δ is established by d ( α , δ , γ ) = n → ( γ , δ ) · ( x f + R f y f z f ) = n → ( γ , δ ) · ( - R f cos α + R f - R f sin α Sp α 2 π ) = R f ( 1 - cos α ) sin δ + R f sin α cos δ sin γ + Sp α 2 π cos δcos γ ( 2 )
It is assumed that the position (−R f ,0, 0) of the focus F lies in the image planes for the reference projection angle α r =0. The inclination angle γ and the tilt angle δ of the inclined image plane must be selected such that all points of the sub-segment in question satisfy an error criterion, for example that the average of the squares of the distances in the z-direction of all points of the spiral segment from the image plane is minimized.
When it is assumed that b-t is the coordinate system x-y rotated by an angle α-π/2 around the z-axis, then b-t is the local coordinate system for a projection having the projection angle α.
x=b sin α+ t cos α
y=−b cos α+ t sin α (3)
When a virtual detector array is imaged that corresponds to the projection of the detector array into a plane containing the system axis z, referred to as the virtual detector plane, then t=0 applies to the detector plane.
Each point (x,y,z) on the image plane is characterized by n → ( γ , δ ) · ( x + R f y z ) = ( x + R f ) sin δ - y cos δsinγ + z cos δ cos γ = 0 ( 4 )
When (3) with t=0 is introduced into (4), then the intersecting straight line of the virtual detector plane with the image plane is obtained: z ( b ) = - R f tan δ cos γ - b ( sin α tan δ cos γ + cos α tan γ ) ( 5 )
The z-coordinate on the virtual detector plane is established by z Det ( b ) = z ( b ) - Sp α 2 π = - R f tan δ cos γ - Sp α 2 π - b ( sin α tan δ cos γ + cos α tan γ ) ( 6 )
The inclination angle γ is first optimized in the same way as in the case of U.S. Pat. No. 5,801,134, i.e. for the tilt angle δ=0. The following is obtained as a result: tan γ 0 = - Sp α ⋒ 2 π R f sin α ⋒ , ( 7 )
wherein {circumflex over (α)} is the angle at which the sub-segment penetrates the image plane.
The tile angle δ is optimized for the tilt angle γ 0 obtained with {circumflex over (α)} according to (7). The optimization criterion for the tilt angle δ is that the z-coordinate according to (6) for the detector lines −RFOV≦b≦RFOV that limit the region of the examination subject acquired by the radiation toward the back or front in the z-direction must lie within the active detector area, i.e. within the region of the detector array 5 enabled by the radiation diaphragm 6 and struck by the radiation, also must utilize the detector area optimally well.
For the maximally possible tilt angle ±δ max , the lines for b=±RFOV established by the z-coordinate according to (6) reach the front or back end of the detector surface in the z-direction. When this occurs for the respective sub-segment for the projections at the start and end of the sub-segment, i.e. for the outermost projection angle ±α 1 , the following applies: z Det ( b = ± RFOV ) = ± WM 2 . ( 8 )
wherein M is the number of detector lines and W is the width of a detector line measured in the z-direction.
By introducing (5) for α=α 1 and γ=γ 0 into (7) and solving for δ max , the following results: tan δ max = WM 2 + Sp α 2 π ± RFOV cos α 1 tan γ 0 - R f cos γ 0 - ( ± RFOV ) sin α 1 cos γ 0 or ± δ max = arctan ( - WM 2 + Sp α 1 2 π ± RFOV cos α 1 tan γ 0 - R f cos γ 0 - ( ± RFOV ) sin α 1 cos γ 0 ) ( 9 )
A new δ min is determined for the corresponding δ max by iteration, namely by minimizing the average of the squares of the distances d(α,δ max , γ) in the z-direction of all points of the sub-segment from the image plane according to (2).
The range [−δ max ,δ max ] of the tilt angle that is available is now uniformly subdivided according to the number n ima of the segment images to be reconstructed, preferably as in the case of the described exemplary embodiment. This means that given a uniform subdivision, each image plane 0≦i≦ nima −1 is characterized by the inclination angle Y min (that, as in the case of the described exemplary embodiment, is preferably the same for all image planes) and by the respective tilt angle δ (i) , with the following being applicable for the respective tilt angle: δ ( i ) = δ max 2 i - ( n ima - 1 ) n ima - 1 ( 10 )
The number n ima of the segment images to be reconstructed for the sub-segment is established by n ima = floor [ sM p ] . ( 11 )
wherein s is the arc length of the spiral path S for the sub-segment under consideration.
The reformatting occurs using interpolation functions of a selectable width, as a result of which the slice sensitivity profile and the image noise in the resulting transverse tomogram can be influenced. It is advantageous that the definition of the desired reconstruction slice thickness of the sub-images, and thus of the resulting CT images, ensues retrospectively during the course of the reformatting.
The plurality of segment images required in the reformatting to be implemented for the acquisition of a sub-images is obtained in the following way:
At the edge of the object cylinder parameterized by (x,y)=(R M cos φ), R M sin(φ)), the distance AZR of an image plane inclined by the inclination angle and the tile angle with the normal vector n -> ( γ , δ ) = ( sin δ - cos δ sin γ cos δcos γ )
and with the zero point in the point (−R f , 0, Z r ), is obtained by inserting (x,y,ΔZ R ) is inserted into the plane equation {right arrow over (n)}(δ,γ)·{right arrow over (x=)}0.
The following then results: Δ z R = - tan ( δ ) cos ( γ ) · ( - R f + R M · cos ( Φ ) ) + tan ( γ ) · R M · sin ( Φ ) .
For the reformatting of a transverse tomogram with the image plane in Z R , accordingly, all segment images reconstructed in the interval
[(( z R −sup φ ΔZ R (Φ,δ))),(( z R +sup Φ Δz R (Φ,δ)))] (13)
must be available, i.e. must be stored in the memory 14 .
When an interpolation function whose length z* exceeds the limits placed by the above interval is employed in the reformatting, then the number of segment images required for the reformatting is defined by the length of the interpolation filter.
In the general case, the following is valid for the number NM of the reconstructed images with inclined image plane required for the reformatting of a sub-image:
N M =2·max( z*,sup φ Δz R )/ W·N S (14)
N s is the number of segment images reconstructed per width W of a line of detector elements.
As a result of the fact that the reconstruction slice thickness of a desired sub-tomogram is retrospectively defined, the reconstruction of the segment images preferably ensues by selecting a correspondingly narrow weighting function with the least possible reconstruction slice thickness. This assures utmost sharpness in the z-direction not only of the segment images but also of the sub-images obtained by the reformatting as well as of the CT image acquired therefrom.
In addition to this advantage, the following are further advantages of the described reformatting:
The reconstruction slice thickness can be retrospectively selected without a renewed reconstruction being required;
The reconstruction slice thickness is freely selectable; and
A number of suitable interpolation functions having a freely selectable width is available for the reformatting.
FIG. 5 illustrates the segment image belonging to the image plane Pl 3 as an of example from among the segment images belonging to the sub-segment US 4 . The reference projection angle α r and the outermost projection angles +α 1 and −α 1 belonging thereto are indicated with broken lines. It can be seen that the information density in the segment images that are orthogonal relative to the projection direction corresponding to the respective reference projection angle (referred to below as the reference projection direction) is significantly greater than in the reference projection direction.
There is therefore the possibility of compressing the data corresponding to the segment images. In the described exemplary embodiment and as a result of the fact that the data redundancy would be extremely high for the aforementioned reasons when employing a uniform pixel matrix, the data compression occurs in that the compressed data corresponding to the segment images has such a non-uniform pixel matrix corresponding to the data structure that the resolution R r in reference projection direction is less then the resolution R or orthogonally relative to the reference projection direction. When a given resolution orthogonally relative to the reference projection direction is assumed, then the compression factor that can be achieved in the compression corresponds to the quotient R or /R r .
In the described exemplary embodiment, the non-uniform pixel matrix is realized according to FIG. 6 wherein it can be seen that the compressed data corresponding to the segment images are represented as pixels having an oblong, shape, such as a rectangular shape, with the longest extent of the pixels proceeding in the reference projection direction.
If it is desired to reduce the memory space required for storing the segment images, a first compression operating mode is selected wherein the segment images are converted into the non-uniform pixel matrix after the reconstruction has ensued.
If it is also desired to reduce the calculating outlay required for the reconstruction of the segment images, a second compression operating mode is selected wherein the segment images are already reconstructed in the non-uniform pixel matrix. This offers the advantage that significantly fewer pixels need to be reconstructed than in the case of a uniform matrix that exhibits the same resolution orthogonally to the reference projection direction as the non-uniform pixel matrix.
During the course of the reconstruction in the non-uniform matrix, the coordinate system with the axis and the axis underlying the back-projection is rotated according to FIG. 5 such that the back-projection direction corresponds to the respective reference projection direction.
Regardless of which of the two compression operating modes is selected, the data compression must in turn be canceled no later than during the combining of the sub-images to form a resulting CT image. Therefore in the inventive CT apparatus the sub-images are also generated on the basis of the non-uniform pixel matrix, and the transition to a uniform pixel matrix ensues only during the course of the generation of the resulting CT image. Compared to the procedure, that is likewise possible, of already switching to the uniform pixel matrix in the combining of the segment images belonging to a sub-segment to form a sub-image, this offers the advantage of a reduced memory requirement as well as a reduced calculating outlay.
Regardless of whether the decompression ensues during the course of the combining of segment images to form a sub-image or the combining of sub-images to form a resulting CT image, the pixels of the uniform pixel matrix, in a selectable first operating mode, are acquired by interpolation from the pixels of the uniform pixel matrix. Given selection of a second operating mode, the pixels of the uniform pixel matrix are acquired from the pixels of the non-uniform pixel matrix by weighting.
As a result of the alignment of the non-uniform pixel matrix corresponding to the reference projection direction, the non-uniform pixel matrix must be larger than the uniform pixel matrix in both of the just-described operating modes in order, despite the rotation of the non-uniform pixel matrix relative to the uniform pixel matrix, to assure that the non-uniform pixel matrix contains data suitable for the determination of each pixel of the uniform pixel matrix. In the case of a quadratic uniform pixel matrix and a likewise quadratic non-uniform pixel matrix, this means that the side length (for arbitrary reference projection directions) of the non-uniform pixel matrix must be greater than that of the uniform pixel matrix.
As to the procedure in the data decompression by means of interpolation or weighting, the discussion above in conjunction with the combining of a number of segment images to form a sub-image applies analogously, i.e. the averaging also can ensue weighted.
In the described exemplary embodiment, the data compression ensues on the basis of the employment of a non-uniform pixel matrix. Alternatively, other compression methods standard in the field of image processing can be applied.
In an operating mode with inclined rotary frame 7 illustrated in FIG. 7, the rotational axis Z′ around which the focus F rotates around the system axis Z is not identical with the system axis Z but intersects this at the gantry angle ρ. Then the geometry according to FIG. 2 yields a tilted coordinate system according to FIG. 7 with the z′-axis corresponding to the middle axis of the spiral path S that is tilted relative to the z-axis by the gantry angle ρ, with the y′-axis that is likewise tilted by the gantry angle ρ relative to the y-axis, and with the x-axis retained unmodified.
The following is valid for the spiral path S in this coordinate system: x f ′ -> = ( - R f cos α - R f sin α + Sp α sin ρ 2 π Sp α cos ρ 2 π ) ( 15 )
The above-described procedure for determining the maximum tilt angle δ max can be transferred to the case of the tilted gantry, whereby the following is valid instead of Equation (6): z Det ′ ( b ) = z ′ ( b ) - Sp α cos ρ 2 π = - R f tan δ cos γ - Sp α cos α 2 π - b ( sin α tan δ cos γ + cos α tan γ ) , ( 16 )
The following is derived therefrom for b=±RFOV: z Det ′ ( = ± RFOV ) = ± WM 2 1 - ( b R f ) 2 + α sin b R f Sp cos α 2 π ( 17 )
The inclination angle γ′ in the coordinate system (x,y′,z′) for the case of the inclined gantry, however, is now to be introduced into the definition equation for the maximum tilt angle δ max , i.e. into Equation (9).
The following is valid for the inclination angle γ′ in the case of the inclined gantry: tan γ ′ = ∂ z ∂ z ′ ∂ s = ∂ z ′ ∂ α · ∂ α ∂ s = Sp · cos ρ 4 π 2 · R f + S 2 ρ 2 + 4 π · R f cos α sin ρ · Sp
or
γ ′ = arctan S ρ · cos ρ 4 π 2 · R f + S 2 p 2 + 4 π · R f cos α sin ρ · Sp ( 18 )
It has been found that the inclination angle γ′ for the case of the tilted gantry is nearly independent of the reference projection angle α r . It was also found with respect to the maximum tilt angle δ max that this is nearly independent of the reference projection angle α r .
There is also the possibility in the case of the inclined gantry of determining the appertaining optimum value for the inclination value γ′ for a given amount of the maximum value of the tilt angle |δ max | that, for example, is acquired from ( 9 ) on the basis of the result acquired according to ( 18 ) from the slope of the spiral path S in such a way that an error criterion is met, for example the minimum average of the squares of the distances measured in z-direction of all points of the sub-segment from the image plane.
In the described exemplary embodiment, the relative motion between the measuring unit 1 and the support mechanism 9 is generated by displacing the support mechanism 9 . However, there is also the possibility within the framework of the invention of leaving the support mechanism 9 stationary and instead displacing the measuring unit 1 . Within the framework of the invention, there is also the possibility of generating the necessary relative motion by displacing both the measuring unit 1 as well as the support mechanism 9 .
The conical x-ray beam in the described exemplary embodiment has a rectangular cross-section. In the framework of the invention, however, other cross-sectional geometries are also possible.
A CT apparatus of the third generation was described in conjunction with the above-described exemplary embodiments, i.e. the x-ray source and the detector system are displaced in common around the system axis during the image generation. The invention, however, also can be employed in conjunction with CT apparatuses of the fourth generation wherein only the x-ray source is displaced around the system axis and interacts with a fixed detector ring, insofar as the detector system is a matter of a multi-line array of detector elements.
The inventive method also can be employed with CT apparatuses of the fifth generation, i.e. a CT apparatus wherein the x-radiation emanates from not only one focus but from a number of foci of one or more x-ray sources displaced around the system axis, insofar as the detector system comprises a multi-line array of detector elements.
The CT apparatus employed in conjunction with the above-described exemplary embodiments have a detector system with detector elements arranged in the fashion of an orthogonal matrix. The invention, however, also can be employed in conjunction with CT apparatus having a detector system with detector elements arranged in a planar array or in some other way.
The above-described exemplary embodiments relate to the medical application of the inventive method. The invention, however, also can be employed beyond medicine, for example in baggage inspection or when investigating materials.
Although modifications and changes may be suggested by those skilled in the art, it is the intention of the inventors to embody within the patent warranted hereon all changes and modifications as reasonably and properly come within the scope of their contribution to the art.
|
In a method and apparatus for computed tomography, a subject is scanned with a conical ray beam emanating from a focus and the attenuated beam is detected with a matrix-like detector array. The focus is moved on a spiral path around a system axis relative to the subject, and the detector array supplies output data corresponding to the received radiation. The output data are supplied during the motion of the focus on a spiral segment and have a length adequate for the reconstruction of a CT image, and are divided into output datasets with respect to sub-segments. Segment images having an inclined image plane relative to the system axis are reconstructed for the sub-segments. The segment images respectively belonging to the sub-segments are combined into a partial image with respect to a target image plane, and the partial images are combined into a resulting CT image with respect to the target image plane.
| 0
|
TECHNICAL FIELD
[0001] The present disclosure generally relates to medical devices, systems and methods for that include an inflatable member in biomedical and other medical and non-medical applications, and in particular to apparatuses, systems, methods and kits for preventing over inflation of an inflatable member.
BACKGROUND
[0002] Various types of inflatable members are used during medical procedures to expand an internal cavity of a patient in order to perform a medical procedure.
[0003] One type of inflatable member is the balloon catheter. In general, balloon catheters can exist in a deflated state and an inflated state; intermediate states are also available. In use, the balloon catheter in its deflated state is inserted into a cavity of a patient. After positioning within the patient, the balloon catheter is inflated via any of various means using various inflation media, for example, using a syringe to inject a liquid mass into the balloon or using an inflation bulb to provide air into the balloon. Some systems utilize a pressure gauge to monitor the pressure to prevent over pressurization of the balloon.
[0004] In particular, in some medical procedures an imaging device is used to image an internal cavity of a patient. In order to capture clear images of the cavity tissue, the imaging device can be positioned within a balloon catheter that can be inserted into the cavity. The balloon is then inflated to provide clear access to the imaging device of the system. In these balloon catheter systems, the balloon catheter and most components connected thereto require disposal due to being in contact with the patient.
[0005] In some instances, if an operator is not properly monitoring the pressure gauge, the balloon may be inflated to an over inflated or over pressurized state. This over pressurization of the balloon can cause damage to or even rupturing of the balloon, or even worse can cause damage to the surround tissue within the cavity of the patient. Also if the balloon is underinflated, the imaging device may not be able to properly capture and image of the surrounding tissue. This disclosure describes an improvement over these prior art technologies.
SUMMARY
[0006] Accordingly, an inflation apparatus with pressure relief is provided that includes an inflatable member having a proximal end and a distal end and defining a deflated state, an inflated state, and a cavity therein; a first shaft having a first end connected to the proximal end of the inflatable member and defining a cavity along a longitudinal axis thereof; an imaging device having an imaging assembly at a distal end thereof and extending into said cavity of said inflatable member and connectable to an imaging system at a proximal end thereof; a second shaft configured to contain said imaging device, said second shaft having a closed end approximate to the imaging assembly and a open end approximate to the imaging system, said second shaft defining a cavity along a longitudinal axis thereof and configured to be positioned within said cavity of said first shaft; said first shaft and said second shaft defining a channel therebetween in communication with said cavity of the inflatable member; an inflator connected to said first shaft and in communication with said channel for inflating said inflatable member; and a relief valve in communication with said channel and positioned between said inflatable member and said inflator.
[0007] In one embodiment, an inflation apparatus with pressure relief includes an inflatable member having a deflated state and an inflated state, and defining a cavity therein; a first shaft defining a cavity therein and having a proximal end and a distal end, said distal end connected to said inflatable member; a second shaft defining a cavity therein and having a closed end and an open end, said second shaft disposed within said first shaft such that said closed end is disposed within said inflatable member, said first shaft and said second shaft defining a channel therebetween in communication with the cavity of the inflatable member; an inflator in communication with the channel configured to inflate the inflatable member; a relief valve in communication with the channel to prevent over pressurization if the inflatable member; and a pass-through component configured to maintain an isolation of the cavity of the second shaft from said channel and permit communication between said inflator and said channel.
[0008] In one embodiment, an inflation kit with pressure relief includes more than one air supply for supplying air through a pathway to an inflatable member; a valve connected in the pathway to control the flow of the inflatable member; a pressure gauge connected in the pathway for monitoring the pressure of the inflatable member; and a pressure relief valve connected in the pathway for venting the pressure at a preset pressure.
[0009] In one embodiment a method for testing an inflation kit includes receiving an inflation kit; attaching a test valve to the pathway and configured to seal the pathway; closing test valve to seal the pathway; opening the valve to increase pressure in the pathway; monitoring pressure gauge; closing the valve upon reaching a preset pressure; determining is the pressure is maintained for a preset period of time; after the preset period of time, opening the valve to again increase the pressure in the pathway; monitoring the pressure gauge; determining if the relief valve opens; identifying on the pressure gauge the pressure at which the relief valve opens.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The present disclosure will become more readily apparent from the specific description accompanied by the following drawings, in which:
[0011] FIG. 1 is a schematic diagram of an inflation system with pressure relief in accordance with the principles of the present disclosure;
[0012] FIG. 2 is a partial front view of the inflation system of FIG. 1 ;
[0013] FIG. 3 is a cross sectional view of the system of FIG. 1 at a balloon end thereof; and
[0014] FIG. 4 is a cross sectional view of an upper end of the system of FIG. 1 .
[0015] Like reference numerals indicate similar parts throughout the figures.
DETAILED DESCRIPTION
[0016] The present disclosure may be understood more readily by reference to the following detailed description of the disclosure taken in connection with the accompanying drawing figures, which form a part of this disclosure. It is to be understood that this disclosure is not limited to the specific devices, methods, conditions or parameters described and/or shown herein, and that the terminology used herein is for the purpose of describing particular embodiments by way of example only and is not intended to be limiting of the claimed disclosure.
[0017] The present disclosure is described herein in connection with an imaging system. It is understood that the present disclosure is applicable to any systems that include an inflatable member, the pressure of which is to be monitored and controlled.
[0018] Also, as used in the specification and including the appended claims, the singular forms “a,” “an,” and “the” include the plural, and reference to a particular numerical value includes at least that particular value, unless the context clearly dictates otherwise. Ranges may be expressed herein as from “about” or “approximately” one particular value and/or to “about” or “approximately” another particular value. When such a range is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. It is also understood that all spatial references, such as, for example, horizontal, vertical, top, upper, lower, bottom, left and right, are for illustrative purposes only and can be varied within the scope of the disclosure. For example, the references “superior” and “inferior” are relative and used only in the context to the other, and are not necessarily “upper” and “lower”.
[0019] Reference will now be made in detail to the exemplary embodiments of the present disclosure, which are illustrated in the accompanying figures.
[0020] System 10 includes an imaging device 20 , e.g. an optical coherence tomography (OCT) imaging device. Although the present disclosure is described using an OCT imaging device, other imaging devices are contemplated. For example, imaging device can include a visual light camera, an ultrasound imaging device or other imaging devices. OCT imaging device 20 includes an imaging assembly 21 comprising one or more components commonly found in rotating and/or translating imaging devices. These components can include mirrors, lenses, filters, prisms and combinations thereof; other components are contemplated. OCT imaging device 20 is connected to a distal end 23 of an inner member 22 . When used in connection with OCT imaging device 20 , inner member 22 can include a fiber optic cable configured to transmit light energy. A proximal end 24 of inner member 22 is connected to one or more imaging systems 150 , e.g. an OCT visualization system.
[0021] OCT imaging device 20 is contained within an inner shaft 30 having a distal end 31 and a proximal end 32 . Inner shaft 30 is sealed at distal end 31 and can attach to imaging system 150 at proximal end 32 . Inner shaft 30 provides a working environment for OCT imaging device 20 to freely rotate and/or translate within. Inner channel 33 is defined between inner member 22 and inner shaft 30 . Inner shaft 30 can be rigid or flexible depending on the system requirements.
[0022] Distal end 31 of inner shaft 30 containing OCT imaging device 20 is contained within an inflatable member 40 , e.g. a balloon, having a proximal end 41 and a distal end 42 . Balloon 40 defines an inner cavity 43 . Balloon 40 can be manufactured from various compliant and/or non-compliant materials, for example, latex and/or polyethylene terephthalate (PET), polyurethane, nylon or polyether block amide. Other materials are contemplated. Whichever material is used, balloon 40 is designed to transition between a deflated state and an inflated state; intermediate states are contemplated. Balloon 40 is shown in an inflated state.
[0023] Proximal end 41 of balloon 40 is connected to a distal end 51 of an outer shaft 50 . Outer shaft 50 can be rigid or flexible depending on the system requirements. Outer shaft 50 is configured to slidingly receive inner shaft 30 and OCT imaging device 20 . Distal end 31 of inner shaft 30 can be attached to distal end 42 of balloon 40 . An outer channel 53 is defined between inner shaft 30 and outer shaft 50 . Outer channel 53 is in communication with cavity 43 of balloon 40 . Outer channel 53 is used to deliver or remove air to/from cavity 43 to inflate or deflate balloon 40 . Inner channel 33 is sealed from and does not communicate with outer channel 53 .
[0024] A proximal end 52 of outer shaft 50 is connected to a first end 61 of a branch tee 60 . Although a branch tee is described herein, other fillings are contemplated, for example, a heal tee or Y shaped fitting can also be used. Branch tee 60 is designed to allow inner shaft 30 and inner member 22 to pass therethrough but retain the seal between inner channel 33 and outer channel 53 . Inner shaft 30 and inner member 22 extend from a second end 62 of branch tee 60 to connect to imaging system 150 . As shown in FIG. 4 , inner shaft 30 and inner member 22 extend from second end 66 of branch tee 60 . A space 64 between an outer surface of inner shaft 30 and an inner surface of second end 62 is sealed to seal channel 53 from the outside environment. Seal of space 64 can be a sealant or can be monolithically formed with tee 60 to tightly seal around inner shaft 30 . As another example, branch tee 60 can be molded over the inner shaft 30 and thermally bonded thereto to seal around it.
[0025] The bull 63 of branch tee 60 is connected to a first end 73 of a branch tee 72 via tube 71 . A second end 74 of branch tee 72 is connected to a first end 83 of a branch tee 82 via tube 81 . A second end 84 of branch tee 82 is connected to an outlet 92 of a valve 90 via tube 91 . An inlet 93 of valve 90 is connected to air supply 100 via tube 101 . Tubes 71 , 81 , 91 and/or 101 can be rigid or flexible depending on system requirements. Although tubes are described as connecting various components (e.g. tees 72 and 82 ), direct connections between the components are contemplated. In addition, the orientation of the components can vary depending on system configuration.
[0026] Air supply 100 can include mechanical, electromechanical or pressurized air supplies. For example, air supply can include an inflation bulb, a syringe, an electric pump or an air tank containing pressurized air. Other air supplies are contemplated. In addition, as stated above, the present disclosure is not limited to using air to inflate the balloon. For example other gases such as nitrogen or helium or liquids such as saline or contrast media are contemplated.
[0027] A relief valve 70 is connected to bull 75 of tee 72 . Relief valve 70 is designed to prevent an over pressuring of balloon 40 . For example, in a system wherein an esophagus of a patient is to be imaged, balloon 40 , in a deflated state and containing OCT imaging device 20 , is inserted into the patient. Before imaging can commence, balloon 40 requires inflation. A PET balloon for this application may require a pressure of 5 pounds per square inch (psi) as a nominal pressure to properly inflate. Such a PET balloon 40 may have a pressure tolerance rating of +5 psi. As such, a relief valve 70 designed to release at 8 psi +/−2 can be used to. maintain balloon 40 within its tolerance ranges. Based on the specifications of the balloon 40 , differing pressure valves can be used.
[0028] A pressure gauge 80 is connected to bull 85 of tee 82 . Pressure gauge 80 is used to monitor the pressure in the balloon 40 as cavity 43 is connected to pressure gauge 80 through channel 53 .
[0029] The present disclosure describes a inflation apparatus with pressure relief that can be reused. That is, the components from branch tee 60 through air supply 100 are tangential to the path of balloon 40 and shaft 50 , and thus the patient, and therefore can be reused and remain non-sterile.
[0030] In use and operation, balloon 40 , in a deflated state and containing imaging device 20 , is inserted into a cavity of a patient to be imaged. Once at the desired position, air pressure created by air supply 100 is allowed to enter the system 10 by the opening of valve 90 . As the air pressure increases, balloon 40 transitions from its deflated state to its inflated state. During this process, pressure gauge 80 can be monitored to monitor the increasing pressure in the system 10 . In normal operation this process continues until a desired pressure, e.g. 5 psi, is reached, at which time valve 90 would be closed to prevent over pressurization. In the event the monitoring of pressure gauge 80 is interrupted, thus allowing the air pressure in the system to continue to increase, relief valve will open at its set pressure, e.g. 8 psi +/−2, to prevent damage to the system 10 or the patient.
[0031] Due to the design of the system 10 , the system 10 can maintain a required balloon 40 pressure and allow the operation of the OCT imaging device 20 to translate and/or rotate the image 21 within the patient.
[0032] An inflation kit is also contemplated. The kit can include more than one air supply 100 , for example, an inflation bulb and a syringe. Also included in the kit are relief valve 70 , pressure gauge 80 and valve 90 connected via tubing as described herein. The kit comes ready to connect to branch tee 60 .
[0033] The inflation apparatus with pressure relief can also be subject to a pressure testing procedure. A sub-system of components 71 through 100 are assembled as described. A test valve (not shown) is attached to end of tubing 71 , replacing branch tee 60 . With the test valve in a closed position and valve 90 in an opened position, pressure is applied to the sub-system via air supply 100 . Pressure gauge 80 is monitored until a preset pressure is obtained, e.g. 5 psi. This pressure is maintained, i.e. valve 90 is closed, for a preset time period, e.g. 30 seconds. After the preset time period has elapsed, the pressure is again increased by opening valve 90 . The pressure is monitored via pressure gauge 80 until relief valve 70 opens at its preset pressure, e.g. 8 psi. A calibrated and tested secondary relief valve can be incorporated into the sub-system to prevent damage to the sub-system should relief valve 70 fail to operate properly. In addition, a calibrated and tested secondary pressure gauge can be incorporated into the sub-system to accurately determine if the relief valve opens within its specified range and determine if pressure gauge 80 is accurate.
[0034] The present disclosure has been described herein in connection with an imaging system including an OCT imaging device contained within a balloon. It is understood that the present disclosure is applicable to any systems that include an inflatable member, the pressure of which is to be monitored, with or without imaging devices as disclosed herein. For example, the present disclosure is applicable to systems for performing procedures such as angioplasty. Other applications are contemplated.
[0035] Where this application has listed the steps of a method or procedure in a specific order, it may be possible, or even expedient in certain circumstances, to change the order in which some steps are performed, and it is intended that the particular steps of the method or procedure claim set forth herebelow not be construed as being order-specific unless such order specificity is expressly stated in the claim.
[0036] While the preferred embodiments of the devices and methods have been described in reference to the environment in which they were developed, they are merely illustrative of the principles of the inventions. Modification or combinations of the above-described assemblies, other embodiments, configurations, and methods for carrying out the invention, and variations of aspects of the invention that are obvious to those of skill in the art are intended to be within the scope of the claims.
|
Systems, devices, methods and kits for an inflation system with pressure relief are provided. The system includes an inflatable member, a first shaft connected to the inflatable member, an imaging device extending into said cavity of the inflatable member, a second shaft configured to contain the imaging device, the second shaft having a closed end approximate to the imaging assembly and a open end approximate to the imaging system, the second shaft defining a cavity along a longitudinal axis thereof and configured to be positioned within the cavity of the first shaft; the first shaft and the second shaft defining a channel therebetween in communication with the cavity of the inflatable member; an inflator connected to the first shaft and in communication with the channel for inflating the inflatable member; and a relief valve in communication with the channel and positioned between the inflatable member and the inflator.
| 0
|
CROSS-REFERENCE TO RELATED APPLICATION
This application is based upon, and claims the benefit of, United States Provisional Patent Application No. 60/181,871 filed Feb. 11, 2000, the disclosure of which are incorporated by reference herein in its entirety.
BACKGROUND OF THE INVENTION
1. Technical Field
This invention relates to vane pumps.
2. Related Art
A vane pump typically includes a cylindrical rotor supported for rotation inside of an oval-shaped rotor chamber defined by a cam ring surrounding the rotor. The cam ring and the rotor define crescent-shaped cavities therebetween which are divided in to a plurality of pump chambers by a corresponding plurality of flat vanes carried in radial vane slots of the rotor. The pump chambers expand into an inlet sector of the crescent-shaped cavities and collapse in a discharge sector of the cavities as the rotor rotates. A thrust plate and a pressure plate are disposed on opposite sides of the cam ring and are squeezed together under spring tension to cover the rotor chamber. An opposite thrust face of the thrust plate is pinned between the cam ring and end wall of the housing. A significant fluid pressure differential is developed across the thrust plate which induces flexure of the thrust plate away from the rotor toward the end wall. A clearance dimension between the housing, thrust plate, and rotor calculated to accommodate such flexure exceeds a corresponding clearance dimension needed for high volumetric efficiency. Fluid leakage from the pump chambers attributable to the extra clearance for flexure of the thrust plate reduces the volumetric efficiency of the vane pump.
U.S. Pat. No. 6,050,796 discloses a vane pump having a hydraulically balanced rotor for improving the efficiency of the pump. The present invention provides further improvements to vane pumps.
SUMMARY OF THE INVENTION AND ADVANTAGES
A vane pump constructed according to the invention comprises a pump housing having a longitudinal axis, a cavity for hydraulic fluid, and a substantially planar end wall of the housing which is exposed to the cavity. A thrust plate is disposed in the cavity having a first thrust face disposed in adjacent facing relation to the end wall of the housing, and an opposite second thrust face. The thrust face has at least one fluid inlet port communicating with the cavity. A pressure plate is disposed in the cavity in axially space relation to the thrust plate. A cam ring is disposed in the cavity between the thrust plate and pressure plate and has a circumferentially extending inner cam wall defining a rotor chamber of the cavity. A rotor is supported in the rotor chamber for rotation about the longitudinal axis of the housing relative to the inner cam wall of the cam ring. A plurality of vanes are slideably supported by the rotor for radial reciprocation in communication with the inner cam wall of the cam ring to define a plurality of dynamically expanding and diminishing volume sectors of the rotor chamber and which are operative to draw hydraulic fluid into the rotor chamber under low pressure and expel the hydraulic fluid under elevated pressure from the rotor chamber. A resilient gasket is disposed between the first thrust face of the thrust plate and the end wall of the housing to define a sealed balance chamber therebetween.
Provision of the balance chamber is operative to exert counteracting controlled fluid pressure on the first thrust face to oppose the fluid pressure exerted on the second thrust face so as to support the thrust plate in hydraulic equilibrium within the pump housing. The balance of fluid force on axially opposite sides of the thrust plate minimize or eliminate thrust plate flexure away from the rotor, allowing for tighter dimensional tolerance of the thrust plate and rotor which in turn lessens leakage of high pressure fluid past the thrust plate and lessens the loss of volumetric efficiency associated therewith. When combined with a hydraulically balanced rotor, a pump constructed according to the invention has been shown to improve volumetric efficiency by as much as 57% over traditional vane pumps without such balanced thrust plate and rotor components.
THE DRAWINGS
A presently preferred embodiment of the invention is disclosed in the following description and in the accompanying drawings, wherein:
FIG. 1 is a longitudinal sectional view of a vane pump constructed according to the invention;
FIG. 2 is a sectional view taken generally along lines 2 — 2 of FIG. 1;
FIG. 3 is a sectional view taken generally along lines 3 — 3 of FIG. 1;
FIG. 4 is a sectional view taken generally along lines 4 — 4 of FIG. 1;
FIG. 5 is a fragmentary perspective view of a rotor;
FIG. 6 is a fragmentary sectional view taken generally along lines 6 — 6 of FIG. 5;
FIG. 7 is a sectional view taken generally along lines 7 — 7 of FIG. 1; and
FIG. 8 is an enlarged fragmentary sectional view showing further features of the thrust plate and housing.
DETAILED DESCRIPTION
Referring now in more detail to the drawings, a vane pump 10 constructed according to the invention includes a pump housing 12 having therein a drive shaft bore 14 open through a first end 16 of the housing 12 and intersecting a flat bottom or end wall 18 of a large counter bore or cavity 20 in a second end 22 of the housing 12 . A control valve bore 24 in the housing 12 communicates with the counter bore 20 through a schematically represented internal passage 26 in the housing 12 . An inlet passage 28 in the housing 12 communicates with a reservoir of fluid (e.g., hydraulic fluid), not shown, and with the internal passage 26 through an aperture 30 .
A “rotating group” 32 of the vane pump 10 is captured in the cavity 20 between the end wall and a disc-shaped cover 34 closing the open end of the cavity 20 . An annular chamber 36 is defined between a cylindrical side wall 38 of the cavity 20 and the rotating group 32 . A seal ring 40 suppresses fluid linkage between the housing 12 and the cover 34 . The rotating group 32 is stationary relative to the pump housing 12 and includes a thrust plate 42 seated on the flat end wall 18 of the cavity 20 , a pressure plate 44 spaced axially from the thrust plate 42 , and a cam ring 46 disposed in the cavity 20 between the thrust plate 42 and the pressure plate 44 . A plurality of dowel pins 48 traverse the thrust plate 42 , pressure plate 44 , cam ring 46 , and the housing 12 and prevent relative rotational movement therebetween about a longitudinal center line or axis 50 of the pump housing 12 .
The cam ring 46 has an oval-shaped inner wall 52 that is circumferentially continuous and faces the longitudinal center line 50 . The thrust plate 42 has an aperture or shaft bore 54 in line with the bore 14 of the housing 12 . The thrust plate 42 has a first thrust face 56 facing the end wall 18 of the housing 12 and an axially opposite second thrust face 57 facing and bearing against an end 58 of the cam ring 46 . The pressure plate 44 has a planar side 60 facing and bearing against an end 62 of the cam ring 58 and an annular shoulder 64 on which the cover 34 is seated. The oval-shaped inner wall 52 of the cam ring 46 and the planar sides 57 , 60 of the thrust plate 42 and pressure plate 44 cooperate in defining a generally oval-shaped rotor chamber 66 of the cavity 20 , as best shown in FIG. 3 .
The cover 34 compresses the rotating group 32 against the end wall 18 of the cavity 20 to seal the rotor chamber 66 against fluid leakage against the planar side 57 of the thrust plate 42 and the end 58 of the cam ring 46 and between the planar side 60 of the pressure plate 44 and the end 62 of the cam ring 46 . A retaining ring 68 is mounted in the cavity 20 to engage and prevent dislodgment of the cover 34 from the cavity 20 . A discharge chamber 70 of the vane pump 10 is defined between the cover 34 and the pressure plate 44 and within the housing 12 around the drive shaft bore 14 . A seal ring 72 suppresses fluid leakage between the cover 34 and the pressure plate 44 .
A drive shaft 74 is jounaled by a bearing of the pump housing 12 for rotation about the longitudinal axis 50 . A splined inboard end of the drive shaft 74 engages a splined bore 76 of a rotor 78 disposed in the rotor chamber 66 for rotation with the shaft 74 within the rotor chamber 66 about the longitudinal axis 50 . An outboard end (not shown) of the drive shaft 74 is coupled to a rotary drive source, such a motor of a motor vehicle, when the vane pump 10 is employed for providing a source of pressurized fluid for a steering assist fluid motor of a motor vehicle.
The rotor 78 has a cylindrical outer surface 80 which is symmetric with respect to the longitudinal 50 of the pump 10 . The rotor 78 has a pair of planar end walls 82 A, 82 B disposed in parallel planes perpendicular to the longitudinal axis 50 . The end walls 82 A, 82 B of the rotor 78 are separated from the planar sides 60 , 57 of the pressure plate 44 and the thrust plate 42 by respective ones of a pair of clearance dimensions D 1 , D 2 , illustrated in exaggerated fashion in FIG. 6 . The outer surface 80 of the rotor 78 cooperates with the inner wall 52 of the cam ring 46 in defining a pair of crescent-shaped cavities 84 A, 84 B of the rotor chamber 66 on radially opposite sides of the rotor 78 , as best illustrated in FIG. 3 .
The rotor 78 is formed with a plurality of radial vane slots 86 which intersect the outer surface 80 and each of the end walls 82 A, 82 B. A corresponding plurality of flat vanes 88 are supported in respective ones of vane slots 86 for sliding radial reciprocation relative to the rotor 78 . Each flat vane 88 has an outboard lateral edge 90 (FIG. 1) bearing against the oval-shaped inner wall 52 of the cam ring 46 , and a pair of radial edges 92 (FIG. 5) separated from the planar side 66 of the pressure plate 46 and the planar side 57 of the thrust plate 44 by clearance dimensions D 1 , D 2 , respectfully (FIG. 6 ). The vanes 88 divide the crescent-shaped cavities 84 A, 84 B into a plurality of pump chambers 93 (FIG. 3) which expand in each of a pair of diagonally opposite inlet sectors of the crescent-shaped cavities, and collapse in each of a pair of diagonally opposite discharge sectors of the crescent-shaped cavities in conventional fashion concurrent with the direction of rotation R of the rotor 78 .
The thrust plate 42 has a pair or diametrically opposed notches 94 A, 94 B which are open to the annular chamber 36 . The pressure plate 44 has a pair of diametrically opposed notches 96 A, 96 B which are open to the annular chamber 36 . The notches 94 A, 96 A and 94 B, 96 B are angularly aligned with the inlet sector of the crescent-shaped cavities 84 A, 84 B, respectively. The notches 94 A, 96 A and 94 B, 96 B define first and second inlet ports of the vane pump for directing hydraulic fluid from the chamber 36 into the rotor chamber 66 .
As shown best in FIGS. 1, 7 , and 8 , the thrust plate 42 has a pair of diametrically opposed through ports 98 A, 98 B extending through the plate 42 from in the second thrust face 57 thereof to the first thrust face 56 . The pressure plate 44 has a pair of diametrically opposed shallow recesses or grooves 100 A. 100 B in the planar side 60 thereof which are angularly aligned with the ports 98 A, 98 B, respectively, and with the discharge sectors of the crescent-shaped cavities 84 A, 84 B, respectively. The shallow grooves 100 A, 100 B communicate with the discharge chamber 70 through a pair of schematically represented passages 102 in the pressure plate 44 , as shown best in FIGS. 1 and 2, and define respective ones of a pair of discharge ports of the vane pump 10 . The discharge chamber 70 communicates with an external device, such as the aforementioned steering assist fluid motor (not shown) through a discharge passage (not shown) in the pump housing 12 .
As seen best in FIGS. 3, 5 , and 6 , the planar end wall 82 A of the rotor is interrupted by an annular groove 106 having a depth dimension D 3 of about 1.0 mm which intersects each of the radial vane slots 86 and faces a groove 107 in the planar side 60 of the pressure plate opposite the inboard ends of the vane slots 86 . Radially outboard of the annular groove 106 , the end wall 82 A of the rotor defines an annular outer land 108 between the annular groove and the cylindrical outer surface 80 of the rotor. The annular outer land 108 is interrupted by each of the radial vane slots and turns toward the longitudinal centerline 50 on opposite sides of each vane slot to define a plurality of pairs of radial lands 110 integral with the outer land. Radially inboard of the annular groove 106 , the end wall 82 A of the rotor defines an annular inner land 112 between the annular groove 106 and the splined bore 76 in the rotor. The surface area of the annular groove 106 between the outer land 108 and the inner land 112 constitutes a reaction portion of the planar end wall 82 A of the rotor having a surface area of at least 30% of the surface area of the planar end wall 82 A.
The planar end wall 82 B of the rotor is interrupted by an annular groove 114 , FIG. 6, identical to the annular groove 106 in the end wall 82 A facing a groove 115 in the planar side 56 of the thrust plate opposite the inboard ends of the vane slots 86 . The surface area of the annular groove 114 between outer and inner lands corresponding to the outer and inner lands 108 , 112 constitutes a reaction portion of the planar end wall 82 B of the rotor having a surface area of at least 30% of the surface area of the planar end wall 82 B.
The groove 106 cooperates with the planar side 60 of the pressure plate in defining an annular first longitudinal balance chamber 116 . The groove 114 cooperates with the planar side 56 of the thrust plate in defining an annular second longitudinal balance chamber 118 . The first longitudinal balance chamber communicates with the discharge chamber 70 through a schematically represented passage 120 in the pressure plate. The second longitudinal balance chamber communicates with the first balance chamber 116 through the vane slots 86 under the vanes 88 therein.
The annular inner and outer lands 112 , 108 cooperate with the planar side 60 of the pressure plate in defining fluid seals on opposite sides of the annular groove 106 even though separated by the clearance dimension D 1 . Likewise, the inner and the outer lands on opposite sides of the annular groove 114 in the end wall 82 B of the rotor cooperate with the planar side 56 of the thrust plate in defining fluid seals on opposite sides of the annular groove 114 even though separated from the planar side 56 by the clearance dimension D 2 . The close fit between the vanes 88 and the vane slots 86 suppresses fluid leakage from the balance chambers through the vane slots. The outer lands also separate the first and the second balance chambers from the aforesaid inlet and discharge ports of the vane pump.
As shown best in FIGS. 1, 7 and 8 , a resilient gasket or seal 122 fabricated of a suitable rubber or synthetic plastic material resistant to hydraulic fluid is disposed between the first thrust face 56 of the thrust plate 42 and the facing end wall 18 of the housing 12 . The gasket 122 is compressed between the thrust plate 42 and housing end wall 18 and defines at least one and preferably at least two bounded, sealed balance chambers 124 A, 124 B which are isolated by the gasket 122 from the chamber 36 and the drive shaft bore 14 of the housing 12 . The thrust plate 42 preferably is formed with grooves 126 in the first thrust face 56 which outline the balance chamber regions 124 A, 124 B. The gasket 122 is accommodated in the grooves 126 , with a sealing portion 128 of the gasket 122 projecting out of the grooves 126 beyond the first thrust face 56 for sealing contact with the end wall 18 of the housing 12 . The grooves 126 and gasket 122 disposed therein are arranged to surround the through ports 98 A, 98 B of the thrust plate 42 , as shown best in FIG. 7, such that the through ports 98 A, 98 B open into the balance chambers 124 A, 124 B on the first thrust face 56 for the containment of high pressure hydraulic fluid at the discharge pressure across an area of the thrust face 56 substantially greater than that of the area occupied by the through ports 98 A, 98 B. The size and shape of the balance chambers 124 A, 124 B are selected to capture within the balance chambers 124 A, 124 B a volume of the high pressure hydraulic fluid under the discharge pressure which is distributed evenly across the area of the first thrust face surface 56 confined by the balance chambers 124 A, 125 B and exerts an axial hydraulic balancing force F 3 (FIGS. 1 and 8) in the axial direction against the first thrust face 56 which is preferably equal to and counteracts the hydraulic fluid force F 4 exerted on the second thrust face 57 from the rotor chamber 66 , so as to balance the thrust plate 42 in hydraulic equilibrium in the direction of the axis 50 , as will be explained in greater detail below.
In operation, fluid at substantially atmospheric pressure is delivered to the annular chamber 36 around the rotating group through the inlet passage 28 , the aperture 30 , and the internal passage 26 in the pump housing 12 . As the drive shaft 74 rotates the rotor 78 , the expanding pump chamber 93 in the inlet sectors of the crescent-shaped cavities 84 A, 84 B are filled with hydraulic fluid through the inlet ports defined by the notches 94 A, 96 B and 94 A, 96 B. The fluid in the pump chambers is transported by the rotor 78 to the discharge sectors of the crescent-shaped cavities 84 A, 84 B and expelled through the discharge ports 98 A, 98 B of the thrust plate 42 and the recesses 100 A, 100 B of the pressure plate 44 into the discharge chamber 70 . The fluid pressure prevailing in the discharge chamber 70 is a high discharge pressure of the vane pump 10 . The discharge chamber 70 is connected to the aforementioned steering assist fluid motor or similar device through a flow control valve, not shown, in the bore 24 of the housing 12 . The flow control valve maintains a substantially rate of fluid flow from the vane pump 10 by recirculating a fraction of the fluid expelled from the pump chambers back through the annular chamber 36 around the rotating group through the internal passage 26 and the pump housing 12 .
The fluid in the discharge chamber induces a net pressure force on the pressure plate 44 represented by a schematic force vector F 1 , FIG. 1, which reacts evenly across the exposed area of the pressure plate. The net pressure force represented by the schematic vector F 1 thrusts the rotating group toward the flat bottom 18 of the counterbore 20 for enhanced suppression of fluid leakage from between the planar side of the thrust plate and the end 58 of the cam ring and between the planar side of the pressure plate and the end 62 of the cam ring.
At the same time, fluid at the discharge pressure of the pump is conducted or ported to the annular first balance chamber 116 through the passages 102 in the pressure plate and from the first balance chamber into the second balance chamber 118 through the vane slots 86 under of the flat vanes 88 . The fluid pressure under the flat vanes thrusts the outboard lateral edges 90 of the vanes against the oval-shaped wall 52 of the cam ring to suppress fluid leakage from the pump chambers 93 between the vanes and the oval-shaped wall.
The fluid pressure in the first balance chamber 116 of the rotor 78 induces a net pressure force on the pressure plate represented by a schematic force vector F 2 opposite to the net pressure force represented by the schematic vector F 1 . The fraction of the net pressure force represented by the schematic vector F 1 , reacting on the pressure plate within the silhouette of the oval-shaped rotor chamber 66 is effectively offset or balanced by the net pressure force represented by the schematic vector F 2 because the reaction portion of the planar end wall 82 A of the rotor constitutes a substantial fraction of the area of the silhouette of the rotor chamber 66 . Accordingly, the flexure of the pressure plate 44 into the rotor chamber characteristic of the prior van pumps referred to above is substantially reduced so that the clearance dimension D 1 is smaller than corresponding clearance dimensions in such prior van pumps for improved volumetric efficiency.
The fluid pressure in the first balance chamber 116 also reacts against the reaction portion of the planar end wall 82 A of the rotor and thrusts the rotor toward thrust plate. Concurrently, however, the same fluid pressure in the annular second balance chamber 118 reacts against the reaction portion of the opposite end wall 82 B of the rotor and thrusts the rotor toward the pressure plate. Because the reaction portions of the planar first and second end walls of the rotor are equal, the net pressure force on the rotor attributable to fluid in the annular first balance chamber equal s the net pressure force on the rotor attributable to fluid in the annular second balance chamber. Accordingly, the rotor is suspended longitudinally in static equilibrium between the planar sides of the pressure plate and the thrust plate with the substantially equal clearance dimensions D 1 , D 2 minimizing both sliding friction and fluid leakage between the rotor and the flat vanes thereon and the planar sides of the thrust plate and the pressure plate.
The fluid in the discharge sectors exerts a hydraulic pressure force F 3 on the second thrust face 57 of thrust plate 42 which urges the thrust plate 42 axially away from the rotor 78 and cam ring 46 toward the end wall 18 of the housing 12 .
The balance chambers 124 A, 124 B defined on the opposite first thrust face 56 of the thrust plate 42 enclose a sealed space in fluid communication with fluid at the discharge pressure through the ports 98 A, 98 B in the thrust plate 42 and through flow passages 136 A, 136 B formed in the housing 12 (FIGS. 1 and 8 ) which extend from the discharge chamber 70 through the end wall 18 for porting the high pressure hydraulic fluid to the sealed balance chambers 124 A, 124 B to exert the counteracting balance force vector F 4 in opposition to the opposing force vector F 3 . As mentioned, the size and shape of the balance chambers 124 A, 124 B and thus the shape of the grooves 126 and gasket 122 are engineered to provide a counteracting force F 4 to the opposing force F 3 so as to balance the thrust plate 42 , placing it in a state of hydraulic equilibrium in the axial direction within the cavity 20 of the housing 12 . One such shape is illustrated in FIG. 7, although it will be appreciated that the invention is not limited to this particular gasket configuration. The gasket 122 of the illustrated embodiment includes an outer perimeter portion 130 A, 130 B which generally traces but is spaced inwardly of the outer perimeter of the thrust plate 42 so as to isolate the chambers 124 A, 124 B from the thrust plate notches 94 A, 94 B and the dowel pins 48 . The gasket 122 includes an inner perimeter seal portion 132 A, 132 B which encircles the drive shaft bore 54 of the thrust plate 42 . The outer and inner seal portions are joined by a transverse bridge portion 134 to partition the area between the outer and inner perimeter portions into a pair of adjacent balance chamber portions denoted as 124 A, 124 B. Each balance chamber portion 124 A, 124 B has associated therewith the aforementioned fluid passages 136 A, 136 B fluid inlet port of the housing 12 (FIGS. 1 and 8) for communicating the high pressure hydraulic fluid into the chamber portions 124 A, 124 B. The gasket 122 keeps the high pressure fluid from escaping the balance chambers 124 A, 124 B into the chamber 36 or drive shaft bore 14 . Accordingly, the thrust plate 42 is supported axially in static equilibrium, minimizing or altogether eliminating axial distortion of the thrust plate 42 and fluid leakage between the flat vanes 88 and the second thrust face 57 of the thrust plate 42 , thereby increasing the volumetric efficiency of the vane pump 10 .
The hydraulically balanced thrust plate 42 has been surprisingly shown to perform best when used in combination with the hydraulically balanced rotor 78 . The balanced thrust plate 42 has shown to improve volumetric efficiency of a vane pump by about 20% when used with a conventional non-hydraulically balanced rotor. A gain in volumetric efficiency of about 58% was shown when the hydraulically balanced thrust plate 42 was used together with the hydraulically balanced rotor 78 .
The disclosed embodiments are representative of presently preferred forms of the invention, but are intended to be illustrative rather than definitive thereof. The invention is defined in the claims.
|
A vane pump includes a cylindrical rotor rotatable inside of an oval-shaped rotor chamber defined by a cam ring around the rotor. A thrust plate and a pressure plate on opposite sides of the cam ring cover the rotor chamber and are squeezed together by a pressure force attributable to fluid in a discharge chamber of the vane pump at a discharge pressure thereof. A first thrust face of the thrust plate is pressed against an end wall of a cavity of a pump housing in which the components are installed. Fluid at the discharge pressure is ported to one or more balance chambers between the thrust plate and the end wall of the housing. The balance chambers are defined by a gasket received in a groove of the first thrust face. Fluid at the discharge pressure within the balance chamber balances a fraction of the pressure force on the thrust plate on an opposite second thrust face thereof attributable to fluid discharged from a rotor chamber in which the rotor operates, in order to place the thrust plate in axial static equilibrium.
| 5
|
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application is a continuation of U.S. patent application Ser. No. 09/990,243 filed 21 Nov. 2001 now U.S. Pat. No. 7,008,425 which claims the benefit of U.S. Provisional Patent Application No. 60/252,536 filed 22 Nov. 2000, and is a continuation-in-part of International Patent Application No. PCT/US00/14840 filed 26 May 2000, which is a continuation-in-part of U.S. patent application Ser. No. 09/321,369 filed 27 May 1999, now abandoned all of which are each incorporated by reference herein.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to devices and methods for repairing bone fractures, and, more particularly, to intramedullary nails and related internal fixation methods especially suitable for repairing long-bone fractures in children.
2. Description of Related Art
The use of intramedullary nails in the repair of long-bone fractures, such as in the femur, has been known in the orthopedic field. Exemplary devices include those known as the Rush and Enders and the Kuntschner nails, as well as those disclosed in U.S. Pat. No. 5,713,902 to Friedl; U.S. Pat. No. 5,697,930 to Itoman et al.; U.S. Pat. No. 5,573,536 to Grosse et al.; U.S. Pat. No. 5,562,666 to Brumfield; U.S. Pat. No. 5,374,235 to Ahrens; U.S. Pat. No. 5,312,406 and U.S. Pat. No. 5,167,663 to Brumfield; U.S. Pat. No. 5,122,141 to Simpson; U.S. Pat. No. 5,066,296, U.S. Pat. No. 5,041,114, and U.S. Pat. No. 4,776,330 to Chapman et al.; U.S. Pat. No. 4,976,258 to Richter et al.; U.S. Pat. No. 4,875,475 to Comte et al.; U.S. Pat. No. 4,846,162 to Moehring; U.S. Pat. No. 4,506,662 to Anapliotis; and U.S. Pat. No. 4,475,545 to Ender.
Referring to FIG. 1 , a special problem in pediatric orthopedics exists in that reaming through the typical entry point in a femur 10 , i.e., the piriformis fossa 11 , can be too dangerous for the child. This is due to the presence of an artery 12 that supplies blood to the proximal femur. Specifically, this is the lateral epiphyseal artery 12 which is a branch of the femoral artery. If this artery 12 is damaged during the fixation procedure, such as while the intramedullary canal is being reamed to accept a nail, or possibly during insertion or after insertion of the nail, various complications can result. The lateral epiphyseal artery 12 supplies 75% of the blood to the growing femoral head 16 . If this artery 12 is damaged, then much of the femoral head 16 will die or necrose. The femoral head 16 will then heal with an irregular shape which inevitably leads to hip arthritis.
Various nails, such as flexible Rush nails, are non-interlocked meaning that cross fasteners are not used to secure the nail to the bone. These nails are often small diameter rods, on the order of approximately 3-4 mm in diameter. In addition to being flexible to a significant degree prior to plastic deformation, non-interlocked solid nails or rods can be relatively easily bent with plastic deformation to a desired shape. A plurality of these nails or rods are typically driven into the intramedullary canal depending on the support necessitated by the fracture and bone characteristics of the patient. Other more rigid solid or hollow nails are interlocked to the bone using cross fasteners typically at the proximal and distal ends of the nail. Unlike non-interlocked nails, interlocked nails require sufficient cross-sectional dimensions to accommodate holes necessary for the cross fasteners. Currently available interlocked nails can be inserted away from the lateral epiphyseal artery 12 but are so rigid that they migrate during insertion dangerously close to the artery 12 and can endanger it. In addition, the large proximal size of small adult interlocked nails, which have typically been used in children, increases the potential for damage to the growth plate 17 at the proximal femur.
Among possible solutions, retrograde nailing avoids the proximal femur but also has at least one potential problem. The nails must be introduced close to the distal femoral growth plate or physis 19 ( FIG. 5 ) at an awkward angle, potentially causing growth arrest distally on the femur, i.e., adjacent the knee. An approach through the greater trochanter 18 is also well recognized, but usually only one small diameter non-interlocked nail or rod can be used because of the narrow safe entry zone of the greater trochanter. A second small diameter nail or rod needs to be inserted retrograde or through the opposite end of the femur in these situations. These small diameter, flexible nails allow flexure after insertion and the slightly added stress to the bone allowed by this flexure promotes faster bone healing. These non-interlocked nails work well for transverse fractures. However, spiral or comminuted fractures often need additional external support, such as with a cast or brace. This is due to the inability of the non-interlocked nail to effectively prevent rotation or length compromise at the fracture.
It would therefore be desirable to provide an interlocked intramedullary nail, especially suitable for pediatric use, which provides flexibility along a majority of the length of the nail to facilitate faster healing of a fracture, but which also provides for secure interlocking of the nail to the bone with cross fasteners to prevent compromising the fracture due to rotation or shortening at the fracture site. Ideally, such a nail and related methods of insertion would minimize trauma to the growth plates of the femur as well as the arteries that supply blood to the proximal end of the femur while still allowing easy insertion and fixation within the intramedullary canal.
SUMMARY OF THE INVENTION
In one general aspect, the present invention provides an intramedullary nail for insertion within an intramedullary canal of a long bone and fixing a fracture in the long bone. The nail is especially suitable for adolescent or preadolescent aged children, however, the nail may be useful in other orthopedic applications as well. The nail generally comprises an elongate member having a longitudinal axis, a proximal end section, a distal end section and a solid central section extending between the proximal and distal end sections. The proximal and distal end sections respectively have fastener receiving areas of greater cross sectional dimensions than the central section. The fastener receiving areas each include at least one hole extending transverse to the longitudinal axis of the elongate member for receiving a cross fastener adapted to secure to the bone on opposite sides of the elongate member. The proximal and distal end sections provide rigid anchoring locations relative to the central section and the central section provides flexibility to promote healing of the fracture.
In the preferred embodiment, the central section of the elongate member is curved in the sagital plane to generally follow the curvature of a femur. The proximal and distal end sections are bent out of this plane and form acute angles with respect to the sagital plane. The proximal and distal end sections are each bent laterally to one side of the central section. The side to which the proximal and distal end sections are bent depends on whether the nail will be used in a right or left femur and also allows easier insertions across the fracture. The bend of the distal end section allows for easier insertion of the nail from an insertion point extending through the greater trochanter of the femur. The bend of the proximal end section ensures that the proximal tip is presented directly at the insertion point after fixation so that it may be easily accessed for removal purposes upon healing of the bone.
In general, a method of fixing a fracture in a long bone of a patient, in accordance with the invention, includes providing an elongate member having a solid central section with a cross sectional dimension and having proximal and distal fastener receiving areas of increased cross sectional dimension relative to the cross sectional dimension of the central section. The fastener receiving areas each have at least one hole extending transverse to a longitudinal axis of the elongate member. The method involves inserting the elongate member into the intramedullary canal of the long bone through an insertion point and across the fracture and inserting cross fasteners through each of the holes and into the bone on opposite sides of the elongate member to fix the fracture of the long bone against rotational and lengthwise movements.
The bone nail and method of this invention allow the surgeon to better avoid the critical arterial blood supply to the femoral head which crosses at the piriformis fossa, i.e., the traditional point of entry for an adult nail. Instead, the entry point is on the greater trochanter, a location distinctly lateral of the critical region of the piriformis fossa. The very vulnerable growth plate between the greater trochanter and the femoral neck is also avoided using the nail and entry point in accordance with this invention. Another unique feature of the invention is the ability of the bone nail to be flexible, yet custom bent to match the exact geometry of the proximal femur, while also allowing interlocking with cross fasteners. In general, the preferred inventive nail provides interlockability, a relatively small solid cross section to provide flexure along at least the majority of the length of the nail, and malleability to allow custom bending especially at the proximal end.
The features that characterize the invention, both as to organization and method of operation, together with further objects, features and advantages thereof, will be better understood from the following written description taken in conjunction with the accompanying drawings. It is to be expressly understood that the drawings and detailed description thereof are for the purpose of illustration and description and is not intended as a definition of the limits of the invention. These and other objects attained, and advantages offered, by the present invention will become more fully apparent as the description that now follows is read in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a portion of a femur including the femoral head and the greater and lesser trocantic regions.
FIG. 2 is a side elevational view of an intramedullary nail of the present invention shown in the anterior-posterior plane.
FIG. 3 is an elevational view of the nail shown in FIG. 2 , but illustrating proximal and distal bends.
FIG. 4 is an elevational view of the nail shown in FIG. 3 , but rotated 90°.
FIG. 5 is a schematic view of the step of initially inserting the bone nail of FIGS. 3 and 4 into a femur.
FIG. 6 is a schematic view similar to FIG. 5 , but illustrating the nail further inserted across the bone fracture.
FIG. 7 illustrates a drill rig and fastener inserting rig being used to cross fastened the nail after full insertion.
FIG. 8 is a schematic illustration of the fully inserted and cross fastened bone nail.
FIG. 8A is a fragmented, partially sectioned view of the distal end section of the bone nail and the cross fastener of the present invention.
FIG. 9 is an elevational view showing one illustrative bending device being used to bend the proximal end section of the bone nail.
FIG. 10 is an elevational schematic view of another embodiment bone nail according to the present invention fully inserted in the femur.
FIG. 11 is an enlarged view of the distal end portion of the nail of FIG. 10 .
FIG. 12 is a sectional view taken through line 12 - 12 of FIG. 10 .
FIG. 13 is an elevational schematic view of a further embodiment bone nail according to the present invention fully inserted in the femur.
FIG. 14 is an elevational schematic view of yet another embodiment bone nail according to the present invention fully inserted in the femur.
DETAILED DESCRIPTION
An exemplary intramedullary nail 20 , as illustrated in FIGS. 2-4 , comprises an elongate member 22 . In an embodiment intended for use in a femur of a child or adolescent, typically ages 6-14, for example, the nail 20 is formed from titanium and has a generally cylindrical shape with a diameter along a solid central section 24 of between 4 mm and 7 mm, although this is not intended as a limitation. Central section 24 should have a certain amount of elastic flexibility to permit accurate placement within the femoral canal as discussed below. Such elastic flexibility, which permits some flexure during movement and weight bearing activity, confers an additional benefit in that it has been found to stimulate bone healing. The nail 20 preferably ends in a rounded, smooth and tapered distal tip 26 .
The nail 20 has two widened sections or fastener receiving areas 28 , 30 in respective proximal and distal end sections 32 , 34 . Each fastener receiving area 28 , 30 is formed with an increased cross sectional dimension relative to central section 24 . Also, smooth, gradual transitions 36 , 38 with the central section 24 avoid sharp edges along the length of nail 20 . The distal fastener receiving area 28 is positioned adjacent to but in spaced relation from distal tip 26 . The distal fastener receiving area 28 tapers on both proximal and distal sides thereof. The proximal fastener receiving area 30 extends to proximal tip 42 ; that is, there is a distal taper but no proximal taper, and the widened proximal fastener receiving area 30 instead continues to the proximal tip 42 and forms the entire proximal end section 32 .
Each fastener receiving area 28 , 30 includes a generally cylindrical hole 50 , 52 extending generally normal to the portion of the longitudinal axis 54 in which it is located for receiving a fastener (not shown). Holes 50 , 52 preferably have diameters in a range of 3 mm to 4½ mm.
Proximal tip 42 includes attachment structure 58 for receiving a driver, described below, which may be a conventional driver used in the bone nail art. Preferably, attachment structure 58 comprises a threaded axial bore 60 extending along axis 54 and engageable with an externally threaded driver. A notch 62 extends across bore 60 and, as is known, aligns the driver for purposes of later drilling and cross fastening nail 20 , as will be discussed below. As further shown in FIGS. 2 and 4 , nail 20 is curved in an anterior direction along a radius of curvature 70 to generally conform nail 20 to the typical femoral curvature. Preferably, this radius of curvature 70 is in the range of 30 inches to 60 inches. A proximal bend 72 and a distal bend 74 are formed, respectively, in central section 24 directly adjacent proximal and distal end sections 32 , 34 . These bends 72 , 74 are made in the same direction, i.e., laterally to one side of nail 20 or the other as shown best in FIG. 3 . The solid lines in FIG. 3 illustrate lateral bends 72 , 74 out of the sagital plane and generally in the coronal plane at angles A, B for inserting nail 20 into a left femur. Angles A′, B′ corresponding to the respective lateral bends of proximal and distal end sections 32 , 34 , shown in phantom, facilitate use of nail 20 in the right femur. As a unique feature of this invention, interlocking nail 20 may be custom bent by the surgeon just prior to use, not only to facilitate insertion in the right or left femur, but also to accommodate other particular shapes necessary for a particular patient. For example, some patients may have deformities necessitating one or more corrective osteotomies or fractures made by the surgeon. These osteotomies may also be fixed using nail 20 .
In the preferred embodiment, nail 20 is formed from titanium, although other materials such as those known in the art may be used as well. Central section 24 is of solid cross section and at least substantially constant diameter with a smooth outer surface to facilitate removal in 6-9 months. Proximal and distal end sections 32 , 34 are also solid, except for holes 50 , 52 , bore 60 and notch 62 . As appreciated from FIG. 2 , the axes of holes 50 , 52 are coplanar. In order to provide the desired flexibility of central section 24 , while retaining the cross fastening feature of the invention, fastener receiving areas 28 , 30 have a cross sectional dimension greater than the cross sectional dimension of central section 24 . In general, central section 24 may be formed with a solid cylindrical cross section having a diameter of between 4 mm and 7 mm. Fastener receiving area 28 has a generally bulbous, rounded shape, while proximal fastener receiving area 30 , which is preferably continuous with distal end section 32 , has a cylindrical cross sectional shape. At the cross section taken along the axes of respective holes 50 , 52 , the respective ratios of the cross sectional dimensions at these locations is at least about 1.3:1 relative to the cross sectional dimension of central section 24 . In exemplary embodiments of the invention, a nail 20 substantially as shown in FIG. 2 , had a cross sectional dimension of 5.5 mm for central section 24 , an 8.5 mm cross sectional dimension for proximal end section 32 , and also a maximum 8.5 mm cross sectional dimension at the largest diameter portion of distal fastener receiving area 28 . This nail was used on children generally weighing less than 100 lbs. For children weighing more than 100 lbs., the 8.5 mm dimensions at the proximal and distal fastener receiving areas remained the same, while the cross sectional dimension for central section 24 was increased slightly to 6.5 mm to provide additional strength but still provide the desirable flexure.
The insertion and fixation techniques according to the preferred embodiment of the invention are best illustrated in FIGS. 5-8 . In accordance with the invention, an insertion point 80 is created in the greater trochanter 18 of the femur 10 of a child, for example, at a distinctly lateral position relative to the piriformis fossa 11 . Intramedullary canal 10 a of femur 10 is drilled and reamed in a known manner to accept bone nail 20 . A driver 82 is coupled with proximal tip 42 , also in a known manner, and the surgeon impacts the head 84 of the driver 82 while holding the handle portion 86 . Bend 74 facilitates better positioning of distal tip 26 upon insertion of nail 20 by allowing distal tip 26 to naturally follow the intramedullary canal 10 a relative to the angle of the insertion point 80 in the greater trochanter 18 . As shown in FIG. 6 , bone nail 20 may be rotated in either direction represented by arrow 90 as the distal tip 26 approaches and crosses the fracture 92 . This allows the surgeon, using fluoroscopy, to more easily locate and enter the intramedullary canal 10 a of the distal bone segment 94 . After the bone nail 20 is fully inserted, as shown in FIG. 7 , a drill rig 100 is attached to the proximal tip 42 through securement to handle portion 86 . The drill rig 100 aligns a drill guide 102 with the proximal fastener receiving hole 52 and a drill (not shown) is used to form a hole through femur 10 in line with hole 52 . A screw driving mechanism 104 is then used to insert a cross fastener 110 at this location. Using conventional fluoroscopy techniques, a second hole is drilled and a second cross fastener 112 , preferably of the same design as fastener 110 , is inserted through the distal hole 50 , as shown in FIGS. 8 and 8A . More specifically, and as represented by distal fastener 112 in FIG. 8A , fastener 112 comprises a drive head 150 , a proximal threaded portion 152 , a distal threaded portion 154 , and a central unthreaded portion 156 which is received within hole 50 . Threaded portions 152 , 154 are securely engaged within cortical layer 10 b of femur 10 . In this manner, bone nail 20 is interlocked to femur 10 at proximal and distal locations thereby preventing undesirable rotational and/or lengthwise bone movements at the fracture site. In this interlocked or fixed position, proximal tip 42 is presented directly at the insertion point 80 on the greater trochanter 18 so that, upon healing of the fracture, the cross fasteners 110 , 112 may be removed and threaded bore 60 may be engaged to withdraw nail 20 from intramedullary canal 10 a.
Although bends 72 , 74 may be pre-made by a manufacturer of nail 20 , for example, the present invention further contemplates a manual bending device as shown in FIG. 9 . Using this device, nail 20 may be placed by the surgeon in a bending device 118 jaw structure comprising three rollers 120 , 122 , 124 with one roller 120 acting as a fulcrum and two opposite rollers 122 , 124 applying forces in the direction of arrows 130 , 132 . When the handles 134 , 136 of the device are squeezed together in the direction of arrows 138 , 140 , proximal end section 32 will be bent relative to central section 24 to form bend 72 as best illustrated in FIG. 3 and as previously described. The same procedure may be used by the surgeon to bend distal end section 34 just prior to insertion within intramedullary canal 10 a . This aspect of the invention allows the surgeon to custom bend these or other portions of the nail 20 to suit the anatomy and/or needs of a particular patient prior to or during surgery.
Other embodiments for an intramedullary nail for insertion in an intramedullary canal to repair fractures or osteotomies of a long bone are also contemplated. According to one aspect, the nail includes an elongate member having a longitudinal axis, a proximal end section, and a distal end section and a central solid section extending therebetween. The proximal end section includes a fastener receiving portion enlarged relative to the central section and having at least one hole extending therethrough normal to the longitudinal axis. The distal end section includes a fastener receiving portion enlarged relative to the central section.
In one form, the distal fastener receiving portion includes a first hole therethrough normal to the longitudinal axis and a second hole therethrough normal to the longitudinal axis and normal to the first hole. In another form, the distal fastener receiving portion includes a first upper hole therethrough normal to the longitudinal axis and a second lower hole therethrough normal to the longitudinal axis and parallel to the first hole. In yet another form, the distal fastener receiving portion includes at least one hole therethrough normal to the longitudinal axis, and there is at least one middle fastener receiving portion formed along the central solid section between the proximal end section and the distal end section. The middle fastener receiving portion is enlarged relative to the central solid section and has a hole therethrough normal to the longitudinal axis.
Referring now to FIGS. 10-12 , there is illustrated another embodiment intramedullary nail 220 . Nail 220 has structural features and properties that are similar to nail 20 described above; however, nail 220 includes a distal end that allows placement of additional fasteners to provide added stability. While nail 220 has a length that makes it particularly suited for femur 10 having supracondylar fracture or osteotomy 92 , applications for other types of femoral fractures and osteotomies are also contemplated.
Nail 220 includes a central solid section 222 extending between a proximal end section 234 and a distal end section 232 . Except as otherwise provided herein, nail 220 generally has the structural, dimensional and elastic properties discussed above with respect to nail 20 . Nail 220 has two widened sections or fastener receiving areas 228 , 230 in respective distal and proximal end sections 232 , 234 . Smooth gradual transitions are provided between central section 222 and the fastener receiving areas 228 , 230 . Distal fastener receiving area 228 is positioned adjacent to and in spaced relation from distal tip 226 with a distal taper therebetween. The proximal fastener receiving area 230 extends to proximal tip 242 , and can include a tool attachment structure as described above with respect to nail 20 . Nail 220 can be bent and installed into femur 10 in a manner similar to that described above with respect to nail 20 .
Proximal fastener receiving area includes a generally cylindrical hole 252 extending generally normal to the central longitudinal axis 254 . Proximal fastener 264 can be placed through hole 252 . Distal fastener receiving area 228 includes a lower generally cylindrical hole 250 extending normal to central axis 254 , and an upper generally cylindrical hole 251 extending normal to axis 254 and also generally normal to hole 250 , as shown in FIGS. 11 and 12 . Upper distal fastener 260 can be placed through upper hole 251 and lower distal fastener 262 can be placed through lower hole 250 , providing added stability when distal end portion 232 of nail 220 is secured to femur 10 .
Referring now to FIG. 13 , there is illustrated another embodiment bone nail 320 according to the present invention. Nail 320 preferably has a length that is particularly suited for a femur having an intertrochanteric osteotomy 94 , which allows de-rotation of a twisted femur. Nail 320 has an enlarged distal fastener portion for receiving multiple fasteners therethrough. It is also contemplated that nail 320 also has application with other types of femoral fractures and osteotomies.
Nail 320 includes a central solid section 322 , a proximal end section 334 and a distal end section 332 . Except as otherwise provided herein, nail 320 generally has the structural, dimensional and elastic properties discussed above with respect to nail 20 . Nail 320 has two widened sections or fastener receiving areas 328 , 330 in respective distal and proximal end sections 332 , 334 . Smooth gradual transitions are provided between central section 322 and the fastener receiving areas 328 , 330 . Distal fastener receiving area 328 is positioned adjacent to and in spaced relation from distal tip 326 with a distal taper therebetween. The proximal fastener receiving area 330 extends to proximal tip 342 , and can include a tool attachment structure as described above with respect to nail 20 . Nail 320 can be bent and installed in a manner similar to that described above with respect to nail 20 .
Proximal fastener receiving area includes a generally cylindrical hole 352 extending generally normal to the central longitudinal axis 354 . Proximal fastener 364 can be placed through hole 352 . Distal fastener receiving area 328 includes a lower generally cylindrical hole 350 extending normal to central axis 354 , and an upper generally cylindrical hole 351 extending normal to axis 354 and also generally parallel to hole 350 . Upper distal fastener 360 can be placed through upper hole 351 and lower distal fastener 362 can be placed through lower hole 350 , providing added stability to distal end portion 332 of nail 320 secured to femur 10 .
Referring now to FIG. 14 , there is illustrated another embodiment bone nail 420 according to the present invention. Nail 420 is particularly suited for multiple level osteotomies 93 a , 93 b for correction of femoral deformity, or for multiple fractures of the femur. It is also contemplated that nail 420 has application with other types of femoral fractures and osteotomies.
Nail 420 includes a pair of central solid sections 422 , 423 extending from a middle fastener receiving section 429 towards a proximal end section 434 and a distal end section 432 , respectively. Except as otherwise provided herein, nail 420 generally has the structural, dimensional and elastic properties discussed above with respect to nail 20 . Nail 420 has widened sections or fastener receiving areas 428 , 430 in respective distal and proximal end sections 432 , 434 . Nail 420 further has a middle widened fastener receiving area 429 between central sections 422 , 423 . Preferably, central sections 422 , 423 have respective lengths that position middle receiving area 429 between upper osteotomy 93 a and lower osteotomy 93 b . Although the embodiment of FIG. 14 has one middle receiving area 429 , it is contemplated that two or more middle receiving areas could be provided for use in multiple level fractures or osteotomies so that each section of bone has a fastener associated therewith. Smooth gradual transitions are provided between central section 422 , 423 and the fastener receiving areas 428 , 429 , 430 . Distal fastener receiving area 428 is positioned adjacent to and in spaced relation from distal tip 426 with a distal taper therebetween. The proximal fastener receiving area 430 extends to proximal tip 442 , and can include an attachment structure as described above with respect to nail 20 . Nail 420 can be bent and installed in a manner similar to that described above with respect to nail 20 .
Proximal fastener receiving area 430 includes a generally cylindrical hole 452 extending generally normal to the central longitudinal axis 454 . Proximal fastener 464 can be placed through hole 452 . Distal fastener receiving area 428 includes a generally cylindrical hole 450 extending normal to central axis 454 . Middle fastener receiving area 429 includes a generally cylindrical hole 451 extending normal to axis 254 . Middle fastener 460 can be placed through hole 451 and distal fastener 462 can be placed through hole 450 , securing nail 420 to each of the fractured sections of femur 10 .
It may be appreciated by one skilled in the art that additional embodiments may be contemplated, including combinations of the above described embodiments. For example, the dual hole distal end portion of nail 220 , 320 could be used with nail 20 or nail 420 . It is also contemplated that additional embodiment may be similarly designed for nails used to fix fractures in long bones other than the femur in child and adolescent patients. It is also contemplated that similar nails could be used in repair of animal long-bone fractures.
In the foregoing description, certain terms have been used for brevity, clarity and understanding, but no unnecessary limitations are to be implied therefrom beyond the requirements of the prior art, because such words are used for description purposes herein and are intended to be broadly construed. Moreover, the embodiment of the apparatus illustrated and described herein are by way of example, and the scope of the invention is not limited to the exact details of construction illustrated herein.
While the invention has been illustrated and described in detail in the drawings and foregoing description, the same is to be considered as illustrative and not restrictive in character, it being understood that only the preferred embodiments have been shown and described and that all changes and modifications the come within the spirit of the invention are desired to be protected.
|
An intramedullary nail ( 20 ) and related method for fixing a fracture in a long bone. The nail ( 20 ) comprises an elongate member ( 22 ) having a longitudinal axis ( 54 ), a proximal end section ( 32 ), a distal end section ( 34 ) and a solid central section ( 24 ) extending between the proximal and distal end sections ( 32, 34 ). The proximal and distal end sections ( 32, 34 ) respectively include proximal and distal fastener receiving areas ( 28, 30 ) of greater cross sectional dimensions than the central section ( 24 ). Each fastener receiving area ( 28, 30 ) includes at least one hole ( 50, 52 ) extending transverse to the longitudinal axis for receiving a cross fastener ( 110 ) adapted to secure to the bone on opposite sides of the elongate member ( 22 ). The proximal and distal end sections ( 32, 34 ) thereby provide rigid anchoring locations relative to the central section ( 24 ) and the central section provides flexibility to promote healing of the fracture.
| 0
|
BACKGROUND OF INVENTION
1) Field of the Invention
This invention relates to semiconductor devices and more particularly to an improved structure and method for producing electrically programmable read only memory devices (EPROM's) and flash EPROM's devices.
2) Description of the Prior Art
In the last decade, semiconductor memories have been the fastest growing segment of the semiconductor industry, with the large increase due to the rapid growth of digital electronics market with multiplying applications. Moreover, flash electrically programmable read only memories devices (flash EPROM's) are being produced in larger quantities. Lately, high density flash memory has been expected to replace some pan of the large computer external storage device market. One of the goals in the fabrication of flash electrically programmable read only memories (flash EPROM's) is the production of a memory circuit that is capable of storing a maximum amount of information using a minimum amount of semiconductor surface area. However, photolithographic limits imposed by conventional semiconductor processing technology impede the achievement of this goal. Thus, the inability to pattern and etch semiconductor features closed together prevents a memory cell from occupying a smaller portion of a semiconductor's surface. Another goal of flash EPROM manufacturing is use of a simple cheap high yielding process. Many previous methods to reduce device size add too much complexity and cost.
Flash EPROM's frequently use a floating gate avalanche injection metal oxide semiconductor (FAMOS) structure to store information. Floating gate dimensions in a FAMOS memory cell are conventionally established with reference to minimum photolithographic limits and therefore produce undesirable large memory cells. A conventional configuration for an EPROM device is the stacked gate structure as shown in FIG. 1. Source 12 and Drain 14 regions are formed in substrate 10. The floating gate 16 overlies the channel region, the area between the source and drain. The control gate 18 overlays the floating gate 16. An insulating structure 20 insulates the substrate, floating gate and control gate. The minimum size of the conventional stack gate structure is determined by the photolithographic limits which determine the floating gate, control gate, source and drain widths.
A less than optimal solution to this problem of sizing the floating gate at minimum photolithographic limits is provided by the use of a side wall floating gate formed on a sidewall of a control gate. However, since the floating gate is merely added to a sidewall of a photolithographic defined control gate, the resulting structure is actually larger than a structure achievable at minimum photolithographic limits. In addition, it provides an undesirable diminished capacitive coupling between the floating gate and the control gate. Accordingly, a need exists for a memory cell in which a floating gate structure is provided with dimension less than minimum photolithographic limits, but which is not formed on a sidewall of a control gate.
A method of producing an EPROM having sidewall floating gates that seeks to reduce cell size is shown in U.S. Pat. No. 5,143,860. Floating gates are formed on the sidewalls of oxide layers overlying the source and drain regions. A control gate layer overlies two adjacent floating gates. This method produces EPROM cells smaller than that achievable using conventional the photolithographic limited stacked gate structure. However, this cell has the limitation of a small control gate to floating gate contact area which reduces the capacitive coupling which in turn makes the floating gate less responsive to voltage charges from the control gate. More importantly, this method is not the optimal solution and a need for a smaller cell structure still exists.
SUMMARY OF THE INVENTION
A general object of the invention is to provide an improved structure for a flash electrically programmable read only memory device.
A more specific object of the present invention is to provide an improved structure of a flash electrically programmable read only memory device having a dual sidewall floating gate structure.
Yet another more specific object of the present invention is to provide an improved structure of an flash electrically programmable read only memory device having a dual sidewall floating gate structure which reduces the memory cell size, increases the capacitive coupling between the floating gate and the control gate, and reduces manufacturing costs.
In accordance with the above objects, a structure and a method for an improved flash EPROM is provided. A thin insulating layer and then an oxidation resistant masking layer, typically a nitride, are formed on the surface of a semiconductor substrate with a background doping of a first conductivity type. Openings are formed in the masking layer and thick field oxide is grown in the openings. Next, the nitride masking layer is patterned to form nitride lines with vertical sidewalls that will determine the locations of the source regions and the floating gates. Following this, a gate oxide layer and then a conformal polysilicon layer are formed on the substrate surface. The polysilicon layer is anisotropically, etched to form floating gates on the vertical sidewalls of the nitride lines.
Subsequently, the nitride lines are removed. The source and drain regions are formed by ion implantation through space between the field oxide and the floating gates. The photoresist layer is then removed. Now, the substrate is oxidized to thicken the thin insulating layers over the source and drain regions forming a thick insulating layer. A composite insulating layer is formed over portions of the field oxide, the drain, floating gate and source regions. Then, a conductive layer which acts as the control gate, is formed over the composite insulting layer.
Lastly, a dielectric layer is form over the substrate surface. Electrical contacts and metallurgical lines with appropriate passivation are formed that connect the source, drain and gate elements to form an electrically programmable memory device.
BRIEF DESCRIPTION OF THE DRAWINGS
The drawings show the following:
FIG. 1 is cross-sectional views in broken section in greatly enlarged scale that illustrate a stacked gate EPROM fabricated in accordance with the prior an processes
FIGS. 2A, 2B through 9 are a sequence of cross-sectional views in broken section in greatly enlarged scale that illustrate a device structure including dual floating gates in various stages of fabrication in accordance with the process of the invention.
FIGS. 10 and 11 are cross-sectional views taken along axis 10 in FIG. 9.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will be described in detail with reference to the accompanying drawings. It should be noted that the drawings are in greatly simplified form. In practice the memory device structure will be one of many supported on a common substrate connected with suitable metallurgy in various electronic circuit configurations.
Referring now to FIG. 2A, there is shown substrate 10 which shall be a monocrystalline silicon semiconductor body with many devices fabricated therein, as is well known in the art. The substrate 10 is preferable formed of monocrystalline silicon having a surface plane with a crystalline orientation of <1 0 0>. The background substrate dopant is preferably boron with a concentration in the range of 1E14 to 1E16 atoms/cm 3 . Substrate 10, embodies a background doping of a first type conductivity, preferably P-type. For this illustration, the devices will be formed in a P-well 11 in substrate 10. In an alternative, a conventional twin well process can be used wherein nMOS devices can be formed in the wells. This allows both nMOS and pMOS devices to be formed on the same substrate.
Next, a first insulating layer 32 is formed on the surface of the semiconductor substrate, The thin insulating layer 32 is preferably composed of silicon oxide with a thickness in the range of 50 to 300 angstroms and preferably 200 angstroms. Insulating layer 32 can able grown in a dry oxygen or steam environment at a temperature of approximately 900° C. Insulating layer 32 covers the entire surface of the substrate 10.
After the formation of the first insulating layer 32, an oxidation resistant masking layer 34 is formed overlying layer 32. The oxidation resistant masking layer is preferably formed of silicon nitride with a thickness in the range of 1000 to 3000 angstroms and with a thickness more preferably 1500 angstroms. Layer 34 can be formed of silicon nitride layer by reacting silane and ammonia at atmospheric pressure at 700° to 900° C., or by reacting dichlorosilane and ammonia at reduced pressure (LPCVD) at approximately 700° C. Also, silicon nitride can be formed by plasma enhanced chemical vapor deposition (PECVD) by reacting silane with ammonia or nitrogen in a glow discharge between 200° and 350° C.
Next, using standard photolithographic processes, openings in oxidation resistant layer 34 are formed that define the thick field oxide regions 38. Subsequently, thick field oxide regions 38 are formed in the openings that define the field oxide layer. The field oxide layer 38 has a thickness in the range of 3000 to 7000 angstroms and more preferably a thickness of 5000 angstroms. Field oxide layer 38 can be formed by a conventional atmospheric thermal process where water vapor is reacted with the exposed substrate at a temperature in the range of 700° to 1200° C. In the reaction forming the oxide layer 38, a portion of the underlying silicon is consumed. Typically, for a given silicon oxide thickness, the amount of substrate consumed is approximately one half of the oxide thickness. As illustrated in FIG. 2A, this consumption of the silicon substrate forms a depression in substrate surface 10.
As shown on FIG. 2B, following the field oxide growth, a photoresist layer is patterned and etched to form plurality of elongated spaced parallel line pattern 36 on the oxidation resistant masking layer 34 surface. These resist lines 36 are formed between field oxide regions. Layer 34 is anisotrophically etched using resist layer 36 as mask to form a plurality of elongated spaced parallel lines 42 with vertical sidewalls on the thin isolating layer 32. Nitride masking lines 42 have a width in the range of 0.3 to 1.0 microns and a width more preferably 0.5 microns.
At this point an optional threshold voltage implant (V t implant) can be performed. The Vt implant is used to adjust the threshold voltage of the flash cell. As shown in FIG. 3, the first doped regions 46 are formed by ion implantation off ions of a first conductivity type, with an implant energy in the range of 20 to 150 Kev. and dosage in the range of 1E12 to 1E14 atoms/cm 2 . The ion implanted to form first doped regions 46 can be boron or BF 2 ions. Doped regions 46 have an impurity concentration in the range of 1E16 to 1E18 atoms/cm 3 . Doped regions 46 have a depth in the range of 0.25 to 0.7 microns.
Layer 32 is removed using a conventional etch process. As shown in FIG. 4, a tunnel oxide 30 is grown on the substrate surface. Tunnel oxide 30 can be grown with a dry oxidation process at 800° to 1000° C. For flash EPROM fabrication, layer 30 has a thickness in the range of 60 to 120 angstroms and more preferable a thickness of 100 Angstroms. To make an EPROM, layer 30 has a thickness in the range of 150 to 300 Angstroms.
Next, a conformal layer of polycrystalline silicon 44 is formed over the substrate surface. The polycrystalline silicon layer 44 can be deposited by pyrolyzing silane in a low pressure chemical vapor deposition process at approximately 620° C. Polysilicon layer 44 has a thickness in the range of 2000 to 5000 angstroms and preferably a thickness of approximately 4000 angstroms. The thickness of polysilicon layer 44 determines the channel width D2 shown on FIG. 5.
Conformal layer 44 is then anisotropically etched to form dual sidewall floating gates 48, 50. Preferably the conformal polysilicon layer 44 is etched by a commercially available plasma dry etcher with significantly high polysilicon to silicon oxide selectivity and preferably higher than 20 to 1.
Polysilicon floating gates 48,50 have a width in the range of 0.15 to 0.5 angstroms. Also, the thickness of floating gates 48,50 is determined by the thickness of masking lines 42. The shape of the floating gates 48,50 can be controlled by the conformal polysilicon process and the anisotropic etch process. A square shaped floating gate 48,50 can be formed by using a highly conformal polysilicon deposition and a highly anisotropic etch. Polysilicon floating gates 48, 50 can be doped by a conventional phosphorus diffusion using POCl 3 , an in-situ doping process or by ion implantation, of for example phosphorous ions.
Next, optionally, as shown in FIG. 6, a large angle tilt implanted drain 40 (LATID) can be formed. Next, a P-type ion, boron (B) or BF 2 is implanted into the substrate at a large angle tilt from vertical. This implant will form a second doped region 40 which extends under the floating gate 50. Second doped region 40 will improve the punchthrough voltage due to the higher concentration P- region under the floating gates 48, 50.
A large angle tilt implanted drain (LATID) 40 is optionally used to improve punchthrough and to improve program speed if EEPROM or like flash is fabricated. LATID is an optional implant if hot electron programming approach is used, that is if a EEPROM or like flash cell is used. If EEPROM or like flash approach is adopted, that is Fowler-Nordheim tunneling to program, then the LATID formation step may be skipped.
Next, an anisotropic etch with a high nitride to silicon oxide selectivity is used to remove oxidation resistant lines 42.
As shown in FIG. 7, ions of a second conductivity type are implanted into the substrate. A photolithography step is needed before this implantation to block areas inside the array which it is not necessary to implant in order to reduce the contact and connection resistance. This step is called the buried N+ (BN+) step. For this implant, the ions are N-type. This forms a source region 56 in-between the floating gate structures. Also drain regions 54, 58 are formed between the floating gates and the field oxide regions. The source 56 and drain 54, 58 regions are formed by ion implantation with an implant energy in the range of 30 to 80 Kev. and dosage in the range of 1E14 to 1E16 atoms/cm 2 . The ion implanted can be arsenic, phosphorus or antimony ions. The regions 54, 56, 58 have an impurity concentration in the range of 1E19 to 1E21 atoms/cm 3 .
Subsequently, the substrate is oxidized to thicken tunnel oxide layer 30 forming thick insulating layer 34 and also form an oxide layer on the floating gates 48, 50. Layer 34 should have a resulting thickness in the range of 40 to 150 angstroms.
Next, a second insulating layer is formed over the substrate surface. Layer 60 can be formed of any suitable material, but is preferably a composite layer of silicon oxide, silicon nitride and silicon oxide, which is called ONO. The bottom silicon oxide (SiO 2 ) layer is the previously formed oxide layer 34. The middle nitride layer has a thickness in the range of 100 to 200 angstroms. The nitride layer is form by a conventional low pressure chemical vapor deposition process. The top second oxide layer has a thickness in the range of 40 to 150 angstroms. The second oxide layer is formed by a conventional steam oxidation or a high temperature oxidation performed at a temperature of approximately 790° C. and with a LPCVD process.
As can be seen in FIG. 9, a second conformal polycrystalline silicon layer 62 is deposited on the substrate surface. Layer 62 can be doped with POCL 3 . Layer 62 will function as control gates for the device.
Next, a polycide layer 64 is formed over layer 62. Layer 64 will be used to define the word lines. Polycide layer 64 can be formed by applying a refectory metal to polysilicon layer 62, such as chemical vapor depositing (CVD) tungsten silicide, titanium silicide (TiS x ), or cobalt silicide.
As shown in FIGS. 10 and 11, conventional photolithography processes are used to define wordline patterns in polysilicon and polycide layers 62, 64. FIGS. 10 and 11 are taken along axis 10 in FIG. 9. Referring to FIG. 11, a self-aligned etch is used to etch control gate layer 62, insulating layer 60 and floating gate layers 48, 50 to form wordlines 62, 64 and to define the channel width D4, (shown in FIG. 11 ) of the cell.
Finally, conventional finishing steps (not shown in FIGS.) are performed, such as applying approximately 5000 to 8000 angstroms of Boron or Phosphorus doped tetraethoxysilane (TEOS) oxide on the substrate. Next, conventional silicon metal contacts can be formed of aluminum and copper alloys. Then conventional metal interconnections can be formed of titanium and tungsten alloys, for example Ti/TiW/W-plug.
This invention allows a smaller cell size than possible using conventional processes which are limited by photolithography limits. The sidewall formation of the floating gates allows cell size to be determined by the thickness of the polysilicon layer 44 which is smaller than the photolithography minimum dimension of the conventional process. Also, the invention uses fully self-aligning processes to form the source 56, drains 54, 58, floating gate 48, 50 and control gates layer 62. These self-aligning processes allow smaller devices to be formed because of the greater precision over non-self-aligned photolithography processes.
While the invention has been particularly shown and described with reference to the preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made without departing from the spirit and scope of the invention.
|
An improved method and structure for producing electrically programmable read only memory devices (EPROM's) and flash EPROM's having dual sidewall floating gates is provided. A conformal polysilicon layer is formed over a masking line with vertical sidewalls. The conformal layer is anisotrophically etched to form dual floating gates on the sidewalls of the masking line. The masking lines is removed. Source and drain regions are formed in-between and on either side of the dual gates. An insulating layer is formed over the dual gates and substrate surface. A control gate is formed over the dual gates. Word lines and other electrical contracts are formed to complete the EPROM or flash EPROM device.
| 7
|
FIELD OF THE INVENTION
The present invention relates to the purification of a serine proteinase inhibitor, α 1 -proteinase inhibitor.
BACKGROUND OF THE INVENTION
Alpha 1 -Proteinase Inhibitor (α 1 -PI), also known as α 1 -antitrypsin, is a serum glycoprotein with a molecular weight of 52,000. Alpha 1 -PI is synthesized in the liver and is present in the serum at levels between 150 and 350 mg/dl (equivalent to 30-80 μM) when assayed with plasma standards.
Alpha 1 -PI functions in the lungs to inhibit neutrophil elastase, a serine protease, which in large quantities can lead to the destruction of the alveolar walls. In the normal lung, α 1 -PI provides more than 90% of the anti-neutrophil elastase protection in the lower respiratory tract.
Alpha 1 -PI deficiency is an autosomal, recessive hereditary disorder displayed by a large number of allelic variants and has been characterized into an allelic arrangement designated as the protease inhibitor (Pi) system. These alleles have been grouped on the basis of the α 1 -PI levels that occur in the serum of different individuals. Normal individuals have normal serum levels of α 1 -PI (normal individuals have been designated as having a PiMM phenotype). Deficient individuals have serum α 1 -PI levels of less than 35% of the average normal level (these individuals have been designated as having a PiZZ phenotype). Null individuals have undetectable α 1 -PI protein in their serum (these individuals have been designated as having a Pi(null)(null) phenotype).
Alpha 1 -PI deficiency is characterized by low serum (less than 35% of average normal levels) and lung levels of α 1 -PI. These deficient individuals have a high risk of developing panacinar emphysema. This emphysema predominates in individuals who exhibit PiZZ, PiZ(null) and Pi(null) (null) phenotypes. Symptoms of the condition usually manifests in afflicted individuals in the third to fourth decades of life.
The emphysema associated with α 1 -PI deficiency develops as a result of insufficient α 1 -PI concentrations in the lower respiratory tract to inhibit neutrophil elastase, leading to destruction of the connective tissue framework of the lung parenchyma. Individuals with α 1 -PI deficiency have little protection against the neutrophil elastase released by the neutrophils in their lower respiratory tract. This imbalance of protease:protease inhibitor in α 1 -PI deficient individuals results in chronic damage to, and ultimately destruction of the lung parenchyma and alveolar walls.
Individuals with severe α 1 -PI deficiency typically exhibit endogenous serum α 1 -PI levels of less than 50 mg/dl, as determined by commercial standards. Individuals with these low serum α 1 -PI levels have greater than an 80% risk of developing emphysema over a lifetime. It is estimated that at least 40,000 patients in the United States, or 2% of all those with emphysema, have this disease resulting from a defect in the gene coding for α 1 -PI. A deficiency in α 1 -PI represents one of the most common lethal hereditary disorders of Caucasians in the United States and Europe.
Therapy for patients with α 1 -PI deficiency is directed towards replacement or augmentation of α 1 -PI levels in the serum. If serum levels of α 1 -PI are increased, this is expected to lead to higher concentrations in the lungs and thus correct the neutrophil elastase:α 1 -PI imbalance in the lungs and prevent or slow destruction of lung tissue. Studies of normal and α 1 -PI deficient populations have suggested that the minimum protective serum α 1 -PI levels are 80 mg/dl or 11 μM (about 57 mg/dl; using pure standards). Consequently, most augmentation therapy in α 1 -PI deficient patients is aimed toward providing the minimum protective serum level of α 1 -PI, since serum α 1 -PI is the source of alveolar α 1 -PI.
Alpha 1 -PI preparations have been available for therapeutic use since the mid 1980's. The major use has been augmentation (replacement) therapy for congenital α 1 -PI deficiency. The half-live of human α 1 -PI in vivo is 4.38 days with a standard deviation of 1.27 days. The currently recommended dosage of 60 mg α 1 -PI/kg body weight weekly will restore low serum levels of α 1 -PI to levels above the protective threshold level of 11 μM or 80 mg/dl.
Previously α 1 -PI has been purified by various techniques. One such process combined chromatography on an anion-exchange chromatography medium followed by PEG precipitation. Other purification procedures have used PEG precipitation followed by anion-exchange chromatography and others have used multiple PEG precipitation steps followed by anion-exchange chromatography. Still other methods have used phase separation techniques to purify α 1 -PI. Specific activities of 1.26 units/mg have been reported for purified α 1 -PI.
SUMMARY OF THE INVENTION
The present invention is directed to a process for purifying a,-proteinase inhibitor. The process comprises providing an impure protein fraction which comprises α 1 -proteinase inhibitor. The impure protein fraction is precipitated with a precipitant comprising PEG. In a preferred embodiment the precipitant further comprises ZnCl 2 . The supernatant from the PEG precipitation, which comprises α 1 -proteinase inhibitor is collected and applied to an anion-exchange medium. A fraction comprising α 1 -proteinase inhibitor is recovered from the anion-exchange medium and applied to a metal chelate medium. A fraction comprising α 1 -proteinase inhibitor is then recovered from the metal chelate medium. In a preferred embodiment the fraction comprising α 1 -proteinase inhibitor recovered from the metal chelate medium is further purified by chromatography on a second ion-exchange medium.
Alpha 1 -proteinase inhibitor purified by the process has a specific activity greater than 0.6 units/mg.
DETAILED DESCRIPTION
The present invention describes a purification process for the purification of α 1 -PI. This purification procedure uses a unique combination of known purification steps to produce a high specific activity α 1 -PI preparation.
Alpha 1 -Proteinase Inhibitor Purification
Alpha 1 -PI is purified from an impure protein fraction. The impure protein fraction may be plasma, α 1 -PI produced by recombinant methods or any other source comprising α 1 -PI protein. In a preferred embodiment α 1 -PI is prepared from frozen plasma. The plasma is thawed and the Cohn IV 1 +IV 4 fraction is prepared. The preparation of the Cohn IV 1 +IV 4 fraction (the Cohn IV 1 +IV 4 precipitate) is well known in the art and is described briefly here.
Preparation of IV 1 +IV 4 Fraction
Plasma is maintained at a temperature of 1.5° C. ±1.5° C. and the pH is adjusted to 7±0.2 with either sodium bicarbonate or acetate buffer, pH 4.0. Sufficient cold SD3A ethanol (95% v/v ethanol and 5% v/v methanol) is added to bring the plasma to a final alcohol concentration of 8% v/v. During the alcohol addition the temperature of the plasma is lowered to −2° C.±1° C. The precipitate which forms is removed by centrifugation in a Sharples or Westphalia centrifuge or by filtration through a filter press, at −2° C.±1° C. The result precipitate and supernatant are designated the Fraction I precipitate and supernatant.
The Fraction I supernatant is adjusted to pH 6.9±0.1 by the addition of pH 4 acetate buffer (0.8 M sodium acetate adjusted to pH 4 with acetic acid) and is brought to 20% v/v alcohol by the addition of cold SD3A alcohol. During the alcohol addition the temperature is lowered to −5.5° C.±1.5° C. The precipitate which forms is removed by centrifugation in a Sharples or Westphalia centrifuge or by filtration through a filter press, at −5.5° C.±1.5° C. The result precipitate and supernatant are designated the Fraction II+III precipitate and supernatant.
If required, the Fraction II+III supernatant is filtered through a 5 to 30 micron filter to remove particulate matter.
In one embodiment of the present invention, Antithrombin III (AT-III) Poor Fraction II and III is prepared as follows.
Heparin immobilized medium is equilibrated with 10 mM ±5 mM sodium citrate, pH 6.5-7.5 and then 10 mM±5 mM sodium citrate, pH 6.5-7.5, 150 mM±50 mM NaCl, 20% w/v SD3A alcohol. The medium is equilibrated in a −4° C. to −7° C. environment until the effluent is −4° C. to −7° C.
The Fraction II+III supernatant is passed through the heparin immobilized medium packed in a column. The medium adsorbed AT-III is washed with 10 mM ±5 mM sodium citrate, 150 mM ±50 mM NaCl, 2% w/v SD3A alcohol pH 6.5-7.5. The AT-III-poor effluent and the wash effluent are pooled and processed further.
Alternatively, the plasma suspension containing 8% v/v alcohol, at −2° C.±1° C., pH 7±0.2 described above is adjusted to pH 6.9±0.1 by the addition of pH 4 acetate buffer, and is then processed further without the removal of the precipitate. The alcohol concentration is raised to 20% v/v by the addition of cold SD3A alcohol and the temperature is gradually lowered to −5.5° C.±1.5° C. The precipitate which forms is removed by centrifugation in a Sharples or Westphalia centrifuge or by filtration through a filter press, at −5.5° C.±1.5° C. The resultant precipitate and supernatant are designated the Fraction I+II+III precipitate and supernatant.
The Fraction II+III, the Fraction II+III, AT-III poor and/or the Fraction I+II+III supernatant is/are maintained at −5.5° C.±1.5° C. and the pH is adjusted to 5.2±0.1 by the addition of pH 4 acetate buffer.
The resultant suspension is allowed to settle for at least 6 hours at −5.5° C.±1.5° C., after which time the pH is adjusted to 5.8±0.1 with either sodium acetate, pH 4.0 or sodium bicarbonate buffer, pH 4.0. The alcohol concentration is adjusted to 40% v/v by the addition of cold SD3A alcohol. The precipitate which forms is removed by centrifugation in a Sharples or Westphalia centrifuge or by filtration through a filter press, at −5.5° C.±1.5° C. The result precipitate and supernatant are designated the Fraction IV 1 +IV 4 precipitate and supernatant. The Fraction IV 1 +IV 4 precipitate is further purified for production of α 1 -PI.
The Fraction IV 1 +IV 4 precipitate may be frozen until processed further or until sufficient material has been accumulated for further processing.
PEG/ZnCl 2 Precipitation
The IV 1 +IV 4 precipitate is resuspended in water for injection (WFI), in a ratio of about 3 to 10 parts of water per part of IV 1 +IV 4 precipitate, at about 0° to 10° C. and the pH is adjusted to 8.5±0.5 (the Water Extract). After the precipitate is resuspended solid Tris is added to a final concentration of 10±5 mM and NaCl (5±0.5 M) is added to a final concentration of 150±20 mM. Polyethylene glycol 3350 (PEG) and ZnCl 2 are added to a final concentration of 15±7.5% w/w PEG and 0.5±0.25 mM ZnCl 2 . The suspension is adjusted to pH 8±1 and mixed for about one hour.
The PEG/ZnCl 2 precipitate which forms is removed by passing the suspension through a filter press at 0° C.−10° C. The filter press is washed before and after filtering with 150±25 mM NaCl, 15±7.5% w/w PEG and 5±5 mM ZnCl 2 , pH 8±1. Alternatively, the precipitate may be removed by centrifugation at about 6,000 rpm for 10-15 minutes.
ZnCl 2 Precipitation
ZnCl 2 (100±10 mM) is added to the supernatant (the 15% PEG-ZnCl 2 supernatant) to a final concentration of 10 ±5 mM and the solution is adjusted to pH 8±1. The solution is mixed for about one hour. The ZnCl 2 precipitate which forms is recovered by centrifugation, filter press, or other suitable method of recovery. The precipitate may be frozen for future processing.
For further processing the ZnCl 2 precipitate (the 10 mM ZnCl 2 precipitate) is re-solubilized in about 50 mM EDTA and adjusted to a conductivity of not more than 5 mS and to a pH of 8±1.
Anion-Exchange Chromatography
The re-solubilized ZnCl 2 precipitate is then applied to diethyl(2-hydroxpropyl)aminoethyl (QAE) chromatography medium or other similar anion-exchange medium. Either batch or column chromatography may be used. The medium is equilibrated at 0°-10° C. with cold water for injection (CWFI), prior to absorption of α 1 -PI to the chromatography medium. After α 1 -PI has been absorbed onto the medium it is washed with 50±25 mM NaCl, 10±5 mM sodium phosphate, pH 8±1 to remove unbound material. Alpha 1 -PI is then eluted from the anion-exchange chromatography medium with 150±50 mM NaCl, 10±5 mM sodium phosphate, pH 8±1. The eluate which includes α 1 -PI (the 1st QAE Eluate) is collected for further processing.
After the removal of α 1 -PI, the anion-exchange medium is cleaned by washing with, in sequence: 2±0.2 M NaCl, 10±5 mM sodium phosphate, pH 8±1; WFI or 500 mM NaOH; WFI. The chromatography medium is then stored in either 2±0.2 M NaCl, 10±5 mM sodium phosphate, pH 8±1 or 50 mM NaOH until required.
SD Treatment
The anion-exchange medium eluate is concentrated/diafiltered by ultrafiltration against 150±25 mM NaCl, 50±10 mM sodium phosphate, 1±0.1 mM imidazole, pH 7.5±1 to concentrate the α 1 -PI and to remove EDTA which co-elutes from the anion-exchange chromatography medium with the α 1 -PI, to form the 10K UF.
A solution of 10±1% w/v polysorbital 80 and 3±0.3% w/v tri-n-butyl phosphate is added to the diafiltered α 1 -PI to a final concentration of 1±0.5% w/v polysorbital 80 and 0.3±0.15% w/v tri-n-butyl phosphate. The solution is then incubated at 27°±3° C., pH 8±1 for 6.5±0.5 hours to inactivate any viruses which may be present in the α 1 -PI. After the incubation the treated α 1 -PI solution is cooled to 0°-10° C. and, if necessary, the pH is adjusted to 7.5±1. In other embodiments of the present invention the SD treatment is performed after ultrafiltration, as described below or the SD treatment may be performed at this step as well as at the step described below.
Metal Chelate Chromatography
The α 1 -PI is then applied to a copper, zinc or similar metal ion primed medium, such as MATREX-CELLUFINE CHELATE (supplied by Chisso of Japan), at 0°-10° C. Prior to use the medium is washed with, in sequence: WFI; 6±0.6 mg/ml CuSO 4 .5H 2 O; WFI and 150±25 mM NaCl, 250±25 mM sodium acetate, pH 5±1. The resin is then equilibrated with 150±25 mM NaCl, 50±10 mM sodium phosphate, 1±0.1 mM imidazole, pH 7.5±1 at 0°-10° C. Either batch or column chromatography can be used. The SD treated fraction is applied to the metal chelate chromatography medium to absorb α 1 -PI to the metal chelate chromatography medium. The α 1 -PI absorbed medium is washed with 500±50 mM NaCl, 50±10 mM sodium phosphate, 1±0.1 mM imidazole, pH 7.5±1 to remove any unbound material from the chromatography medium. The α 1 -PI is eluted with 150 ±25 mM NaCl, 50±10 mM sodium phosphate, 5±2.5 mM imidazole, pH 7.5±1. The α 1 -PI containing eluate (the Cu ++ Eluate) is collected and may be frozen until processed further.
The chromatography medium is cleaned with, and may be stored in, 500±50 mM NaCl, 50±25 mM EDTA, pH 7±1 or the medium may be washed with CWFI and cleaned with 500 mM NaOH and stored in 50 mM NaOH.
Ultrafiltration
The α 1 -PI containing eluate is ultrafiltered using a high (100,000) molecular weight cut-off ultrafiltration membrane, to remove high molecular weight contaminants and any viral contaminants which may be present in the metal chelate medium eluate.
The filtrate is collected and concentrated/diafiltered by ultrafiltration against 50±25 mM NaCl, 10±5 mM sodium phosphate, pH 8±1, containing up to 20 mM EDTA, to form the 100K UF.
SD Treatment
A solution of 10±1% w/v polysorbital 80 and 3±0.3% w/v tri-n-butyl phosphate is added to the diafiltered α 1 -PI to a final concentration of 1±0.5% w/v polysorbital 80 and 0.3±0.15% w/v tri-n-butyl phosphate. The solution is then incubated at 27°±3° C., pH 8±1 for 6.5±0.5 hours to inactivate any viruses which may be present in the α 1 -PI. After the incubation the treated α 1 -PI solution is cooled to 0°-10° C. and, if necessary, the pH is adjusted to 7.5±1.
Anion-Exchange Chromatography
The concentrated α 1 -PI is then applied to QAE chromatography medium or other similar anion-exchange medium, equilibrated at 0°-10° C. with CWFI, as described above. The chromatograph medium is then washed with 50±25 mM NaCl, 10±5 mM sodium phosphate, pH 8±1. Alpha 1 -PI is eluted from the anion-exchange medium with 150±50 mM NaCl, 10±5 mM sodium phosphate, pH 8±1. The eluate (the 2nd QAE Eluate) is collected and its pH adjusted to 7.5±1. The eluate may be frozen until processed further. If necessary the eluate is concentrated by ultrafiltration.
The α 1 -PI is filtered through a 5 micron filter to remove any particulate matter. The concentration of the α 1 -PI is adjusted to a desired level and the α 1 -PI is sterile filtered through a 0.22 micron filter, dispensed into vials and lyophilized (the 5μ Filtrate).
The lyophilized α 1 -PI is redissolved in sterile water for injection for administration to patients (the Final Container).
Alpha 1 -PI is stored at 2-8° C.
Alpha 1 -PI Activity Assays
A chromogenic assay is used to detect α 1 -PI activity. The assay utilizes a trypsin sensitive chromogenic substrate which releases p-nitroaniline in the presence of trypsin (supplied by Sigma Chemical Co. of St Louis, Mo.). The p-nitroaniline released is detected at 405 nm. α 1 -PI inhibits the release of p-nitroaniline from the substrate. The activity of α 1 -PI in the product can be determined by reference to a standard α 1 -PI activity curve.
Protein Content
Protein content is determined by a Bio-Rad® assay method utilizing differential color change of a Coomassie Blue dye in response to various concentrations of protein measured at 595 nm. The protein content is calculated from a standard curve.
Administration
Alpha 1 -PI is infused into a patient at a rate of about 0.08 ml/kg body weight per minute for the first 10 minutes. If the patient does not experience any discomfort, the rate is increased as tolerated. If tolerated, subsequent infusions to the same patient may be at the higher rate. If adverse events occur, the rate should be reduced or the infusion interrupted until the symptoms subside. The infusion may then be resumed at a rate which is tolerated by the patient.
If large doses are to be administered, several reconstituted vials of α 1 -PI may be pooled in an empty, sterile I.V. infusion container using aseptic technique.
EXAMPLE 1
Purification of Alpha 1 -PI
Twenty kg of IV 1 +IV 4 precipitate was resuspended in 180 kg of WFI at 3.8° C. and the pH was adjusted to 8.94. After the precipitate was resuspended 242.3 g of Tris, 6.7 kg of 1 M NaCl, and 35.4 kg of PEG were added and the solution mixed for 60 minutes. Then 2.2 kg of 100 mM ZnCl 2 was added and the suspension was adjusted to pH 7.92 and mixed for an additional 60 minutes at 0-8° C.
The PEG/ZnCl 2 precipitate which formed was removed by passing the suspension through a filter press at 0-8° C. after the addition of 977 g of filtra-Cell BH 20 filter Aid (supplied by Celite of Germany). The filter press was washed before and after filtering with 30 kg of 150 mM NaCl, 15% w/w PEG, 0.5 mM ZnCl 2 , pH 8.0.
27.8 kg of 100 mM ZnCl 2 was added to the supernatant and the solution was adjusted to pH 8. The precipitate which formed in the presence of the ZnCl 2 was recovered by centrifugation in a Sharples centrifuge. The ZnCl 2 precipitate was re-solubilized in 20 kg of 50 mM EDTA and adjusted to a conductivity of 6.48 mS and to a pH of 7.97.
The re-solubilized ZnCl 2 precipitate was then applied to diethyl(2-hydroxpropyl)aminoethyl (QAE) chromatography medium (supplied by Toso Haas) packed into a 20 l column with an internal diameter of 250 cm. The QAE medium was equilibrated at 4° C. with CWFI. The α 1 -PI was then absorbed into the chromatography medium. The chromatograph medium was then washed with 60 l of 50 mM NaCl, 10 mM sodium phosphate, pH 7.92. Alpha 1 -PI was eluted from the anion-exchange medium with 60 l of 150 mM NaCl, 10 mM sodium phosphate, pH 8.06. The flow rate of the column was maintained at 600 ml/minute. The α 1 -PI containing eluate was collected.
The anion-exchange medium eluate was concentrated/diafiltered by ultrafiltration in a Millipore PELLICON unit (supplied by Millipore of Bedford Mass.) against 150 mM NaCl, 50 mM sodium phosphate, 1 mM imidazole, pH 7.5 to concentrate the α 1 -PI and to remove EDTA which co-elutes with the α 1 -PI.
1.1 kg of a solution of 10% w/v polysorbital 80 and 3% w/v tri-n-butyl phosphate was added to the diafiltered α 1 -PI and the solution was incubated at 25° C. for 1 hour to inactivate any viral contaminants present in the diafiltered α 1 -PI. The solution was then cooled to 4° C. and the pH adjusted to 7.33.
The α 1 -PI was then applied to 10 l of MATREX CELLUFINE CHELATE, a copper chelating medium (supplied by Chisso of Japan) at 4° C. Prior to use the medium was washed with, in sequence: WFI; 6 mg/ml CuSO 4 .5H 2 O; WFI and 150 mM NaCl, 250 mM sodium acetate, pH 5. The column was then equilibrated with 150 mM NaCl, 50 mM sodium phosphate, 1 mM imidazole, pH 7.5 at 4° C. The α 1 -PI absorbed medium was washed with 100 l of 500 mM NaCl, 50 mM sodium phosphate, 1 mM imidazole, pH 7.52 to remove any unbound material from the medium. The α 1 -PI bound to the chromatography medium was eluted with 150 mM NaCl, 50 mM sodium phosphate, 5 mM imidazole, pH 7.47. The flow rate was maintained at about 550 ml/minute. The α 1 -PI containing eluate was collected.
The eluate was ultrafiltered using a 100K CENTRASETTE supplied by Filtron. The filtrate was collected and concentrated/diafiltered by ultrafiltration in a Millipore PELLICON filtration unit against 50 mM NaCl, 20 mM EDTA, 10 mM sodium phosphate, pH 7.9.
The concentrated α 1 -PI was again applied to 5l of QAE chromatography medium, equilibrated at 0°-10° C. with CWFI, to absorb α 1 -PI to the chromatography medium. The chromatograph medium was then washed with 24l of 50 mM NaCl, 10 mM sodium phosphate, pH 8. Alpha 1 -PI was eluted from the chromatography medium with 150 mM NaCl, 10 mM sodium phosphate, pH 8. The pH of the eluate was adjusted to 7.5. The eluate was concentrated/diafiltered by ultrafiltration in a Millipore PELLICON filtration unit against 50 mM NaCl, 10 mM sodium phosphate, pH 7.9.
Throughout the purification, aliquots of the α 1 -PI containing solutions were collected and analyzed. The results are summarized in Table I.
TABLE I
α 1 -PI
Specific
Activity
A 280 nm
U A 280 nm
Activity
Sample
(%)
(kg)
(%)
(U/mg)
Water
3,460
31.3
156,500
0.022
Extract
(100)
(5,000)
(100)
15% PEG-ZnCl 2
2,478
5.22
26,507
0.093
Supernatant
(72)
(5,078)
(17)
10 mM ZnCl 2
2,322
7.72
27,792
0.084
Precipitate
(67)
(3,600)
(18)
1st QAE
1,612
3.95
11,882
0.136
Eluate
(47)
(3,008)
(8)
10 K UF
1,764
19.5
11,720
0.151
(51)
(601)
(7)
Cu ++ Eluate
1,445
1.08
3,521
0.443
(42)
(3,261)
(2)
100 K UF
1,371
0.59
3,184
0.431
(40)
(5,396)
(2)
10 K UF
1,406
5.98
3,007
0.467
(41)
(503)
(2)
2nd QAE
1,181
2.13
1,787
0.661
Eluate
(34)
(839)
(1)
The purification procedure produced a final α 1 -PI fraction with a specific activity of 0.661 U/mg and a yield of 34%.
Example 2
The purification procedure described in Example 1 was repeated except the α 1 -PI was filtered through a 0.22 micron filter. The filtrate was then dispensed into sterile vials and lyophilized.
The results are summarized in Table II.
TABLE II
α 1 -PI
Specific
Activity
A 280 nm
U A 280 nm
Activity
Sample
(%)
(kg)
(%)
(U/mg)
Water
75,800
16.8
3,360,000
0.023
Extract
(100)
(200)
(100)
15% PEG-ZnCl 2
45,713
1.58
394,684
0.116
Supernatant
(60)
(249.8)
(12)
10 mM ZnCl 2
30,995
9.03
301,602
0.103
Precipitate
(41)
(33.4)
(9)
1st QAE
36,762
1.87
112,574
0.327
Eluate
(49)
(60.2)
(3)
10 K UF
26,938
11.34
109,998
0.336
(49)
(9.7)
(3)
After S/D
34,906
11.81
127,548
0.274
Treatment
(46)
(10.8)
(4)
Cu ++ Eluate
23,435
0.76
45,904
0.510
(31)
(60.4)
(1)
100 K UF
21,952
0.45
40,320
0.545
(29)
(89.6)
(1)
10 K UF
21,859
3.43
37,696
0.580
(29)
(10.99)
(1)
2nd QAE
10,270
1.14
21,204
0.909
Eluate
(25)
(18.6)
(1)
10 K UF
24,461
10.99
26,926
0.909
(32)
(2.45)
(1)
5μ
21,648
10.94
27,109
0.799
Filtration
(29)
(2.478)
(1)
Final
17,850
11.02
23,142
0.773
Container
(24)
(2.1)
(1)
The purification procedure produced a final α 1 -PI fraction with a specific activity of 0.773 U/mg and a yield of 24%.
Example 3
Stability of the Purified Alpha 1 -PI
Final container samples of α 1 -PI were stored in temperature controlled incubators at 5° C. After three months, storage samples were analyzed and compared to samples analyzed prior to storage. After reconstitution, the samples were incubated at 20° C. for 0, 2 or 4 hours prior to analysis. Results for storage at 5° C. for 0 and 3 months are summarized in Table III.
TABLE III
Months of storage at 5° C.
Test Description
0
3
α 1 -PI activity
205
U/vial
203
U/vial
α 1 -PI Activity after reconstitution:
0 hours
213
U/vial
203
U/vial
2 hours
223
U/vial
210
U/vial
4 hours
188
U/vial
208
U/vial
Elastase inhibitory activity
after reconstitution
0 hours
323
U/vial
323
U/vial
2 hours
305
U/vial
298
U/vial
4 hours
318
U/vial
308
U/vial
Protein content
0.440
g/vial
0.453
g/vial
Physical
Appearance
Pass
Pass
Moisture
0.50% w/w
0.37% w/w
Solubility
1 minute
1 minute
Vacuum
Present
Present
After 3 months of storage at 5° C., samples of α 1 -PI retained 99% of their original activity. At manufacture, α 1 -PI activity of samples at 0, 2 or 4 hours after reconstitution was 213, 223, and 188 U/vial, respectively. Following storage at 5° C. for 3 months the α 1 -PI activity following reconstitution was 203, 210, and 208 U/vial at 0, 2 and 4 hours, respectively.
Elastase inhibitory activity was also measured following reconstitution of the samples. At the time of manufacture, elastase inhibitory activity at 0, 2 or 4 hours after reconstitution was 323, 305, and 318 U/vial, respectively. Following storage for 3 months at 5° C., the elastase inhibitory activity was 323, 298, and 308 U/vial at 0, 2 or 4 hours after reconstitution, respectively.
Moisture content of the α 1 -PI sample at manufacture was 0.50% and after 3 months of storage at 5° C. it was 0.37%.
Further experiments have shown that alpha 1 -PI remains stable for at least 9 months following storage at 5° C. Samples stored at 5° C. retained 99% of their original α 1 -PI activity.
Example 4
Comparison of α 1 -PI and Commercially Available α 1 -PI
α 1 -PI prepared in Example 2 was analyzed and compared to commercially available α 1 -PI obtained from the Cutter Biological division of Miles, Inc. The protein composition of the samples were analyzed by radial immunodiffusion.
TABLE IV
α 1 -PI prepared
Cutter
Cutter
in Example 2
01J081 mg/
01K047 mg/ml
Protein
mg/ml (% Total)
ml (% Total)
(% Total)
Major Proteins
α 1 -PI
23.80 (95)
29.19 (91)
35.14 (91)
Haptoglobin
1.13 (5)
0.60 (2)
0.68 (2)
Albumin
<0.50
1.53 (5)
2.27 (6)
IgA
<0.01
0.92 (3)
0.90 (2)
Minor Proteins
α 1 -Antichymotrypsin
<0.171
<0.171
<0.171
α 2 -Antiplasmin
0.041
0.083
0.106
α 2 -Macroglobulin
<0.50
<0.50
<0.50
Antithrombin III
<0.060
0.192
0.35
Apolipoprotein A1
0.06
0.21
0.17
Apoliprotein B
<0.095
<0.095
<0.095
C1-Inactivator
<0.045
0.091
0.101
Ceruloplasmin
<0.100
<0.100
<0.100
HMW Kininogen
0.009
<0.001
<0.001
IgG
<0.020
<0.020
<0.020
Prealbumin
0.05
<0.05
<0.05
Protein-C
<0.00125
<0.00125
<0.00125
Protein-S
<0.001
<0.001
<0.001
Transferrin
<0.50
<0.50
<0.50
% Total = Percent of the Major Immunologically-Detected Plasma Proteins
Example 5
In Vivo Use of Alpha 1 -PI
A group of three rabbits was administered α 1 -PI intravenously over a period of approximately one minute at a dose of 240 mg/kg of body weight (4 times the clinical dose of 60 mg/kg of body weight). A control rabbit was injected with 2.73 ml/kg body weight of 750 mM NaCl, 50 mM sodium phosphate, pH 7.5, over a period of one minute. Clinical observations were recorded immediately after administration and again at 30 and 72 hours after administration. Body weights were recorded prior to infusion and at the end of the infusion. A gross necropsy was performed on all animals at the completion of the study.
Clinical signs observed in the α 1 -PI-treated group included decreased activity and dyspnea. There was no apparent effect on mean body weight of the animals in any group during this study. None of the rabbits died in the α 1 -PI-treated groups when a dose equivalent to 240 mg α 1 -PI/kg of body weight (4 times the clinical dose of 60 mg/kg of body weight) was given. Furthermore, no visible lesions were observed in any of the animals at terminal necropsy.
Alpha 1 -PI was non-toxic when administered intravenously at a dose of 240 mg/kg of body weight (4 times the clinical dose of 60 mg/kg of body weight).
Example 6
In Vivo Use of Alpha 1 -PI
A group of three mice were administered α 1 -PI intravenously over a period of approximately one minute at a dose of 1500 mg/kg of body weight (25 times the clinical dose of 60 mg/kg of body weight). A group of three control mice were injected with 17.0 ml/kg of body weight, 750 mM NaCl, 50 mM sodium phosphate pH 7.5, over a period of one minute. Clinical observations were recorded immediately after dosing and again at 24, 48 and 72 hours. Body weights were recorded prior to the infusion and at the end of the infusion. A gross necropsy was performed on all animals at the completion of the study.
The only clinical sign observed was decreased activity. There was no apparent effect on mean body weight of the animals during this study. None of the mice died when a dose of equivalent to 1,500 mg α 1 -PI/kg of body weight (25 times the clinical dose of 60 mg/kg of body weight) was given. Furthermore, no visible lesions were observed in any of the animals at terminal necropsy.
Based upon the results from the acute intravenous toxicity study in mice, α 1 -PI was found to be non-toxic when administered intravenously at 1,500 mg/kg of body weight (25 times the clinical dose of 60 mg/kg of body weight).
Example 7
In Vivo Use of Alpha 1 -PI
A rabbit study lasting 33 days was designed to evaluate the potential toxic effect(s) associated with repeated intravenous exposure to α 1 -PI. For this study, five consecutive daily injections at twice the anticipated clinical dose of 60 mg/kg of body weight were administered. Preliminary hematological, clinical, biochemical, and gross necropsy data obtained from animals at day 6 and day 33 after the fifth repeated intravenous infusion of α 1 -PI were obtained. Alpha 1 -PI was prepared by reconstitution of lyophilized powder with 5 ml Sterile Water for Injection to a concentration of 88 mg α 1 -PI/ml. A 5X buffer (750 mM NaCl, 50 mM sodium phosphate, pH 7.5) containing a concentration of salt similar to that within the reconstituted test-article served as the control. Male and female Albino New Zealand White rabbits (2.0 to 3.0 kg) were used as the test and control recipients.
Twelve (12) rabbits were administered intravenous equivalent-volume injections of either a 5X buffer (6 animals) or α 1 -PI (6 animals) at a dose of 120 mg (1.4 ml)/kg. Infusions of the 5X buffer and α 1 -PI were repeated daily for five consecutive days. The animals were separated into two sex-matched groups of six animals, three received control solution and three received the α 1 -PI solution. Each group of six animals were evaluated at day 6 and day 33 after commencement of the infusions. Following each infusion, all rabbits were observed at 30 and 60 minutes, then hourly for four hours. After the last infusion, the animals were monitored daily for pharmacotoxic signs and mortality.
Repeated administration of α 1 -PI at 120 mg/kg of body weight (two-times the clinical dose of 60 mg/kg of body weight) or an equal volume of 5X buffer control for five consecutive days, resulted in no significant perturbations in hematologic, clinical or biochemical parameters among rabbits examined at day 6 or day 33 after administration of the final dose.
The present invention is not limited to the specific embodiment given. It will be obvious to one skilled in the art that variations, such as variations in buffer concentration and types of buffers and salts, could also be used. Therefore, the present invention is not intended to be limited to the working embodiments described above. The scope of the invention is defined in the following claims.
|
The present invention is directed to a process for purifying α 1 -proteinase inhibitor. The process comprises providing an impure protein fraction which comprises α 1 -proteinase inhibitor. The impure protein fraction is precipitated with a precipitant comprising PEG. The supernatant from the PEG precipitation, which comprises α 1 -proteinase inhibitor, is collected and applied to an anion-exchange medium. A fraction comprising α 1 -proteinase inhibitor is recovered from the anion-exchange medium and applied to a metal chelate medium. A fraction comprising α 1 -proteinase inhibitor is then recovered from the metal chelate medium. Alpha 1 -proteinase inhibitor purified by the process has a specific activity greater than 0.6 units/mg.
| 2
|
FIELD OF INVENTION
The present invention relates to a microwave-actuated ultraviolet (UV) sterilizer for sterilizing or disinfecting articles. More particularly, the invention relates to such a sterilizer for home use which is suitable for readily sterilizing food items, baby bottles, contact lenses and the like.
BACKGROUND ART
Typically, people with weakened or impaired immune systems must disinfect or even sterilize their food and other items which will be ingested or which may otherwise transmit micro-organisms to their bodies. (In this application, "sterilization" includes "disinfection," i.e., "sterilization" means "sterilization or disinfection.") To surface sterilize articles such as baby bottles and contact lenses, the article usually is immersed in a solution or boiled. However, these methods are unsuitable for sterilization of an article which is heat labile or which must be frequently sterilized, since this immersion in liquids or boiling requires a relatively long time for effective sterilization. Therefore, a sterilization process which is quick and which does not involve substantial heating is desirable, so that it may be used with food such as fruit and vegetables.
The surface-sterilizing property of UV light has been described in the patent literature (see, for example, U.S. Pat. No. 2,407,379, issued Sep. 10, 1946). This patent describes a UV lamp for surface sterilization and general bactericidal use.
The concept of using UV light for surface sterilization is well known. For example, U.S. Pat. No. 4,803,364 (issued Feb. 7, 1989), describes a toothbrush conditioner which comprises a housing for a toothbrush and a UV light source inside. One places the toothbrush within a conditioning chamber and closes a lid containing the UV source. The UV source periodically emits radiation in sufficient quantities to effect surface sterilization.
U.S. Pat. No. 4,448,750 (issued May 15, 1984) describes a method for disinfecting and/or sterilizing small objects such as medical and dental instruments wherein the object to be disinfected or sterilized is contacted with a liquid such as an aqueous solution of sodium dodecylsulfate and carbamide. This solution is substantially transparent to UV radiation and has some bactericidal activity itself at normal temperatures, preferably about 25° C. While the articles are so submersed, vibrations in a frequency range of about 8-300 khz, preferably around 15 khz, are used to achieve a synergistic effect in destroying organisms. Additionally, simultaneous use of UV radiation in the wavelength range of about 1500Å to around 4,000Å preferably around 2537Å has a synergistic effect.
While the above-referenced methods of surface sterilization may find some applications, they are expensive, cumbersome, difficult to use at home, and have not enjoyed wide commercial success.
To overcome these and other problems, Boucher, in U.S. Pat. No. 3,926,556 (issued Dec. 16, 1975), describes a method and apparatus for low temperature intermittent or continuous destruction of microorganisms, including viruses, bacteria and fungi in both solid and liquid materials. The method is especially applicable for decontamination of organic fluids. The material to be sterilized is subjected to the synergistic effect of combined UV energy having a wavelength of around 40Å to around 3100Å and a microwave field having a wavelength from roughly 1 cm to about 35 cm while the temperature is maintained below about 100° C. Boucher's apparatus involves placing a UV-emitting lamp with a separate power source inside the chamber of a microwave oven. It is necessary that the oven have an electrical feedthrough to power the UV-emitting tube. Boucher's tube, of necessity, has electrodes attached thereto. Boucher notes that the bactericidal effect of the microwave energy is not due to thermal action but rather to the bipolar interaction of the oscillating microwave dipole with the molecules within the organisms themselves.
In view of the above, it would be desirable to provide a UV sterilizer such as described by Boucher which could be used in a conventional home microwave oven without the necessity of providing feedthroughs for electrical circuitry to power the UV source.
SUMMARY OF THE INVENTION
The present invention is a UV sterilizer formed by a gas contained in a bulb, which gas emits UV light in response to microwaves, and a microwave source.
In a preferred embodiment, the microwave source is a conventional microwave oven. Several bulbs are supported in a non-conductive, microwave-transparent housing, disposed in the microwave. In use, an object to be sterilized is placed in the housing, and the microwave oven is turned on, causing the gas to emit UV light at the object.
In other preferred embodiments, the sterilizer is adapted specifically for sterilizing contact lenses, bottles, baby bottle nipples and liquids. In the bottle sterilizer embodiment, a bulb mounts on a non-conductive base, and a bottle can be sterilized by placing it on the bulb so that the bulb is inside the bottle. In the contact lens sterilizing embodiment, a hollow non-conductive base supports two quartz wells formed in the base. The wells hold liquid and the lenses are disposed in respective wells. In the liquid sterilizing embodiment, the bulb is formed in the shape of a beaker to hold liquid. A non-conductive support is shaped to accommodate the bulb, or the beaker is made of a non-conductive material with a lid, and the bulb is attached to the lid and immersed in the liquid when the lid is on the beaker. In the nipple sterilizing embodiment, the nipple is friction fit into a hook-shaped bulb.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the UV sterilizer of one embodiment of the present invention housed within a conventional microwave oven.
FIG. 2 is a longitudinal sectional view of a UV bulb according to the present invention.
FIG. 3 shows a UV sterilizer of a second embodiment adapted for bottles.
FIG. 4 is a sectional view of a UV sterilizer of a third embodiment adapted for contact lenses.
FIG. 5 is a sectional view of a UV sterilizer of a fourth embodiment adapted for nipples of baby bottles.
FIG. 6 is a sectional view of a UV sterilizer of a fifth embodiment adapted for liquids.
FIG. 7 is a sectional view of a UV sterilizer illustrating a modification of the fifth embodiment.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In general, the invention is a UV sterilizer adapted for home use. The sterilizer includes a quartz bulb containing mercury vapor or any other appropriate gas at low pressure which emits UV light when placed in a microwave field. The microwave field stimulates intense emission of UV light from the vapor within the bulb. The light in combination with the microwave field is bactericidal and can be used for the cold sterilization of objects placed near the bulb. It has been found that the UV light so generated in combination with the microwave intensities normally available within a consumer microwave oven are sufficient to destroy most organisms at the surface of items such as combs, fruit, toothbrushes and even water and other fluids.
Turning now to FIG. 1, a sterilizing unit 1 is placed within a chamber of a conventional microwave oven 2. Unit 1 is adapted to emit UV light in response to microwaves, and thus obviates the need for a separate power supply. Unit 1 consists of a non-conductive, microwave transparent housing 3 of ceramic or plastic (preferably thermoplastic) which is box-like, and a UV source of one or more UV bulbs 4 mounted (e.g., by a microwave-resistant and UV-resistant adhesive or by plastic brackets or slots) to the inside of the walls, ceiling and floor of housing 3. The housing may have an open or a partially open side (also supporting bulbs as appropriate) through which to insert objects. The bulbs 4 are made of a UV transparent material, preferably quartz, and filled with a UV-emitting gas, preferably mercury, at low pressure. The gas is selected so that it will emit UV light in response to microwaves.
An object 14 or article to be sterilized, such as an apple, is placed within housing 3 close to the bulbs 4. The sterilizer is preferably constructed to avoid "shadowing," regardless of the orientation in which the user places the object in the housing. Accordingly, all surfaces of the article will be simultaneously exposed to UV light so that the article is fully sterilized in one step. To help avoid shadowing, a stand 15 with a UV transmitting surface may be provided to support the object. The housing is also preferably constructed of a size and shape which will accommodate as many different sizes and shapes of articles as possible, yet have the articles as close to the UV light as possible to minimize transmission loss.
To sterilize, the microwave is turned on. Surface sterilization is achieved in a relatively short time, e.g., 30 to 40 seconds, and thus any heating due to the microwaves is limited. The sterilization time depends on a number of factors, such as how close the UV lamps are to the object, how strong the UV rays are, and the microorganisms to be killed. For example, FDA standards require sterilization sufficient to kill aspergillis niger, which can be achieved in as low as 20 seconds or less of UV exposure in the inventive sterilizer. Therefore, 30 or 40 seconds provides some margin of safety. Greater exposure times provide greater safety, but take longer and thus tend to subject the object to heating.
It should be noted that sterilizer 1 preferably has the bulbs 4 mounted on the inside of housing 3 to be closest to the object, but the bulbs can be mounted to the outside as long as the housing is UV transmitting. The housing can also be formed as a frame, with the bulbs extending between bars of the frame. Moreover, the housing and bulbs may even be formed as one element, by providing the housing of a UV transmitting material which itself encases the UV-emitting gas.
A sectional view of a bulb 4 is shown in FIG. 2. Each bulb is a UV transparent envelope 16 housing a UV-emitting gas 17. The envelope is preferably quartz, which has a relatively high UV transparency. Other UV transparent materials may be used, but the exposure time must be increased for lesser transparency. However, quartz is relatively expensive, and therefore the sterilizer is preferably constructed to minimize its use.
To construct the bulb, mercury, preferably along with a carrier gas such as argon or neon, is introduced at low pressures (e.g., about 1 mm of mercury) into an evacuated tube. Then, the tube is sealed, typically forming a nipple 19. The carrier gas functions to minimize the amount of mercury needed in the tube. In addition, the gas can function to help determine whether or not UV emission has started. For example, neon will emit a red color in response to microwaves while mercury will emit a bluish white color. If the bulb appears red, UV emission has not started. The exposure time is thus determined based on the time the bulb appears bluish white.
To enhance UV light emission, it is particularly useful to place a conductor or semi-conductor such as a piece of nichrome or tungsten wire 18 inside the tube before sealing. The wire should be small, e.g., in the range of 0.001 to 0.005 inch diameter and about 1-2 inches long, to avoid appreciable heat production in response to the microwaves. The wire acts like an antenna and facilitates the breakdown or ionization of the gas within the tube and the emission of UV light. It should be noted that mercury may be in its liquid state prior to stimulation by the microwaves, but will become gaseous upon stimulation.
FIG. 3 shows sterilizer 20 adapted for bottles, especially baby bottles. Sterilizer 20 shows an array of UV-emitting bulbs 4 supported on a non-conducting base 22 by means of non-conducting supports 24. The bulbs 4 are dimensioned (e.g., 6" to 7" long) to fit within the interior of a variety of microwave transparent bottles 23. In use, the bottles are placed over the bulbs 4 and the sterilizer 20 is placed within the chamber of a conventional microwave oven. Such a sterilizer can be used in the home, or even in institutions such as hospital maternity wards and day care centers.
FIG. 4 is a sectional view of a sterilizer 33 adapted for hard contact lenses. The sterilizer is formed by a non-conducting base 34 having a hollow section 34a and formed with two openings in which thimble-shaped wells 35 are disposed. The wells are labeled for right and left lenses and are made of UV transmitting material such as quartz. They are shaped to hold liquid 36 in which lenses 37 are placed. The bulb is thus formed by the entire sterilizer, as hollow section 34a contains the UV-emitting gas. To use the sterilizer, liquid 36 and a lens 37 are placed in each well 35, and the sterilizer is placed in a microwave oven. When the microwave is on, the gas irradiates the lenses through the quartz wells.
In this embodiment, the wells may be attached to the base by adhesive or other means suitable for joining quartz and ceramic in an airtight fashion. For example, silicone or epoxy cement could be used to join the quartz and ceramic. The use of ceramic as a base with quartz wells minimizes the use of quartz, which is relatively expensive. More specifically, by constructing the base entirely of ceramic with only the portion where UV light must be transmitted, i.e., the wells formed of quartz, the amount of quartz is greatly reduced. However, the entire sterilizer could be made of quartz. To protect the quartz in this embodiment and others from breaking and/or shattering upon breakage, a UV transparent teflon coating may be applied to the quartz.
In FIG. 5, which is a sectional view of a sterilizer 43 adapted for sterilizing the outside of a baby bottle nipple 44, the nipple is friction fit inside a hook-shaped bulb 45 containing a UV-emitting gas. The bulb is attached to a non-conductive arm 46 in turn mounted on or integral with a platform 47.
In FIG. 6, which is a sectional view of a sterilizer 53 adapted for sterilizing a liquid 54, such as water or juice, a bulb 55 containing UV-emitting gas is shaped like a beaker to hold the liquid. The bulb may form the entire sterilizer. However, to limit the use of UV transmitting material while providing additional strength and stability, the bulb is shown mounted to the inside of a beaker-shaped non-conducting material 56.
Alternatively, to sterilize a liquid, a bulb such as bulb 4 of FIG. 2, may be inserted into liquid 54 to sterilize it. This is shown in the sectional view of FIG. 7. A beaker 56a of a nonconductive, microwave transparent material holds liquid 54. A bulb 4, having a stem 59 fixed to it and held in a non-conductive microwave transparent lid 60, is immersed in the liquid.
The invention thus achieves an inexpensive sterilizer that can be readily used in the home in an existing microwave oven, which already provides appropriate safeguards against user exposure to harmful radiation. For example, the microwave walls and window block UV light or can readily be made to do so In addition, the microwaves, and thus the UV emissions, shut off in response to premature opening of the oven door.
It is to be understood that numerous modifications may be made in the illustrative embodiment of the invention and other arrangements may be devised without departing from the spirit and scope of the invention as set forth in the appended claims. For example, the invention may be useful for production of UV light for processes such as erasing EPROMS and curing resins, in addition to sterilization.
|
A microwave activated ultraviolet sterilizer for surface sterilization of articles such as baby bottles, contact lenses and the like permits rapid irradiation and easy operation. The sterilizer includes a substantially non-conducting housing, a plurality of transparent ultraviolet lamps disposed within the housing, and a microwave source, such as a conventional home microwave oven. In use, the sterilizer is placed within the oven and derives its power from the oven's microwave field.
| 0
|
This invention relates to a power laser preferably but not essentially of the kind described in the co-pending application corresponding to West German Patent Application P 3734570.2, U.S. patent application No. 228,726 of the same inventor, filed simultaneously herewith.
BACKGROUND OF THE INVENTION
Such power lasers have the following features: intermediate corner flanges, an end flange, gas pipelines disposed in a rectangle between the intermediate corner flanges and the end flange, a support for the intermediate corner flanges and the end flange, a blower, heat exchangers, and cooling gas paths from and to the blower and from and to the gas pipelines.
In the field of power lasers, it is desirable to generate a high energy beam which as far as possible irradiates in the TEM00 mode. It is also desirable to achieve higher power inputs.
In the case of lasers used hitherto, special constructions were always necessary insofar as the dimensions of a 500 W laser differ from those of, for example, a 5000 W laser. In terms of cooling, cooling water flow, gas flow, supply and discharge of pump energy, all these lasers have to be differently designed in one way or another. This not only entails the need for special constructions at the manufacturing stage. Rather, it also makes maintenance difficult. It is also scarcely possible to start with a 500 W laser for example and then upgrade it later on to 1000 W. The costs of such a conversion are unacceptable.
OBJECT AND STATEMENT OF THE INVENTION
The object of the invention is to provide a solution by which it is possible, on the basis of the laser mentioned at the outset, to multiply the laser energy easily and rationally while retaining virtually all the structural elements.
According to the invention, this object is achieved by the following features:
(a) the power laser constitutes one module with corners,
(b) at least two modules that are at least substantially the same are connected to each other, and
(c) the modules are connected at corners of the modules by means of a connecting flange having an interior that is permeable to laser beams, the connecting flange establishing a rectilinear joint between two gas pipelines of different modules.
The invention is based on the knowledge that such a laser can be used as a basic component and that the energy can be doubled by coupling together or basic components according to the invention and that the energy can be tripled by using three basic units, and so on. Therefore, as with internal combustion engines, it is possible to employ the same principle by multiplying one "original cell", where of course there are also single cylinders, twin cylinders, etc. The only new structural component required is a connecting flange which is essentially nothing more than a double intermediate corner flange, certainly without a deflecting mirror.
If two such components are coupled together, then one can save on a deflecting mirror, a total reflection mirror and an output mirror. This obviously offers many advantages with regard to costs, mode improvement, even simpler cooling, improved gas flow (because the gas passes lineally through the connecting line and does not have to go around the corner). Fewer mirrors also means easier adjustment. As the mirrors are expensive, there is also a considerable saving on money. The construction remains clear and uncluttered even if a plurality of basic units are assembled together. This means that supplies such as, for example, for electricity or the like, can be set up substantially more systematically and more tidily. The principle can be repeated automatically by multiplication. Therefore, there is no need for fresh calculation because all the components including the turbine remain the same. It could be said that the only inconstant feature of the whole system is the total reflection mirror and the output mirror. With a characteristic extension of less than 1 meter for 500 Watts output for instance the individual component is still very small.
Advantageously the described embodiments include the following additional features:
At least three modules can be connected to one another in a staircase pattern. (FIG. 6). This configuration is recommended if the space allows the length to be accommodated in one room.
At least three modules can be connected to one another in a hockey stick pattern. (FIG. 7). This configuration is recommended if about the same amount of space is available to accept the width and length.
Four modules can be connected together, three of them being connected to three corners of a central module. This feature provides a laser with four module components and avoids having two of these working on only one part of the gas pipelines.
Five modules can be connected together, four of them being connected to four corners of a central module. (FIG. 8). This feature provides a structural principle for five component units.
A plurality of levels of groups of modules can be provided. This feature shows that these structural units can also be arranged in a multi-dimensional disposition.
A structural unit according to co-pending application 228,726 is described hereinafter and reference to it is made in FIGS. 1 to 4. FIGS. 5 to 11 shows the construction according to the invention. In the drawings:
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatic plan view of a horizontally disposed laser,
FIG. 2 is a plan view according to FIG. 1, but larger, showing the interior of the table top,
FIG. 3 is a view as indicated by the arrow 3 in FIG. 1,
FIG. 4 is a view as in FIG. 3, but on an enlarged scale, partly broken open, showing the interior of the engine housing, the blower flange and the broken-line illustration of partial paths,
FIG. 5 shows the coupling together of two structural units created essentially from duplication of FIG. 1,
FIG. 6 is a diagrammatic view showing the disposition of three structural units,
FIG. 7 is a diagrammatic view of a different arrangement of three structural units,
FIG. 8 is a diagrammatic view of five structural units,
FIG. 9 is a diagrammatic view of the coupling together of 4×4=16 structural units,
FIG. 10 is a view showing how four structural units ought not to be coupled to one another, and
FIG. 11 is a diagrammatic view of the arrangement in FIG. 9 viewed from the side and a further duplication by disposing the structural units on two levels.
DESCRIPTION OF PREFERRED EMBODIMENTS
Without limiting the invention to the embodiments described, a CO2 laser 11 with an output power of 500 W stands on a table 12 to which it is rigidly connected. Provided underneath the table 12 is a turbo-radial blower 13 which is rigidly bolted to the underside of the table 12. The device shown in FIGS. 3 and 4 is one unit. It stands on a frame, not shown. The laser has a beam path 14 shown by a dash-dotted line. It extends in a quadratic pattern. The beam length is 2650 mm. The diameter of the beam is 10 mm and it irradiates in the TEM00 mode. The beam path 14 comprises three intermediate corner flanges 16, 17, 18 which accommodate both diagrammatically shown 45 degree mirrors and also fittings 19 for gas pipes. Provided at the fourth corner is an end flange 21 comprising a totally reflecting mirror 22 and an output mirror 23. In the end flange 21, the beam path 14 intersects at 90 degrees. Exactly in the center between the first intermediate corner flange 16 and the second interemediate corner flange 17 there is in a first gas pipeline 24 a first through-flange 26 which has fittings 19 on both sides. Extending between the intermediate corner flange 16 is a gas pipe 27 which is held in gas-tight fashion at both ends, and between the through-flange 26 and the intermediate corner flange 17 there is a gas pipe 28 which is held in gas-tight fashion in fittings 19. Both gas pipes 27, 28 are enclosed by HF electrodes 30. Exactly in the center of the second gas pipeline 29 there is a second through-flange 31. Exactly in the center of the third gas pipe 32 there is a third through-flange 33 and in the fourth gas pipe 34 there is a fourth through-flange 36. The gas pipelines are in each case at right angles to one another and, if one disregards the beam path which extends beyond the point of intersection 37, they form a geometrical square. Since the proportions in terms of gas pipes 27, 28 and electrodes 30 are identical in the lines, they require no further explanation.
Diagonals 38, 39 drawn through the corners of the square intersect at 41.
Apart from the visible chamfers at the corners, the table 12 likewise forms a square measuring 850 mm along each edge. Its height is 80 mm. It has a flat upper wall 42 and a flat lower wall 43 which are in each case one-piece steel plates. The steel plate itself is gas-tight with the exception of the apertures provided to suit the intended purpose. The table 12 has on its periphery peripheral walls 44 which close off the resultant cavity 46 in gas-tight fashion in respect of the outside environment, being welded to the upper wall 42 and the lower wall 43. Coaxially with the point of intersection 41, the lower wall 43 has a central hole 47. On a radius of about 1/3 of half the diagonal length, the lower wall comprises four holes 48, 49, 51, 52. The diagonal 39 passes through the holes 49, 52 while the diagonal 38 passes centrally through the holes 48, 51. Bolted securely in gas-tight manner to the underside of the lower wall 43 in a housing 53 of the blower 13. A motor 54 comprises a stator 56 and a rotor 57, the shaft 58 of which has a geometrical longitudinal axis 59 which passes through the point of intersection 41. Mounted on the shaft 58 is a turbine rotor 61 which has above its upper end face a vacuum space 62 which communicates directly with the central hole 47. A pressure space 63 is provided in the housing 53 downstream of the turbine rotor 61. The pressure space 63 has upwardly extending arms 64 which communicate directly with the holes 48-52. Emanating from the hole 48 is a first partial path 66 in which the gas flows as indicated by the arrow 67. Between the upper wall 42 and the lower wall 43 are welded gas-tight partitions 68, 69 which are at right angles to each other. In accordance with FIG. 2, the partition 68 extends from 6 o'clock to 12 o'clock while the partition 69 extends from 9 o'clock to 3 o'clock. They are spaced everywhere from the hole 48 so that gas can emerge freely from it. From the partitions 68, 69, two mutually parallel positions 71, 72 extend at a considerable distance from each other and parallel with the diagonal 38. Provided in the partial path 66 is a heat exchanger 73, the connections of which traverse the lower wall 43. They are not shown. Under the intermediate corner flange 16, the upper wall 42 comprises a hole, not shown, which corresponds to the hole 48. This hole which is not shown communicates directly with the interior of the gas-tight intermediate corner flange 16. According to the dash-dotted lines 74, 76, gas is able to flow out of the partial path 66 into the intermediate corner flange 16 and thence into the gas pipe 27 and the gas pipe 77. Since the partial paths 78, 79, 81 are virtually identical in construction, they are not described in further detail. It is evident that the partial paths 78, 81 are disposed under the diagonal 39 while the partial paths 66, 79 are under the diagonal 38. It can also be said that the partial paths 66, 78, 79, 81 are symmetrically stellate and extend in a like configuration. The flow directions are shown as arrows.
Parallel with one another and spaced apart by a considerable distance and parallel with the angle bisector of the diagonals 38, 39, two straight partitions 82, 83 extend from the central hole 47 and its environment, vertically upwardly in FIG. 2. This provides a partial path 84 for gas dispersal. The gas flows out of the gas pipes 27, 28 into the through-flange 26 which is in this respect hollow. In the direction of the upper wall 42, it comprises a hole, not shown, which communicates with a likewise not shown hole disposed directly underneath it in the upper wall 42. The line 74 symbolising the gas flow meets a line 85 symbolising a further gas flow, in the through-flange 26. Both gas flows are of the same magnitude. They pass through the holes not shown and into the partial path 84, where they flow through a heat exchanger 86 and are drawn off through the hole 47 into the vacuum space 62. In the same way, a partial path 87 containing a heat exchanger leads from the through flange 31 to the central hole 47, a partial path 88 leads from the through-flange 33 to the central hole 47 and likewise a partial path 89 leads from the through-flange 36. The partitions 82, 83 form with the walls bounding the other partial paths a large cross the corners 91 of which end substantially before the central hole 47. This makes for good flow conditions since the flows are symmetrical and of the same size, encountering no obstacles and being guided along a linear path. This linear guidance naturally also applies to the other partial paths 66, 78, 79, 81. Around the holes 48, 49, 51, 52 which represent sources there is a lot of space and likewise around the hole 47 which constitutes a sink. The distances between the partitions of each partial path are the same so that also the specific flow resistance is the same.
The height of the assembly shown in FIG. 3 is approx. 80 cm. Therefore, it is necessary only to provide a space 80 cm high and approx. 85 cm square.
The laser according to FIG. 5 is created from two lasers as shown in FIG. 1, the structural unit shown in the bottom left hand corner having been connected to the identical structural unit shown in the top right hand corner, by a connecting flange 21'. Therefore, the unit shown bottom left is missing the intermediate corner flange 17', in comparison with FIG. 1, while the unit shown top right has neither a mirror 22 for total reflection nor an output mirror 23. Instead, the beam path there is continuously linear at exactly 90° to the connecting flange 21'. The beam crosses the centre of the connecting flange 21' and it is well known that this does not entail any structural or heat problems.
If one wished to see how the blower, the heat exchangers and the cooling gas paths are disposed in relation to the gas pipelines, then it would be necessary only to take FIG. 2 and--as happened in FIG. 5--link two pictures together by the corner, using a connecting flange and one would then be able to see the structural details which are disclosed by FIG. 5.
FIG. 6 shows the interconnection of three structural units in comparison with the two units shown in FIG. 5. The arrow shown bottom left in FIG. 6 indicates the laser beam output. As can be seen, seven deflecting mirrors are needed each offering a 45° deflection, and also two identical connecting flanges. It is easy to count up the deflecting mirrors, total reflection mirror and output mirrors which it is possible to save by this arrangement.
FIG. 7 shows that it is not always necessary to build on by connection to the diagonally opposite corner. Instead, it is also possible to build on at two adjacent corners of the first unit.
The configuration of five units shown in FIG. 8 can be imagined as being a development from FIG. 6, a unit having been attached to the still free corners of the middle unit. As the illustration shows, only four simple continuous connecting flanges are needed. If one follows the laser beam in FIG. 8, one can see that all the gas pipelines are used for the laser.
FIG. 9 shows an arrangement of 16 units arranged in a chessboard pattern. The laser beam produced is represented by an arrow pointing downwards. However, the output could be located at any other desired outer corner. One structural unit has been picked out by the cross hatching. Although there are 4×4=16 units, only 20 45° deflecting mirrors are needed. In proportion to the number of units, this is only a small number and demonstrates the law by which it is possible to economise more and more on deflecting mirrors the more the system is brought up in such a way as to be closed in itself. 21 connecting flanges are needed but, as explained above, there are structurally simple. Here, as with the other interlinking arrangement, no mirror has to be cooled in the connecting flanges which is why the invention becomes simpler. Naturally, a total reflection mirror and an output mirror wall always be required somewhere.
According to FIG. 11, it is also possible to work on two levels and so double the output once again in comparison with the arrangement in FIG. 9, without having to provide for a larger or 8. Here all that is required are the 45° mirrors shown by the broken lines which, instead of reflecting in the plane of the drawing in FIG. 9, reflect perpendicularly and once from one plane or level into the other. These linking mirrors which connect two levels to one another are identified by reference numerals 91 and 92. As can be seen, the motors 54 of the lower level project downwardly while the motors 54' of the upper level project upwardly. Where the basis unit is concerned, it is of course possible to provide this in any position in the room. For example, the device according to FIG. 9 need not necessarily be disposed horizontally. Instead, it can also be disposed vertically like a wall and accordingly, too, the device according to FIG. 11 could so to speak form a vertical double wall.
FIG. 10 shows how the structural elements ought to be connected to one another: if one follows the path of the beam which extends according to the loop 94, then it is evident that those gas pipelines which lie in the loop 96 which is shown by the broken lines, are not used. Therefore, the result is far less than four times the energy output. This arrangement would however be feasible if one were to want to generate two independent laser beams. It would then be necessary in addition to have the output as indicated for example by the arrow 97 shown by the broken lines, naturally omit the 90° mirror there and also provide an end flange 21 of the type shown in FIG. 1. Then there would be two laser beams in a stereo arrangement.
|
The invention is based on the knowledge that a laser can be used as a basic component and that the energy can be doubled by coupling together two basic components according to the invention and that the energy can be tripled by using three basic units, and so on. The power laser constitutes one module with corners, at least two modules that are at least substantially the same are connected to each other, and the modules are connected at corners of the modules by means of a connecting flange having an interior that is impermeable to laser beams, the connecting flange establishing a rectilinear joint between two gas pipelines of different modules.
| 7
|
CROSS-REFERENCE TO RELATED APPLICATIONS
The present patent application is a divisional application of Ser. No. 08/559,193, filed on Nov. 13, 1995, which is pending.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to buckets, particularly large buckets (on the order of 5 or 6 gallon size). More particularly, the present invention relates to a selectively raisable shield for a bucket which serves to retain roller spray within the confines of the bucket when a paint roller is being cleaned by spinning.
2. Description of the Related Art
One tool frequently used by painters is a paint roller tool. The rollers thereof become laden with paint during the painting process. Since the roller is not usually worn-out by a single usage, a painter must thoroughly clean the roller if it is desired to reuse the roller in the future. If the roller is not clean any remaining paint will harden, thereby matting at least a portion of the roller nap, could possibly contaminate the next used paint color, or may cause flecks of the dried paint in and on the roller to be left behind as unsightly specks on a surface being painted.
Rollers are able to hold a vast quantity of paint. One method of cleaning rollers relies upon centrifugal force to cause paint to be flung from a roller. Centrifugal cleaning involves spinning the roller at a very fast rate, whereupon the paint is caused to fly outwardly from the roller. In order to generate the rotation speed necessary for centrifugal cleaning to work well, a commercially available spinning tool is used to clean a roller. The commercially available spinning tool (which is depicted in FIG. 1) includes a barrel, a handle, a screw member connected with the handle and threadably engaged with respect to the barrel, and a roller holder which is bearingly engaged with the barrel opposite the handle and spinably connected with the screw member. When the handle is pushed in toward the barrel, the roller holder spins and continues spinning even after the handle has stopped moving, whereby the centrifugal force generated thereby causes a roller placed thereupon to become cleaned. Problematically, the centrifugal nature in which the paint drops leave the roller entails paint spraying everywhere. Accordingly, painters try carefully to place the roller as far inside their bucket as possible before spinning it with a commercial spinning tool, with less than perfect results. Inevitably, some paint flies centrifugally to a place where it shouldn't be (i.e., someplace outside the bucket).
Accordingly, what is needed is some way in which a bucket can serve to retain centrifugal paint spray when a roller is cleaned with a spinning tool, without detracting from its ability to function as a bucket for other purposes.
SUMMARY OF THE INVENTION
The present invention is a spin spray shield which is connected with a bucket to thereby assist the bucket to retain centrifugal paint spray when a roller is cleaned with a spinning tool, without detracting from the funtionality of the bucket for other purposes.
The spin spray shield according to the present invention generally includes an annular shield member for being selectively located above the mouth of a bucket to thereby serve as a shield for retaining spin generated paint spray within the confines of the interior of the bucket, and further includes a guide member located adjacent the side of the bucket for guiding selective movement of the shield member with respect to the mouth of the bucket.
In the preferred embodiment of the spin spray shield, the shield member is composed of a loop of sheet material (that is, a sheet material loop) dimensioned to nest within the interior of the bucket, the bucket being for example a five or six gallon size bucket. The shield member is raisable from a nested position within the bucket to a deployed position wherein the shield member extends from just below the mouth of the bucket to a selected location above the mouth, such as for example nine inches above a fourteen inch tall bucket to thereby render a roller mounted to a commercially available spin tool sufficiently shielded so that all the centrifugally originated paint spray therefrom collides with the shield member and the bucket inside wall and thereby staying within the confines of the bucket. The guide member includes a mast connected with the shield member and at least one guide which is directly or indirectly connected with the bucket. The at least one guide vertically guides sliding movement of the mast, whereby the shield member is guidably moved with respect to the mouth of the bucket. Preferably, the mast is removably mounted with respect to the at least one guide so that the shield member is selectively connected with the bucket.
Accordingly, it is an object of the present invention to provide a spin spray shield to thereby increase the height of the bucket so that spray from a roller spun inside the bucket will be entrapped within the bucket and the spin spray shield.
It is an additional object of the present invention to provide a spin spray shield for increasing the height of the bucket so that spray from a roller spun inside the bucket will be entrapped within the bucket and the spin spray shield, wherein the height of the spin spray shield relative to the mouth of the bucket is user selectable.
It is another object of the present invention to provide a spin spray shield for increasing the height of the bucket so that spray from a roller spun inside the bucket wi be entrapped within the bucket and the spin spray shield, wherein the height of the spin spray shield relative to the mouth of the bucket is user selectable, and wherein the spin spray shield is selectively removable from the bucket.
It is a further object of the present invention to provide an adjustable tensioning band for engirding an bucket to thereby mount one or more objects to the bucket by depending therefrom.
These, and additional objects, advantages, features and benefits of the present invention will become apparent from the following specification.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the spin spray shield according to the present invention, shown in operation in connection with a bucket.
FIG. 2 is a side elevational view of the spin spray shield according to the present invention, shown installed with respect to a bucket.
FIG. 3 is a partly sectional side view of the spin spray shield according to the present invention, shown installed with respect to a bucket.
FIG. 4 is a partly sectional detail view along line 4--4 in FIG. 1, showing the interconnection of the guide member of the spin spray shield according to the present invention with a bucket.
FIG. 5 is a partly broken-away side elevational view of the spin spray shield according to the present invention, shown installed on a bucket and particularly detailing the guide member of the spin spray shield.
FIG. 6 is a partly sectional, detail top plan view of the spin spray shield according to the present invention and bucket, seen along lines 6--6 in FIG. 5.
FIG. 7 is a perspective view of the spin spray shield according to the present invention installed with respect to a bucket, wherein an alternate form of guide member is utilized.
FIG. 8 is a detail perspective view showing operation of the alternate form of guide member.
FIG. 9 is a side view along 9--9 in FIG. 8, showing the structural feature for providing mutually sliding, guided movement of the spin spray shield relative to the bucket.
FIG. 10 is a top plan view of the spin spray shield according to the present invention installed with respect to a bucket, wherein the alternate form of guide member is shown.
FIG. 11 is a sectional view of the spin spray shield according to the present invention installed with respect to a bucket, wherein the alternate form of guide member is shown.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the Drawing, FIG. 1 generally depicts the spin spray shield 10 according to the present invention in a typical environment of use. The spin spray shield 10 is connected with a bucket 12, such as for example a five or six gallon (or some other chosen) size commercially obtainable bucket. The bucket 12 has a mouth 14, a sidewall 16 (the lip 16d of the sidewall defining the mouth) and a bottom 18 which collectively define an interior space 20 of the bucket. The mouth 14 is generally annular and has a given cross-section C B at the mouth (see FIG. 3), and the sidewall 16 has a height H (see FIG. 3) which renders an inherent tallness to the bucket. As can be discerned from FIG. 1, the sidewall 16 of the bucket 12 has a taper so that the cross-section C B at the mouth is larger than the cross-section C B ' at the bottom 18 (see FIG. 3). The spin spray shield 10 is structured to cooperate with the bucket to be deployable at the mouth 14 so that when a painter 22 spins a roller 24 of a conventional paint roller tool via a commercial spin tool 26 with the roller located in and about the interior space 20 of the bucket, the paint spray 28 centrifugally leaving the roller will be retained within the confines of the bucket and the spin spray shield. As generally shown in FIG. 1, the spin spray shield 10 includes two major components: a shield member 30 dimensioned to interface with the interior side 16a of the sidewall 16 of the bucket 12 to confine centrifugal roller spray therewithin and a guide member 32 for guiding positioning of the spin spray shield with respect to the mouth 14 of the bucket.
The structure and function of the spin spray shield 10 will now be detailed with greater specificity with reference now being additionally directed to to remaining FIGS. 2 through 11.
The shield member 30 is in the form of a cylindrically shaped sheet material loop 34 for being located adjacent the interior side 16a of the sidewall 16 of a bucket 12 at the mouth 14 thereof. If a bucket has a mouth shape other than circular, the shape of the sheet material loop 34 would be correspondingly shaped to adjacently fit therein. A preferred material for the sheet material loop 34 is a plastic. The selected plastic and the thickness thereof is chosen so that the shape of the sheet material loop is self-supporting when in the deployed position. A preferable plastic for the sheet material loop 34 is one that paint does not well stick to, so that any paint spray thereon is reasonably easy to clean off. The sheet material loop 34 is preferably constructed of a continuous loop of sheet material; however, it is possible to construct the sheet material loop from a length of flat sheet material that has been rolled and the abutting ends thereof fastened together by any suitable interconnection means to thereby form a loop thereof, such as for example glue, a bracket having opposing U-shaped portions for receiving the ends, or fasteners, such as for example rivets.
As mentioned, conventional buckets are usually tapered. Accordingly, it is preferred to configure the sheet material loop into a taper similar to that of a bucket, wherein the cross-section C S at the top edge 34a is greater than the cross-section C S ' at the bottom edge 34b.
As mentioned, the purpose of the shield member 30 is to provide an extension of a bucket above its mouth to thereby effectively increase the height of the bucket sidewall so as to receive centrifugal roller spray when using a commercial spin tool within the bucket. Accordingly, when at the shield member 30 is at the deployed position, the top edge 34a and the bottom edge 34b of the sheet material loop 34 are spaced apart a predetermined distance to provide enough height to the bucket to provide this feature (see FIG. 1 in combination with the phantom lines D in FIG. 2). In this regard as shown in phantom in FIG. 2, the bottom edge 34b is typically located a short distance below the mouth 14 of the bucket 12, whereby any flying spray produced by centrifuging a roller would caught by either the inside 16a of the sidewall 16 or the sheet material loop 34, and any paint oozing down the sheet material loop will thereupon drip into the interior space 20 of the bucket.
It is preferred for the sheet material loop 34 of the shield member 30 to be of sufficient cross-section as to be adjacent the sidewall 16 at the mouth 14. In this regard, the taper of the sidewall 16 is to be taken into account so that the sheet material loop 34 is able to nest into the sidewall, as depicted by phantom lines N in FIG. 2. Further in this regard, when the shield member 30 is in the nested position, having the sheet material loop 34 close the the sidewall 16 of the bucket 12 provides for the interior space 20 of the bucket to be essentially usingly unimpaired by the presence of the shield member, so that articles, water, etc. are situatable within the bucket in a normal manner.
As mentioned, the shield member 30 is selectively positionable with respect to the mouth 14 of the bucket 12. This is accomplished by the aforementioned guide member 32. The guide member 32 includes a first component 36 which is connected with the shield member 30 and a second component 38 connected (directly or indirectly) with the sidewall of the bucket 12. The first and second components 36, 38 slidably interact to thereby guide movement of the shield member 30 with respect to the mouth 14 of the bucket 12 in the bucket axis A (see FIG. 2), wherein the bucket axis is oriented perpendicular to the plane of the lip 16d of the sidewall 16.
There are two preferred forms of the first and second components, as will be detailed below, wherein the first preferred form of the first and second components are depicted by FIGS. 1 through 6, and the second preferred form of the first and second components are depicted by FIGS. 7 through 11.
The first preferred form of first component 36 is a rigid mast 40, such as for example a section of plastic conduit. The mast 40 is connected with the sheet material loop 34 adjacent the top edge 34a thereof via a bracket 42. The preferred bracket 42 is U-shaped, wherein the clevis thereof is connected to the mast 40 near the top thereof by a threaded fastener 25 and a base of the clevis is connected to the sheet material loop 34 by a threaded fastener 35 (of course, other fastening means may be used other than threaded fasteners). Other connection methodologies may be used in place of the bracket, such as for example a pedestal integrally formed with the mast and glued to the sheet material loop. In order for the shield member 30 to nest within the bucket 12, it is preferred for the sheet material loop 34 to include a tongue 45 projecting in the local plane of the sheet material loop at the top edge 34a thereof to which the bracket 42 attaches by an attachment means, such as for example by the threaded fastener 35. The length of the mast 40 is selected to extend preferably about the height H of the bucket 12 for the purpose of providing movement of the shield member 30 between its deployed position D and its nested position N.
The first preferred form of the second component 38 includes two mutually separated guides 44 connected with the bucket 12. Each of the guides 44 has a guide hole 46 which is dimensioned to snugly and slidably receive the mast 40, wherein the guide hole may be fluted (as shown in FIG. 4) to provide guidance with minimal contact friction with respect to sliding of the mast. The connection of the guides 44 to the sidewall 16 of the bucket 12 may be indirect via a band 48 that engirds the sidewall, or direct via threaded fasteners 50 engaging the sidewall. While two guides 44 are preferred, at least one guide 44 is required; more than two guides or a single elongated guide (of a pipe-like configuration) could be utilized.
In the case of connection of a guide 44 via a band 48, the guide may be integrally formed with the band or be connected thereto via feet thereof (see FIG. 4) such as by an adhesive or by threaded fasteners. In order for the band 48 to tightly engird the sidewall 16, a connector 52 is included therewith. The connector 52 is structured to allow a user to install the band 48 engirdingly about the sidewall 16 and then tightly encircle the sidewall so that the band is held firmly thereto under its own tension. In this regard, the band 48 is composed of a band member 54, which may be for example plastic or metallic, which is connected with the connector 52. A preferred connector 52 is depicted in FIGS. 5 and 6. The connector 52 includes a buckle component 56 and an adjustment component 58. The buckle component 56 operates on a conventional buckle principle, wherein an off-set pair of pivots causes the cross-section of the band 48 to contract as the buckle 60 is closed and causes the cross-section of the band to expand as the buckle is opened (along arrow O in FIG. 6). The adjustment component 58 is connected with the buckle component and operates similarly to that of a screw and serrations operated hose clamp. In this regard, the buckle component 56 is connected with one end of the band member 54 the adjustment component 58 is composed of a serrated strip 66 having a series of serially disposed serrations, which is connected to the buckle 60, and a screw 62 connected with a seat 64 to the other end of the band member, wherein the screw is threadably engaged with the serrations of the serrated strip. Turning of the screw 62 in its seat 64 causes the serrations of the serrated strip 66 to threadingly move with respect to the seat and thereby adjust the cross-section of the band 48. Accordingly, with the cross-section of the band 48 adjusted by the adjustment component 58, closure of the buckle 60 effects a tensioned, tight and secure fit of the band 48 with respect to the sidewall 16. In this regard, the band 48 may be placed between sidewall ribs 16c' of the bucket 12 (if they are present), or elsewhere on the sidewall (either case being depicted in FIG. 5).
In the case of connection of a guide 44 directly to the sidewall 16, as shown in FIG. 4, it is preferred for the guide to be threadably connected with a sidewall flange 16c whereby the threaded fasteners 50 engage feet 44a of the guide. In this manner, the threaded fasteners 50 will not pierce the sidewall 16. Alternatively, the feet 44a can be adhered to the sidewall by an adhesive, but this is not preferred if this form of installation results in a permanent connection (however, if the bucket is to be permanently altered, then there would be no objection). Further with regard to feet 44a, spacers can be employed between the feet and the sidewall (or the feet and the band member 54) in order to properly align the locations of the guide hole 46 of each of the guides 44 with respect to to the bucket axis A.
It should be noted that the mast 40 is slidable along the guide holes 46 and may be disengaged therefrom by sliding entirely thereout, whereupon the shield member 30 is disconnected from the bucket 12. Alternatively, it is possible to place a stop nib or other stop mechanism on the mast to prevent removal from the guides.
It should further be noted that the band 48 may be attached to a bucket independently of the guides for the purposes of suspending any other object therefrom alongside the sidewall of the bucket, such as for example a tool holder of some sort that lippingly engages the band.
In order to exemplify the criteria underwhich the present invention is effectable with respect to a bucket and a spin tool, an example will now be detailed. The bucket is a five gallon size, having a height H of about 15 inches, a cross-section C B at the mouth of about 11.25 inches and a cross-section C B ' at the bottom of about 10 inches. The spin tool has a barrel about 8 inches long, the screw member on the handle is extendable about 7 inches from the barrel and the roller holder thereof holds a paint roller typically between about 9 and 12 inches in length. A spin spray shield 10 therefor could be, by way of example only, dimensioned as follows. The sheet material loop 34 is plastic having a thickness of about 1/8 inch, a width measured between the top edge 34a and bottom edge 34b of about 9 inches, and a cross-section C S of about 10.5 inches at the bottom edge and a cross-section C S ' of about 11 inches at the top edge. The tongue 45 extends about 1 inch from the top edge. The mast 40 is a plastic conduit section of 1 inch outside diameter and length of about 15 inches. The guides 44 are separated from each other along the direction of the bucket axis A by about 4 inches, wherein the band member has a width of about 0.5 inch and the guides provide a guide hole 46 that extends about 0.6 inch along the bucket axis. Finally, the bracket 42 has a base separated from the mast by about 0.7 inch. It is to be noted that for the sheet material loop to have an appropriate spray shield function as disclosed generally herein, that its width should preferably be about 4 inches at the minimum.
The second preferred form of first component 36 is a rigid mast 40', such as for example a section of corrosion resistant strap (such as a strap of galvanized steel, aluminum or strong plastic). The mast 40' is connected with the sheet material loop 34 adjacent the bottom edge 34b thereof and at the tongue 45 via a threaded fastener 80 at each location (of course, other fastening means may be used other than a threaded fastener). To facilitate uplifting the shield member 30, a tab 82 may be provided at the uppermost end of the mast 40'. The length of the mast 40' is selected to extend preferably about the height H of the bucket 12 for the purpose of providing movement of the shield member 30 between its deployed position D and its nested position N.
The second preferred form of the second component 38 includes a guide 44' connected with the bucket 12 via a clamp 84. Preferably the clamp 84 and the guide 44' are an integral single piece. The clamp 84 includes a tightening screw 86, preferably a wing-head bolt. The guide 44' has a guide hole 46' in the form of a slot which is dimensioned to snugly and slidably receive the mast 40'. The guide 44' is connected, via the clamp 84, to the sidewall 16 at the lip 16d thereof.
It will be noted that the guide 44' is located between the threaded fasteners 80, thereby serving to define maximum travel limits of the sheet material loop 30 relative to the bucket 12. However, in the event the threaded fastener 80 at the bottom edge 34b is not provided, then the mast 40' is fully removable from the guide 44' and the sheet material loop is thereby then also removable from the bucket.
The advantage of the second form of first and second components 36, 38 is that the external side of the sidewall 16 of the bucket 12 is free of the mast (which is now internal to the bucket).
In operation, the user installs the one or more guides to a selected bucket using fasteners or an engirding band. The mast is placed through each guide hole of the one or more guides. If not already connected, the mast is connected to the sheet material loop. The user then presses upon the shield member to cause the mast to move along the one or more guides to thereby move the sheet material loop into the nested position. When one or more paint rollers are to be cleaned, the user then grabs and pulls upon the mast, for example at the bracket or the tab, to cause the sheet material loop to be raised to the deployed position. At the deployed position, the user then places a spinning tool into the interior space of the bucket and commences spinning of a paint roller to be centrifugally cleaned, whereupon the splatter flies to the sides of the sidewall and the sheet material loop and does not leave the confines of the bucket.
To those skilled in the art to which this invention appertains, the above described preferred embodiment may be subject to change or modification. Such change or modification can be carried out without departing from the scope of the invention, which is intended to be limited only by the scope of the appended claims.
|
A spin spray shield connected with a bucket to thereby assist the bucket to retain centrifugal paint spray when a roller is cleaned with a spinning tool, without detracting from the funtionality of the bucket for other purposes. The spin spray shield generally includes an annular shield member for being selectively located selectively substantially entirely above the mouth of a bucket to thereby serve as a shield for retaining spin generated paint spray within the confines of the interior of the bucket, and further includes a guide member located adjacent the side of the bucket for guiding selective movement of the shield member with respect to the mouth of the bucket.
| 1
|
This is a division of application Ser. No. 08/548,338, filed Nov. 1, 1995, now Pat. No. 5,695,063.
BACKGROUND OF THE INVENTION
The present invention relates to blister packs for pharmaceuticals having a base with a plurality of recesses that are surrounded by a shoulder and a lid foil attached to the shoulder, where removable contents are accommodated in the recesses and may be removed therefrom by pressing on the recess in question making the contents penetrate the lid foil, or by removing the lid foil over the recess, and where the blister pack features a moveable lid that covers the recess, and the lid is arranged such that it can slide over the lid foil.
It is known to fill the bases of blister packs, in particular push-through packs, with contents, to cover the whole of base with a lid material, and to seal the lid material in place. The blister pack is characterised by way of a single or, in particular, by a plurality of single compartments that accommodate e.g. solid items, shaped solid preparations or pharmaceutical products such as tablets or dragees. If a single item e.g. a tablet is to be removed from a blister pack, the recess in the base is pressed in and the tablet is pushed through the lid material.
The present invention embraces various kinds of blister packs. This includes e.g. the so-called push-through packs. Push-through packs are e.g. such that the lid material is of aluminum foil or an aluminum foil laminate. Aluminum foil is a preferred material for the lids on blister packs as the thickness of the material employed requires relatively little force for it to rupture. Consequently, the energy for penetration is low and the aluminum exhibits essentially no elasticity. As a rule the base of the blister pack is made of plastic, for example plastics such as PVC, polyamides, polyolefins, polyesters and laminates or multi-layered materials containing at least one of these materials and, if desired, also containing an aluminum foil. Other blister packs feature a base which is covered by a lid foil. The lid foil may cover the whole of the base area and is usefully provided with a line of weakness in the region of each recess, or each recess may be covered with an individual lid segment. Within the line of weakness or on each lid segment may be a tab for gripping which enables the individual recess to be exposed by peeling back the lid segment. As a rule, the base and the lid are of the above mentioned materials, whereby plastic laminates may also be employed for the lid materials.
Such blister packs have found widespread use in the field of health care and for distribution of sweets such as pastilles and bonbons. Because of the possibility they offer to store sensitive contents carefully, and because of the ease with which the contents can be removed from them, such blister packs are now regarded as indispensable in daily life. With increasing endeavors being made to cut costs in health care, attempts are being made to keep the blister packs as small as possible and to limit the number of different formulations. This can mean that a pharmaceutical formulation is produced at only one concentration level and it may happen that not one whole tablet or dragee has to be taken but, e.g. according to the weight or stage of the illness of a patient, only a partial dose e.g. half of a tablet or a dragee has to be administered. It is also conceivable for one recess to accommodate two or more tablets, dragees, capsules, ampoules and the like and for only a fraction of the contents to be consumed at a given time. Returning e.g. the rest of a tablet divided into two parts to the recess is not straightforward in the case of the normal blister packs, and the recess can not be closed off again as the lid material over the recess has been torn, burst or peeled off.
SUMMARY OF THE INVENTION
The object of the present invention is to propose blister packs which enable unused amounts such a e.g. tablets or parts thereof or a dragee or one or more dragees, capsules or ampoules to be stored safely i.e. against loss or protected from moisture and dirt until consumption.
That object is achieved by way of the invention in that a moveable clamping element is provided over the lid foil surface as a lid, and the clamping element has a lid element which covers at least one opened recess, or the clamping element has two lid elements that are joined together by struts at one or both ends, and one of these two lid elements covers at least one opened recess, or both lid elements each cover at least one opened recess, or at least one opposite lying, opened recess, and the clamping type element can be displaced along the blister pack in a sliding manner, and the clamping type element closes off at least one recess having a ruptured or removed lid foil or at least one recess which was empty and uncovered at first filling.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention may be more readily understandable from a consideration of the accompanying drawings, wherein:
FIG. 1a shows a plan view of a normally used blister pack, FIG. 1b shows a longitudinal section through the blister pack of FIG. 1a, and FIG. 1c shows a cross-section through the blister pack of FIG. 1a;
FIG. 2a shows a plan view of a blister pack of the present invention, FIG. 2b shows a longitudinal section through the blister pack of FIG. 2a along line 2b--2b of FIG. 2a, FIG. 2c shows a cross-section along line 2c--2c of FIG. 2a, and FIG. 2d shows a cross-section along line 2d--2d of FIG. 2a;
FIG. 3a shows a plan view of another embodiment of the blister pack of the present invention, FIG. 3b shows a longitudinal section through the blister pack of FIG. 3a, and FIG. 3c shows a cross-section along line 3c--3c of FIG. 3a;
FIG. 4a shows a plan view of another embodiment of the blister pack of the present invention, FIG. 4b shows a longitudinal section through the blister pack of FIG. 4a, FIG. 4c shows a cross-section through the blister pack of FIG. 4a, and FIG. 4d shows a clamping element; and
FIG. 5a shows a plan view of a blister pack of the present invention which is round in plan view, FIG. 5b shows a section through the plan view of FIG. 5a, and FIG. 5c hows a cross-section through the blister pack of FIG. 5a.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The base of the present blister packs may be embossed, deep drawn or vacuum shaped bases out of plastic, plastic laminates, plastic/paper laminates or plastic/ metal foil laminates. Suitable plastics for base materials are e.g. films and film laminates containing PVC, polyamides, polyolefins, polyesters, polycarbonates etc. The bases may also feature a barrier layer against gases and vapours. Such barrier layers may e.g. be a metal foil such as an aluminum foil embedded in a plastic laminate or, usefully, ceramic layers or metallic layers embedded between two plastic layers. Ceramic layers may be produced e.g. by evaporating metals, oxides or nitrides of aluminum, silicon and other metals and semi-metals in vacuum and depositing the substances on a plastic substrate. These methods are e.g. known as chemical vapor deposition and physical vapor deposition or sputtering. The ceramic layers may by preference contain aluminum oxides or silicon oxides or may be mixtures of various oxides, if desired also mixed with metals such as e.g. silicon or aluminium. Metal layers may be created by evaporating metals in vacuum and depositing the metals on a plastic substrate; aluminum layers may be mentioned here by way of example. The plastic substrate may be a plastic film or a plastic base made of the above mentioned plastics. The lid material for the push-through pack is, as a rule, an aluminum foil or a laminate containing aluminum foil. It has also been proposed to replace the aluminum foil with a plastic that exhibits low elasticity and poor stretching properties. Such plastics are obtained e.g. when large amounts of filler materials are added to the plastic. This last mentioned version would make it possible to obtain easily sorted waste material i.e. no mixture of metal and plastics. Plastics and plastic laminates could also be employed for blister packs with peel back lid material. The bases usually feature between 6 and 30 recesses in the form of cups or dishes. The recesses are surrounded by a shoulder, said shoulders together forming an interconnected flat plane. The bases are prepared e.g. as an endless strip with the contents in the recesses and brought together with the lid material, in particular in lid foil form, likewise in the form of an endless strip. The lid foil covers the base completely and e.g. by sealing or adhesive bonding is joined to the base at the shoulders. The lid foil may be sealed or adhesively bonded to the shoulders over the whole area or, by choosing a special sealing tool or bonding pattern for the purpose, this sealing or bonding may be only partial. Next, the endless strip of lidded base part may be cut to the desired size. This may be performed e.g. using a stamping tool. At the same time, the blister pack may be give outer contours, or it is possible to provide weaknesses in the lid material or the base in order to allow the blister pack to be bent or to create lid segments, making easy removal of the lid segment and removal of the contents possible.
Useful, is a blister pack according to the invention where the base and the lid foil are joined together and the blister pack folded along a line, or two blister packs lie one on top of the other such that two base halves touch each other and two lid foil halves form the outside, and a clamping element comprising two tongues connected by a strut overlap both base halves and the clamping element can be moved, by siding or lifting, over the lid foil surfaces and the breadth of one or both of the tongues is capable of covering at least one opened recess, or the clamping element comprises two lid elements that are joined at the ends by struts and each lid element is of a width that at least corresponds to the breadth of one recess, and each lid element on each lid foil half is capable of covering at least one opened recess, and the clamping element can be displaced along the length or breadth of the blister pack in a sliding manner.
Also useful is a blister pack according to the present invention the base of which features two parallel sides and the base is covered with the lid foil and, a clamping element which covers at least one or more recesses, is positioned over the lid foils in such a manner that it can be moved by sliding, and the clamping element clasps over or engages both parallel sides of the blister pack in the form of a ring.
Also useful is a blister pack according to the present invention in which the base and the lid foils are engaged by a clamping element comprising a strut and tongues on both sides of the strut, and one tongue, acting as a lid element of the clamping element, covers at least one recess on the lid foil side of the blister pack and the other tongue on the base side engages between at least two neighboring recesses or the tongue engages a recess on both sides.
Finally, a useful blister pack according to the present invention is such that the pack features a round periphery and the recesses in the base are arranged in one or more concentric circles, and the base can be rotated in the clamping element comprising lid and clamping or clasping ring, and the lid features at least one opening through which the contents can be expressed.
A clamping element covers at least one recess. A clamping element may also cover two, three or four recesses at the same time. For example, tongues may cover over one of two etc. whole rows or a part of one, two etc. rows of recesses i.e. for example two, three, four etc. recesses. Lid elements may cover one, two etc. whole rows of recesses each having e.g. one, two, three, four etc. recesses. Usefully the maximum number of recesses covered by a clamping element corresponds to the number of recesses in the blister pack minus one.
The present invention is described in greater detail with the aid of exemplified embodiments in FIGS. 1-5.
FIG. 1 shows a blister pack or push-through pack such as are normally used today for packaging pharmaceutical products such as tablets or dragees. Shown in FIG. 1a is a plan view of a blister pack 10 in which the lid foil 13 is joined at the shoulders 11 to the base 14. Indicated are the recesses 12 which are covered by the lid foil. FIG. 1b shows a longitudinal section through the blister pack 10. The base 14 with recesses 12 makes contact with the lid foil 13 at the shoulders 11. In the region of the shoulders 11 the lid foil is joined to the base e.g. by sealing or adhesive bonding (sealing/adhesive not shown). FIG. 1c shows a cross-section through the blister pack 10 with its base 14, lid foil 13 and the recesses 12 formed by them.
FIG. 2a shows a plan view of another version of the blister pack according to the invention. The blister pack 30 features two bases 34 which are covered by lid foil 33. Both bases 34 are laid on each other in such a manner that the recesses 32 in both bases interlock, and the recesses 32 in one base abuts against the shoulder region 31 of the other base; as a result both bases 34 lie against each other. The lid foils 33 of the two bases 34 face each other. In order that both bases 34 do not fall away from each other, an adhesive join 37 is provided e.g. in the form of a an adhesive strip or, in a further version, in the form of a plastic clamp or metal clamp or the like. By opening one of these adhesive joins 37 the pack can be easily opened up. The blister pack according to FIG. 2 also features a clamping element 35 or a ring-shaped clamping element 36. Both of these clamping elements represent alternative versions. Clamping element 35 comprises a strut and two tongues. The height of the strut is selected such that both tongues on the clamping element slide over both lid foils 33. FIG. 2b shows a longitudinal cross-section through the blister pack in FIG. 2a with both bases 34 engaging each other via the recesses 32, both lid foils 33, adhesive join 37 joining both halves together and the clamping element 35. Also shown is an accompanying note 38 or another form of information about the product, which may be held securely in place by the clamping element 35 or the ring-shaped clamping element 36 (not shown here). FIG. 2c shows a cross-section through a blister pack 30 from FIG. 2a along line 2c--2c in FIG. 2a. FIG. 2d shows a cross-section along line 2d--2d in FIG. 2a. FIG. 2c shows both base halves 34 with interlocking recesses 32 and lid foils 33. Clamping element 35 may e.g. feature a strut and two tongues formed on these. The clamping element 35 partially overlaps both halves of the blister pack from one side. The clamping element 35 may engage both halves with a spring action that may be created e.g. by spreading apart a clamping element made of elastic material, for example thermoplastic or elastic plastics; instead of a connecting strut a spring under tension may provide both tongues of the clamping element with the desired elastic force. The length of the tongues is usefully chosen such that the recesses 32 at the edge on both lid foil sides are covered. FIG. 2d, a section along the line 2d--2d in FIG. 2a, shows the alternative version with the ring-shaped clamping element 36. Clamping element 36 overlaps the whole blister pack across its width and clamping element 36 is e.g. rectangular in cross-section. Also the ring-shaped clamping element 36 slides over the lower and upper lid foils 33, and the clamping element 35, as with clamping element 36, is chosen to be at least somewhat larger in breadth than the diameter of a recess. The clamping element 35 can therefore be slid or changed from one side to the other, and a recess 32 that has already been opened can be closed off again. The ring-shaped clamping element 36 can be pushed back and forward and its breadth chosen such that it is at least somewhat larger than the diameter of a recess. By sliding the clamping element 36 along the side of the blister pack 30 it is possible to cover over again any recess that has been opened, and with that hold back any residual contents in the recess.
FIG. 3a shows a further version of a blister pack according to the invention. The blister pack 40 features shoulders 41 via which the lid foil is joined to the base 44 and forms recesses 42. A clamping element 45, in the form of a ring, spans the blister pack 40. The size of the cover 45 is chosen such that one side slides over the lid foil and the other side slides over the limits of the recesses 42 in the base 44. FIG. 3b shows a longitudinal section, FIG. 3c a section along line 3c--3c in FIG. 3a. The breadth of the clamping element 45 is chosen such that a recess is safely covered and e.g. also the shoulder region on both sides of the recess 42. This ensures safe retention of the contents in an opened recess 42.
FIG. 4 shows a blister pack 50 with shoulders 51 and recesses 52 in the base 54 which is covered over by the lid foil 53. FIG. 4a a plan view of the blister pack 50 and in FIG. 4b, a longitudinal section through the blister pack 50, two alternative versions of clamping elements 55 are shown. These clamping elements may e.g. be of plastic. The clamping element 55 features a strut 56 from which two tongues 57 and 59 or a tongue 57 and a double tongue 58 project out. The tongues press together in an elastic manner or by means of spring force. FIG. 4c shows the blister pack 50 sectioned across its breadth with one clamping element 55 displaced. FIG. 4d shows by way of example a clamping element 55 which features a strut 56 and a tongue 57. The breadth of the tongue is 57 is chosen such that it can engage between two recesses 52 in the base 54 and its width is usefully chosen such that the breadth of the tongue corresponds to the smallest distance between two recesses. The clamping element sits tightly between two recesses 52 due to the action of the tongue 57. On the clamping element opposite the tongue 57 is a further sheet-like tongue 59 which forms a lid that can be slid e.g. over two recesses. Also to be seen in FIG. 4a is a further clamping element 55 which, instead of a tongue 57, features a double tongue 58 that engages a recess 52 in the base 54 on two sides and can therefore not be displaced sideways. Opposite the tongue 58 is a sheet-like tongue which is able to cover at least two recesses 52. The clamping elements 55 may be drawn away in one direction from the blister pack 50 and give access to the recess 52. In other words, clamping elements 55 may be pushed onto the blister pack as slides or cursors, in particular self-clamping onto the blister pack.
FIG. 5 shows a blister pack 70 which is round in plan view. Shown in FIG. 5a is the blister pack 70 in plan view with one recess 77, here by way of example a round hole in the lid 75. As shown in FIG. 5b, a section through the plan view of the blister pack 70 and FIG. 5c, a cross-section through the pack 70, a plurality of recesses 72 is arranged in a circle. The base 74 with a plurality of compartments 72 is covered by a lid foil 73. The lid features an opening 77, which is shown in FIG. 5a by way of example as a circular hole. The position of the opening 77 in the lid 75 is situated exactly in the same mid-position as the recesses 72, and the diameter of the opening 77 is approximately the same as the diameter of a recess 72. The filled base 74 with lid foil 73 is placed in the lid 75. The lid 75 features an edge 74 and, in order to secure the base 74, e.g. a clamping or clasping ring 76 forms a clamping element in the lid 75. The clamping ring 76 may feature an edge or a groove that is directed inwards, which holds an accompanying leaflet 78 which, as the base 74, is inserted into the lid 75, As, in the case of the clamping ring 76, it concerns a ring with a large opening in the center, the accompanying leaflet can be easily removed, whereupon the recesses 72 are open from below and their contents can be easily removed via the opening 77 by pushing them through the lid foil 73. By rotating the lid 75 against the base 74, the pack may be securely closed, thus preventing the rest of the contents from falling out of the base 74. An empty recess 72 can be refilled with residual contents and, by rotating the lid 77, be closed off again.
For reasons of clarity the contents were not shown in the drawings. It is, however, obvious that in each case the contents are situated in the recesses. Contents coming into question may be e.g. tablets, dragees, pills, capsules, ampoules, also bonbons, lozenges, and tablets for chewing etc. and not excluded is that the blister packs according to the invention could also be used as packaging for technical articles such as small and very small items or spare parts for machines and equipment.
|
Blister pack for pharmaceuticals containing a base with a plurality of recesses which are surrounded by a shoulder. A lid foil is attached to the shoulders. Removable contents such as a tablet, capsules or ampoules reside in each of the recesses and may be removed therefrom by pressing the recess in question and penetrating the lid foil or by removing the lid foil over the recess. The blister pack features a movable lid or a clamping element which covers at least one recess, and the clamping element is arranged in such a manner that it can be slid over the lid foil, and the clamping element closes off again at least one recess, where the lid foil has been penetrated or peeled back, or closed again at least one recess which on filling was left unfilled and without lid.
| 1
|
This application is a continuation of application Ser. No. 08/256,739 filed Aug. 3, 1994, now abandoned.
This application is a 35 USC 371 PCT/FR93/00111 dated Feb. 4, 1993.
DESCRIPTION OF THE INVENTION
The present invention relates to new anhydrides of general formula: ##STR3## to their preparation and to their use.
In the general formula (I),
Ar represents an aryl radical, and
either R 1 represents a benzoyl or tert-butoxycarbonyl radical, R 2 represents a hydrogen atom and R 3 represents a protecting group of the hydroxyl functional group,
or R 1 represents a tert-butoxycarbonyl radical and R 2 and R 3 together form a 5- or 6-membered saturated heterocycle.
More particularly, Ar represents an optionally substituted phenyl or α- or β-naphthyl radical, it being possible for the substituents to be chosen from halogen atoms (fluorine, chlorine, bromine or iodine) and alkyl, aryl, arylalkyl, alkoxy, alkylthio, aryloxy, arylthio, hydroxyl, mercapto, acylamino, aroylamino, alkoxycarbonylamino, amino, alkylamino, dialkylamino, carboxyl, alkoxycarbonyl, carbamoyl, dialkylcarbamoyl, cyano, nitro and trifluoromethyl radicals, it being understood that the alkyl radicals and the alkyl portions of the other radicals contain 1 to 4 carbon atoms and the aryl radicals are phenyl or α- or β-naphthyl radicals.
More particularly still, Ar represents a phenyl radical optionally substituted with a chlorine or fluorine atom, or with an alkyl(methyl), alkoxy(methoxy), dialkylamino(dimethylamino), acylamino(acetylamino) or alkoxycarbonylamino(tert-butoxycarbonylamino) radical.
More particularly, R 3 represents a protecting group of the hydroxyl functional group chosen from methoxymethyl, 1-ethoxyethyl, benzyloxymethyl, (β-trimethylsilylethoxy)methyl, tetrahydropyranyl, 2,2,2-trichloroethoxymethyl or 2,2,2-trichloroethoxycarbonyl radicals.
More particularly, when R 2 and R 3 together form a 5- or 6-membered saturated heterocycle, the latter represents an oxazolidine ring which is optionally gem-disubstituted in the 2-position.
According to the present invention, the new anhydrides of general formula (I) can be obtained by reacting a dehydrating agent, such as an imide like dicyclohexylcarbodiimide, with the acid of general formula: ##STR4## in which Ar, R 1 , R 2 and R 3 are defined as above.
Generally, 0.5 to 1 mol of dehydrating agent is used per mole of acid used.
Generally, the reaction is carried out in an organic solvent chosen from halogenated aliphatic hydrocarbons, such as dichloromethane or chloroform, and aromatic hydrocarbons, such as benzene, toluene or xylenes.
Generally, the reaction is implemented at a temperature of between 0° and 30° C.
The anhydride obtained can be separated from the reaction mixture according to the usual techniques. However, it can be particularly advantageous to use the anhydride obtained prepared extemporaneously without isolation prior to its use in particular in esterification reactions.
The anhydrides of general formula (I) are generally more stable than the acids from which they derive in esterification reactions and they can lead to reactions which are more easily reproducible.
The new anhydrides of general formula (I) are particularly useful for preparing taxol or taxotere or their derivatives of general formula: ##STR5## in which R represents a hydrogen atom or an acetyl radical and R 1 and Ar are defined as above, which exhibit particularly advantageous antitumour properties.
According to the invention, the products of general formula (III) can be obtained:
either by reacting an anhydride of general formula (I), in which Ar is defined as above, R 1 represents a benzoyl or tert-butoxycarbonyl radical, R 2 represents a hydrogen atom and R 3 represents a protecting group of the hydroxyl functional group, with a derivative of baccatin III or of 10-deacetylbaccatin III of general formula: ##STR6## in which G 1 represents a protecting group of the hydroxyl functional group, such as a 2,2,2-trichloroethoxycarbonyl radical or a trialkylsilyl radical, each alkyl part of which contains 1 to 4 carbon atoms, and G 2 represents an acetyl radical or a protecting group of the hydroxyl functional group, such as a 2,2,2-trichloroethoxycarbonyl radical, in order to obtain a product of general formula: ##STR7## in which Ar, R 1 , R 2 , R 3 , G 1 and G 2 are defined as above, followed by replacement of the G 1 and R 3 , and optionally G 2 , radicals by hydrogen atoms in order to obtain the product of general formula (III).
Esterification of the alcohol of general formula (IV) is generally carried out in the presence of an activating agent, such as an aminopyridine like 4-dimethylaminopyridine, the esterification being carried out in an organic solvent, such as benzene, toluene, xylenes, ethylbenzene, isopropylbenzene or chlorobenzene, at a temperature of between 0° and 90° C.
Generally, 0.6 to 1.6 mol of anhydride of general formula (I) is used per mole of alcohol of general formula (IV).
Generally, 0.1 to 1 mol of activating agent is used per mole of alcohol of general formula (IV).
It is particularly advantageous to carry out the esterification in a medium in which the concentration of alcohol of general formula (IV) in the solvent is between 1 and 30% (weight/volume)
Depending on the nature of the protecting groups G 1 , R 2 and R 3 , their replacement by hydrogen atoms can be carried out by means of zinc in the presence of acetic acid or of an inorganic or organic acid, such as hydrochloric acid or acetic acid, in solution in an aliphatic alcohol containing 1 to 3 carbon atoms in the presence of zinc when the protecting groups represent at least one 2,2,2-trichloroethoxycarbonyl radical, or by means of an acid, such as hydrochloric acid, in an aliphatic alcohol containing 1 to 3 carbon atoms at a temperature in the region of 0° C. when the protecting groups represent at least one trialkylsilyl radical.
When the protecting group R 3 represents a methoxymethyl, 1-ethoxyethyl, benzyloxymethyl, (β-trimethylsilylethoxy)methyl or tetrahydropyranyl radical, it is possible to replace this protecting group with a hydrogen atom, by treatment in acidic medium at a temperature of between 0° and 30° C. to obtain a product of general formula: ##STR8## which can be purified prior to replacement of the protecting groups G 1 and G 2 by hydrogen atoms under the conditions described above.
or by reacting an anhydride of general formula (I), in which Ar is defined as above, R 1 represents a tert-butoxycarbonyl radical and R 2 and R 3 together form a 5- or 6-membered saturated heterocycle, with a product of general formula (IV), in order to obtain a product of general formula (V), in which Ar is defined as above, R 1 represents a tert-butoxycarbonyl radical and R 2 and R 3 together form a 5- or 6-membered saturated heterocycle, which product is treated with an inorganic or organic acid, optionally in an alcohol, under conditions which do not affect the protecting groups G 1 and G 2 , so as to obtain a product of general formula: ##STR9## in which Ar is defined as above, G 1 represents a protecting group of the hydroxyl functional group, preferably a 2,2,2-trichloroethoxycarbonyl radical, and G 2 represents an acetyl radical or a protecting group of the hydroxyl functional group, such as a 2,2,2-trichloroethoxycarbonyl radical, which product is treated with a compound which makes it possible to introduce, onto the amino functional group, a benzyl or tert-butoxycarbonyl radical in order to obtain a product of general formula (VI), in which Ar, G 1 and G 2 are defined as above, the protecting groups G 1 and G 2 of which are replaced by hydrogen atoms under the conditions described above.
Generally, esterification of the product of general formula (IV) is carried out in the presence of an activating agent, such as an aminopyridine like 4-dimethylaminopyridine, the esterification being carried out in an organic solvent, such as benzene, toluene, xylenes, ethylbenzene, isopropylbenzene or chlorobenzene, at a temperature of between 0° and 90° C.
Generally, 0.6 to 1.6 mol of anhydride of general formula (I) is used per mole of alcohol of general formula (IV).
Generally, 0.1 to 1 mol of activating agent is used per mole of alcohol of general formula (IV).
It is particularly advantageous to carry out the esterification in a medium in which the concentration of alcohol of general formula (IV) is between 1 and 30% (weight/volume).
Generally, the product of general formula (VII) is obtained by treating the product of general formula (V), in which Ar is defined as above, R 1 represents a tert-butoxycarbonyl radical and R 2 and R 3 together form a 5- or 6-membered saturated heterocycle, with formic acid, optionally in an alcohol such as ethanol, or with gaseous hydrochloric acid in an alcohol such as ethanol.
The benzoyl or tert-butoxycarbonyl group is introduced by a reacting benzoyl chloride or di(tert-butyl) dicarbonate with the product of general formula (VII), the reaction being carried out in an organic solvent, such as methylene chloride, in the presence of an inorganic base, such as sodium bicarbonate, or of an organic base, such as a tertiary amine like triethylamine.
The products of general formula (III) obtained by the use of the process according to the invention can be purified according to the usual methods.
EXAMPLES
The following examples illustrate the present invention.
EXAMPLE 1
0.206 g of dicyclohexylcarbodiimide in solution in 1 cm 3 of anhydrous methylene chloride is added, at -10° C. and under an argon atmosphere, to a solution of 1.72 g of (2R,3S)-3-phenyl-3-(tert-butoxycarbonylamino)-2-(1-ethoxyethoxy)propionic acid (4.87 mmol) in 4 cm 3 of anhydrous methylene chloride.
The reaction mixture is stirred for 40 minutes, the temperature being allowed to climb to around 20° C.
The dicyclohexylurea formed is separated by filtration under an inert atmosphere and the filtrate is concentrated to dryness under reduced pressure (20 mm of mercury; 2.7 kPa) at 30° C.
1.72 g of (2R,3S)-3-phenyl-3-(tert-butoxycarbonylamino)-2-(1-ethoxyethoxy)propionic acid anhydride are thus obtained, the characteristics of which are the following:
melting point: 43° C.
infrared spectrum (Nujol): characteristic absorption bands at 3450-3330, 1835, 1764 and 1722 cm -1
proton nuclear magnetic resonance spectrum (mixture of three isomers) (360 MHz, CDCl 3 /HMDS, chemical shifts in ppm, T=40° C.):
A isomer: 0.93 (6H, t), 0.99 (6H, d), 1.37 (18H, broad s), 3.27 (4H, multiplet), 4.36 (2H, q), 4.44 (2H, broad s), 5.53 (2H, broad s), 7.11 (4H, d), 7.20 (2H, t), 7.29 (4H, t)
B isomer: 0.93 (6H, t), 9.99 (6H, d), 1.37 (18H, broad s), 3.27 (4H, multiplet), 4.37 (2H, q), 4.44 (2H, broad s), 5.53 (2H, broad s), 7.11 (4H, d), 7.20 (2H, t), 7.29 (4H, t)
C isomer: 0.73 (6H, t), 1.12 (3H, d), 1.13 (3H, d), 1.37 (18H, broad s), 2.61 (2H, m), 3.08 (2H, m), 4.58 (2H, broad s), 4.72 (1H, q), 4.73 (1H, q), 5.53 (2H, broad s), 7.11 (4H, d), 7.20 (2H, t), 7.29 (4H, t).
EXAMPLE 2
22.16 g of (2R,3S)-3-phenyl-3-(tert-butoxycarbonylamino)-2-(1-ethoxyethoxy)propionic acid (6.28×10 -2 mol) and 12.43 g of dicyclohexylcarbodiimide (6.02×10 -2 mol) in 85 cm 3 of dry toluene are introduced into a 250 cm 3 reactor. The mixture is stirred for 30 minutes.
After filtration of the dicyclohexylurea formed, the solution obtained is added, over 8 hours, to a solution of 21 g of 4-acetoxy-2α-benzoyloxy-5β,20-epoxy-1,13α-dihydroxy-9-oxo-7β,10β-bis(2,2,2-trichloroethoxycarbonyloxy)-11-taxene, titrating at 95% (2.24×10 -2 mol), and 0.61 g of 4-dimethylaminopyridine in 84 cm 3 of dry toluene at 75° C.
The mixture is stirred for a further 2 hours after the end of the addition. After cooling to a temperature in the region of 20° C., the dicyclohexylurea is separated by filtration. The filtrate is concentrated to dryness and the residue is taken up in 150 cm 3 of cyclohexane. After completely solubilizing at 60° C. the solution is poured onto 350 cm 3 of heptane cooled to a temperature of between 1° and 5° C. The precipitate formed is separated by filtration, washed with cold heptane and then dried under reduced pressure. 38 g of a slightly brown product are thus obtained, the analysis of which by high performance liquid chromatography (HPLC) shows that it contains 25.5 g of 4-acetoxy-2α-benzoyloxy-5β,20-epoxy-1-hydroxy-9-oxo-7β,10.beta.-bis(2,2,2-trichloroethoxycarbonyloxy)-11-taxen-13α-yl (2R,3S)-3-(tert-butoxycarbonylamino)-3-phenyl-2-(1-ethoxyethoxy)propionate containing 15% of 2S,3S epimer.
The product obtained, treated under the conditions described in American U.S. Pat. No. 4,924,011, provides 4-acetoxy-2α-benzoyloxy-5β,20-epoxy-1,7β,10β-trihydroxy-9-oxo-11-taxen-13α-yl (2R,3S)-3-(tert-butoxycarbonylamino)-3-phenyl-2-hydroxypropionate.
EXAMPLE 3
0.206 g of dicyclohexylcarbodiimide is added, at a temperature in the region of 20° C. and under an argon atmosphere, to a solution of 1.6 g of (4S,5R)-3-(tert-butoxycarbonyl)-2,2-dimethyl-4-phenyloxazolidine-5-carboxylic acid in 5 cm 3 of anhydrous methylene chloride.
The reaction mixture is stirred for 35 minutes.
The dicyclohexylurea formed is separated by filtration and the filtrate is concentrated to dryness under reduced pressure (20 mm of mercury; 2.7 kPa) at 30° C.
1.5 g of (4S,5R)-3-(tert-butoxycarbonyl)-2,2-dimethyl-4-phenyloxazolidine-5-carboxylic acid anhydride are thus obtained, the characteristics of which are the following:
melting point: 46° C.
infrared spectrum (Nujol): main characteristic absorption bands at 1836, 1764 and 1703 cm -1
proton nuclear magnetic resonance spectrum (360 MHz; DMSO/HMDS; chemical shifts in ppm): 1.15 (broad s, 9H), 1.57 (s, 3H), 1.64 (s, 3H), 4.52 (d, 1H), 5.03 (broad s, 1H), 7.28 (m, 5H).
EXAMPLE 4
By proceeding as in Example 2, but using the anhydride of a (4S,5R)-3-(tert-butoxycarbonyl)-2,2-dimethyl-4-aryloxazolidine-5-carboxylic acid prepared under the conditions of Example 3 and passing via the intermediacy of the product of general formula (VII), with which di(tert-butyl)dicarbonate or benzoyl chloride is reacted, the following products are prepared:
4-acetoxy-2α-benzoyloxy-5β,20-epoxy-1,7β,10β-trihydroxy-9-oxo-11-taxen-13α-yl (2R,3S)-3-(tert-butoxycarbonylamino)-3-(4-methylphenyl)-2-hydroxypropionate, the optical rotation of which is [α] D 20 =-32° (c=0.1; methanol),
4-acetoxy-2α-benzoyloxy-5β,20-epoxy-1,7β,10β-trihydroxy-9-oxo-11-taxen-13α-yl (2R,3S)-3-(tert-butoxycarbonylamino)-3-(3-fluorophenyl)-2-hydroxypropionate, the optical rotation of which is [α] D 20 =-34° (c=0.59; methanol),
4-acetoxy-2α-benzoyloxy-5β,20-epoxy-1,7β,10β-trihydroxy-9-oxo-11-taxen-13α-yl (2R,3S)-3-(tert-butoxycarbonylamino)-3-(2-fluorophenyl)-2-hydroxypropionate, the optical rotation of which is [α] D 20 =-42° (c=0.58; methanol),
4-acetoxy-2α-benzoyloxy-5β,20-epoxy-1,7β,10β-trihydroxy-9-oxo-11-taxen-13α-yl (2R,3S)-3-(tert-butoxycarbonylamino)-3-(4-chlorophenyl)-2-hydroxypropionate, the optical rotation of which is [α] D 20 =-27° (c=0.97; methanol),
4-acetoxy-2α-benzoyloxy-5β,20-epoxy-1,7β,10β-trihydroxy-9-oxo-11-taxen-13α-yl (2R,3S)-3-(tert-butoxycarbonylamino)-3-(4-methoxyphenyl)-2-hydroxypropionate, the optical rotation of which is [α] D 20 =-32° (c=0.47; methanol),
4-acetoxy-2α-benzoyloxy-5β,20-epoxy-1,7β,10β-trihydroxy-9-oxo-11-taxen-13α-yl (2R,3S)-3-(tert-butoxycarbonylamino)-3-(4-fluorophenyl)-2-hydroxypropionate, the optical rotation of which is [α] D 20 =-35° (c=0.49; methanol), and
4,10β-diacetoxy-2α-benzoyloxy-5β,20-epoxy-1,7β-dihydroxy-9-oxo-11-taxen-13α-yl (2R,3S)-3-benzoylamino-2-hydroxy-3-phenylpropionate (or taxol).
The present invention also relates to the products of general formula (III) when they are obtained by a process using an anhydride of general formula (I).
The present invention also relates to the antitumour compositions which contain a product of general formula (III) when it is obtained by a process using an anhydride of general formula (I).
Although the invention has been described in conjunction with specific embodiments, it is evident that many alternatives and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, the invention is intended to embrace all of the alternatives and variations that fall within the spirit and scope of the appended claims. The above references are hereby incorporated by reference.
|
This invention relates to novel anhydrides of general formula (I), ##STR1## wherein Ar is an aryl radical, and either R 1 is C 6 H 5 --CO or (CH 3 ) 3 C--O--CO, R 2 is a hydrogen atom and R 3 is a hydroxy function protective grouping, or R 1 is (CH 3 ) 3 C--O--CO and R 2 together form a saturated 5 or 6-membered heterocyclic ring; preparation thereof; and uses thereof for preparing taxane derivatives having general formula (III), ##STR2## wherein R=H, acetyl; R 1 is C 6 --H 5 --CO or (CH 3 ) 3 C--O--CO), and having antitumoral properties.
| 2
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to cavity prevention in preforming plastic optical fiber, and more particularly, to a cavity-preventing type reactor and a method for fabricating a preform for a plastic optical fiber using the same.
2. Description of the Related Art
Optical fibers used in the field of telecommunications are generally classified into a single-mode fiber and a multi-mode fiber in terms of the transmission mode of optical signal. Optical fibers currently used for long distance, high speed communications are mostly step-index, single-mode optical fibers based on quartz glass. These optical fibers have a diameter as small as 5 microns to 10 microns, and as a result, use of these glass optical fibers creates significant difficulties in terms of achieving proper alignment and connection. Accordingly, these glass optical fibers are associated with significant expenses relating to achieving proper alignment and connection.
Multi-mode glass optical fibers have a diameter that is larger than that of single-mode optical fibers and may be used for short distance communications such as in local area networks (LANs). However, these multi-mode glass optical fibers, in addition to being fragile, also suffer from expensive costs relating to achieving proper alignment and connection and therefore are not widely used. Accordingly, these multi-mode glass optical fibers have been mainly used for short distance communication applications of up to 200 meters, such as in LANs, which normally use a metal cable, for example, a twisted pair or coaxial cable. Since the data transmission capacity or bandwidth of the metal cable may be as low as about 150 Mbps, it cannot satisfy standards for transmission capacity, such as a speed of 625 Mbps that is associated with modem asynchronous transfer mode (ATM) for data transmission.
To overcome the foregoing, plastic optical fibers, which can be used in short distance communication applications, such as LANs, have been developed. The diameter of plastic optical fibers may be as large as 0.5 to 1.0 mm which is 100 or more times larger than that of glass optical fibers. Due to the flexibility of plastic optical fibers, proper alignment and connection are much easier to achieve with plastic optical fibers than with glass optical fibers. Moreover, since polymer-based connectors may be inexpensively produced using a compression molding, these connectors may be used for both alignment and connection, thereby further reducing costs.
Plastic optical fibers may have a step-index (SI) structure, in which a refractive index changes stepwise in a radial direction, or a graded-index (GI) structure, in which a refractive index changes gradually in a radial direction. However, since plastic optical fibers having a SI structure are characterized by a high modal dispersion, the transmission capacity (or bandwidth) of a signal cannot be larger than that of cable. On the other hand, since plastic optical fibers having a GI structure are characterized by a low modal dispersion, it can have a large transmission capacity. Therefore, GI plastic optical fibers have become widely used as a communication medium for short distance, high-speed communications.
Conventional methods for fabricating GI plastic optical fiber are mainly classified into two methods. A first method comprises a batch process, wherein a preliminary cylindrical molding product, namely, a preform in which a refractive index changes in a radial direction, is fabricated, and then the resultant preform is heated and drawn to fabricate GI plastic optical fiber. A second method comprises a continuous process wherein a plastic fiber is produced by an extrusion process, and then a low molecular material contained in the fiber is extracted to obtain GI plastic optical fiber. Alternatively, a low molecular material can be introduced to the fiber in a radial direction.
The first method can be used successfully to fabricate a GI plastic optical fiber having a data transmission capacity of 2.5 Gbps, and the second method can be used successfully to fabricate a plastic optical fiber having a relatively large data transmission capacity.
Another conventional method for fabricating GI preforms employs very high rotational speeds, e.g., about 20,000 rpm). This method uses the principle that if a mixture of monomers or polymer-dissolving monomers having different densities and refractive indexes is polymerized in a very strong centrifugal field over 10,000×d −0.5 rpm, where d is a diameter of a preform, a concentration gradient is generated on account of a density gradient, and thereby, a refractive index gradient is generated. While a high rotational speed is known in the art as being advantageous in producing a definite refractive index profile, even in a relatively weak centrifugal field, a concentration (or refractive index) gradient develops, if there is a density difference between the components of a mixture.
A significant disadvantage of the aforementioned methods is a problem caused by volume shrinkage that occurs during (radical) chain polymerization, which is common in the fabrication of GI preform. For example, the extent of volume shrinkage from methylmethacrylate to poly(methylmethacrylate) is over 20%. Since volume shrinkage occurs when monomers are polymerized (to produce a polymer), a preform for a plastic optical fiber fabricated under the rotation of a reactor forms a central cavity in the shape of a tube. Thus, it is required to fill the cavity with additional monomer, prepolymer or polymer-dissolving monomers in order to fabricate a cavity-free preform.
Accordingly, when a plastic optical fiber is fabricated using a cavity-filling type preform, the probability of developing a discontinuity of the refractive index profile increases in proportion to the size of a cavity. This discontinuity can lead to a significant scattering at the interface of the plastic optical fiber. Such scattering may reduce the data transmission capacity of the plastic optical fiber to such a degree that the optical fiber may not be useable at all.
Furthermore, in the process of filling the cavity, the quality of the resultant preform may deteriorate due to contact with minute particles of dust, air and/or moisture. Thus, additional appliance and manufacturing expense may be required in order to prevent this contact and/or to compensate for this degradation.
SUMMARY OF THE INVENTION
A feature of the embodiments of the present invention is to provide a cavity-preventing type reactor, wherein it is not required to introduce an additional monomer.
Another feature of the present invention is to provide a method for fabricating a preform for a plastic optical fiber, wherein the refractive index gradient in a radial direction is regulated by controlling the composition of a reactant in the form of a mixture of monomers, prepolymers or polymer-dissolving monomers used in filling the cavity-preventing type reactor and/or by controlling the rotation speed of the cavity-preventing type reactor according to the desired degree of polymerization of the reactant.
According to one aspect of the present invention, there is provided a cavity-preventing type reactor, comprising an introduction part having a reactant inlet through which a reactant is introduced into the reactor, a reaction part; and at least one cavity-preventing structure, wherein the introduction part and the reaction part are adjacent and separated by a wall having a reactant flow path through which the introduction part is in communication with the reaction part, and the at least one cavity-preventing structure having at least one reactant flow path and disposed in the flow path of the reactant between the reaction part and the reactant inlet of the introduction part to allow the reactant to flow from the introduction part to the reaction part while preventing a cavity from extending into the reaction part during rotation of the reactor. The shape of the cavity-preventing structure may be cylindrical or plate-like. The reactor may be made of glass, quartz, ceramics or plastics. The radius of the reactor may be between approximately 1 and 10 cm and a length of the reactor may be 100 cm or less.
According to another aspect of the present invention, there is provided a method for fabricating a preform for a plastic optical fiber using the cavity-preventing type reactor, comprising filling the reaction part and the introduction part of the reactor with a reactant; and polymerizing the reactant in the reaction part under the rotation of the reactor.
The foregoing method for fabricating a preform may further include an additional step of charging and pressurizing any unoccupied space of the introduction part with inert gas after filling the reaction part of the introduction part of the reactor with a reactant. The foregoing method for fabricating a preform may further include pressurizing both an inner part and an outer part of the cavity-preventing type reactor during one or more of the processing steps. The foregoing method for fabricating a preform preferably may further include rotating the reactor at a constant or a varying speed. In the case of a varying speed, the varying speed may be characterized as having a simple repetition of rotating and stopping, a sinusoidal function or a function whose period, phase and/or amplitude may be varied.
The reactant for the foregoing method for fabricating a preform may be a monomer mixture comprising at least two kinds of monomers having a different refractive index relative to each other, a polymerization initiator and a chain transfer agent. Further, the at least two kinds of monomers are preferably two monomers wherein one monomer has a higher refractive index and a lower density than the other monomer, and a mixture composing the two kinds of monomers, a polymerization initiator and a chain transfer agent are charged into the introduction part and the reaction part of the reactor. In one embodiment, the monomer mixture filling the introduction part preferably has a higher refractive index than that of a monomer filling the reaction part. In another embodiment, the monomer mixture may be prepared by swelling or dissolving crushed fragments of a polymer having a lower refractive index than that of the monomer mixture in the introduction part and filling the reaction part of the reactor with the resultant monomer mixture.
In still another embodiment of the foregoing method for fabricating a preform for a plastic optical fiber according to the present invention, the filling of the reaction part of the reactor may be conducted by, after dissolving a prepolymer having a lower refractive index than that of the monomer mixture in the introduction part, filling the reaction part of the reactor with the resultant monomer mixture or by, after partially filling the reaction part with only a prepolymer, filling the remaining reaction part with a monomer mixture.
The at least two kinds of monomers are preferably selected from the group consisting of methylmethacrylate, benzylmethacrylate, phenylmethacrylate, 1-methylcyclohexylmethacrylate, cyclohexylmethacrylate, chlorobenzylmethacrylate, 1-phenylethylmethacrylate, 1,2-diphenylethylmethacrylate, diphenylmethylmethacrylate, furfurylmethacrylate, 1-phenylcyclohexylmethacrylate, pentachlorophenylmethacrylate, pentabromophenylmethacrylate, styrene, TFEMA(2,2,2-trifluoroethylmethacrylate), PFPMA (2,2,3,3,3-pentafluoropropylmethacrylate), HFIPMA(1,1,1,3,3,3-hexafluoroisopropylmethacrylate) and HFBMA(2,2,3,3,4,4,4-heptafluorobuthylmethacrylate).
Further, the aforementioned polymer may be a homopolymer of a monomer selected from the group consisting of methylmethacrylate, benzylmethacrylate, phenylmethacrylate, 1-methylcyclohexylmethacrylate, cyclohexylmethacrylate, chlorobenzylmethacrylate, 1-phenylethylmethacrylate, 1,2-diphenylethylmethacrylate, diphenylmethylmethacrylate, furfurylmethacrylate, 1-phenylcyclohexylmethacrylate, pentachlorophenylmethacrylate, pentabromophenylmethacrylate, styrene, TFEMA(2,2,2-trifluoroethylmethacrylate), PFPMA(2,2,3,3,3-pentafluoropropylmethacrylate), HFIPMA(1,1,1,3,3,3-hexafluoroisopropylmethacrylate) and HFBMA (2,2,3,3,4,4,4-heptafluorobuthylmethacrylate). Alternatively, the aforementioned polymer may be a copolymer, such as one selected from the group consisting of methylmethacrylate(MMA)-benzylmethacrylate(BMA) copolymer, styrene-acrylonitrile copolymer (SAN), MMA-TFEMA (2,2,2-trifluoroethylmethacrylate) copolymer, MMA-PFPMA (2,2,3,3,3-pentafluoropropylmethacrylate) copolymer, MMA-HFIPMA (1,1,1,3,3,3-hexafluoroisopropylmethacrylate) copolymer, MMA-HFBMA(2,2,3,3,4,4,4-heptafluorobuthylmethacrylate) copolymer, TFEMA-PFPMA copolymer, TFEMA-HFIPMA copolymer, styrene-methylmethacrylate copolymer and TFEMA-HFBMA copolymer.
The aforementioned prepolymer is preferably made from one or more monomers selected from the group consisting of methylmethacrylate, benzylmethacrylate, phenylmethacrylate, 1-methylcyclohexylmethacrylate, cyclohexylmethacrylate, chlorobenzylmethacrylate, 1-phenylethylmethacrylate, 1,2-diphenylethylmetha-crylate, diphenylmethylmethacrylate, furfurylmethacrylate, 1-phenylcyclohexylmethacrylate, pentachlorophenylmethacrylate, pentabromophenylmethacrylate, styrene, TFEMA(2,2,2-trifluoroethylmethacrylate), PFPMA(2,2,3,3,3-pentafluoropropylmethacrylate), HFIPMA(1,1,1,3,3,3-hexafluoroisopropylmethacrylate) and HFBMA (2,2,3,3,4,4,4-heptafluorobuthylmethacrylate). The prepolymer preferably has a viscosity from 500 to 500,000 cps at 25° C.
In all the foregoing embodiments, the reactant of the reaction part may be polymerized using thermal polymerization or UV photopolymerization. Further, in any of the foregoing steps, the reactor may be rotated while set to an angle from −90 to 90 degrees relative to the horizontal surface.
These and other features of the present invention will be readily apparent to those of ordinary skill in the art upon review of the detailed description that follows.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a preferred embodiment of a cavity-preventing type reactor according to the present invention.
FIGS. 2A–2E illustrate a series of diagrams showing the process steps for fabricating a preform for a plastic optical fiber according to a preferred embodiment of the present invention.
FIGS. 3A and 3B illustrate cross-sectional views of another preferred embodiment of the present invention.
FIG. 4 illustrates a cross-sectional view of a reactor showing a cavity formed in a rotating reactor.
FIG. 5 illustrates a schematic view of an inclined reactor.
FIG. 6 illustrates a cross-sectional view of an apparatus used for pressurizing both an inner part and an outer part of a reactor.
FIG. 7 illustrates a cross-sectional view of a reaction apparatus where ultraviolet (UV) light is used for polymerization.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Priority Korean Patent Application No. 2001-43151, filed Jul. 18, 2001 and Priority Korean Application No. 2001-78965, filed Dec. 13, 2001 are hereby incorporated in their entirety by reference.
The present invention will now be described in detail with respect to preferred embodiments as illustrated in the attached drawings.
FIG. 1 illustrates a preferred embodiment of a cavity-preventing type reactor 8 according to the present invention.
The reactor 8 is preferably cylindrical and is preferably divided into an introduction part 10 and a reaction part 20 . The introduction part 10 may be equipped with a reactant inlet 11 through which a reactant is fed into the whole reactor 8 . The reaction part 20 may be equipped with a flow path 21 through which a reactant flows from the introduction part 10 to the reaction part 20 . Between the introduction part 10 and the reaction part 20 , there are preferably provided a wall 32 and a cavity-preventing structure 30 . As a result, the wall 32 and the cavity preventing structure 30 prevent any cavity 34 that may have developed in the introduction part 10 from extending into the reaction part 20 when the reactor 8 is under rotation. The cavity-preventing structure 30 is equipped with flow paths 31 through which reactant flows from the introduction part 10 to the reaction part 20 .
FIGS. 2 a – 2 e illustrates a series of diagrams showing the preferred process steps for fabricating a preform for a plastic optical fiber using the preferred embodiment of the present invention depicted in the FIG. 1 . When the reactor 8 is rotated, a cavity 34 develops in reactant 36 from the unoccupied space as shown in FIG. 2 b . As the rotational force (i.e. speed) is increased, cavity 34 extends (i.e. downward) to the top of cavity-preventing structure 30 as shown in exemplary FIG. 2 c . With further increase in the rotational force, cavity 34 becomes cylindrical as reactant 36 is forced to the sidewalls of the introduction part 10 as shown in FIG. 2 d . However, the cavity 34 does not extend to the reaction part 20 because of the cavity-preventing structure 30 .
As the reactant 36 in the reaction part 20 is polymerized under the continuous rotation of the reactor 8 , volume shrinkage occurs. By introducing an additional volume of reactant—which is equal to the amount of the shrunken volume, the reactant 36 flows from the introduction part 10 to the reaction part 20 through flow paths 31 of cavity-preventing structure 30 as shown in FIG. 2 e . As can be seen in FIG. 2 e , the flow of reactant 36 is forced back to the center of reactor 8 as it enters into reaction part 20 . As a result, the cavity in the introduction part 10 become larger and no cavity is formed in the reaction part 20 . It is preferable to pressurize the reactant in the introduction part 10 with an inert gas in order to assist the reactant flow from the introduction part 10 flow into the reaction part 20 .
A cavity-preventing type reactor according to the present invention is not limited to the reactor 8 depicted in FIG. 1 . Any reactor may be used on the condition that a cavity that developed in an introduction part 10 doesn't extend into a reaction part 20 and that the reactant in the introduction part 10 flows into the reaction part 20 . For example, a diameter of a reaction part and a diameter of an introduction part may be the same as depicted in the FIG. 1 or may be different from each other. The shape of a cavity preventing structure may be cylindrical as depicted in FIG. 1 or may be plate-like. The number of cavity preventing structures may be one as depicted in FIG. 1 or may be 2 or more. An introduction part may exist above a reaction part as depicted in FIG. 1 or vice versa. It is also possible that a reaction part may lie along with the axis of rotation and is encircled with an introduction part.
FIGS. 3( a ) and 3 ( b ) illustrate cross-sectional views of another preferred embodiment of the present invention. FIG. 3( a ) shows a reactor 8 equipped with two cavity-preventing structures 30 having the same structure as depicted in FIG. 1 . FIG. 3( b ) shows a reactor 8 equipped with alternative exemplary plate-like cavity-preventing structures 38 or 32 between an introduction part 10 and a reaction part 20 . The structure may have several flow paths 31 on the peripheral part of the plate as shown in plate-like cavity-preventing structure 38 or have a single flow path 21 as shown in plate-like cavity-preventing structure 32 . The number and type of plate-like cavity-preventing structures may be any combination of the above or some other appropriate geometric arrangement.
The aforementioned embodiments are presented to exemplify the cavity-preventing type reactor of the present invention only, and are not as intended to be limiting of the scope of the present invention.
Hereinafter, a fabrication method of a preform for a plastic optical fiber, using a cavity-preventing type reactor 8 according to the present invention is disclosed in detail.
In the present invention, a reactant 36 is fed into the reaction part 20 of the cavity-preventing type reactor 8 , and then is polymerized during the rotation to provide a preform for a plastic optical fiber. At this time, refractive index distribution in a radial direction of a preform for a plastic optical fiber is regulated by controlling the composition of the reactant 36 introduced to the reaction part 10 and the introduction part 20 , the rotation speed of a reactor, etc.
Preferred embodiments of fabrication methods of a preform for a plastic optical fiber, wherein the cavity-preventing type reactor is used, are explained hereinafter. In the following embodiments, when particular things items are not explicitly referenced, the words such as ‘reactant’ should be interpreted as monomer(s), prepolymer(s) or polymer-dissolving monomer(s) containing a thermal or photo initiator and a chain transfer agent, which are available in polymerization reaction.
In a first preferred embodiment according to the present invention, the refractive index gradient of a reactant 36 filling a reaction part 20 may be made to be different from that of a reactant filling an introduction part 10 by regulating the ratios of compositions of monomers.
In a first step, two kinds of reactants 36 having the different ratios of composition of monomers are preferably prepared using two or more kinds of monomers having different refractive indexes. Then, a reaction part 20 of a reactor 8 is preferably filled with a reactant 36 having a low refractive index, and an introduction part 10 of a reactor 8 is thereafter filled with a reactant 36 having a high refractive index. Finally, the reactant in the reaction part 20 is polymerized while the reactor 8 is rotated in at either a constant or variable speed.
At this time, volume shrinkage occurs in the reaction part 20 as reaction progresses and simultaneously, the reactant 36 having a high refractive index flows from the introduction part 10 to the center of the reaction part 20 . Thus, the volume shrinkage is transferred to the introduction part 20 and the refractive index of the center of the reaction part becomes high. Because volume shrinkage occurs during the polymerization process, the reactant introduced to the center of the reaction part diffuses into polymer or oligomer in the reaction part 20 to provide the preform with continuous refractive index gradient. As a result, when polymerization is completed, a preform for a plastic optical fiber with a continuous refractive index gradient in a radial direction is provided.
In a second preferred embodiment according to the present invention, a reaction part 20 and an introduction part 10 of a reactor 8 are filled with only one kind of reactant.
In a first step, a monomer having a low refractive index and high density is preferably mixed with a monomer having a high refractive index and low density to provide a reactant. The reactant is then fed into a reaction part 20 and an introduction part 10 of a cavity-preventing type reactor 8 . Thirdly, the reactant in the reaction part is thermally polymerized without rotation. When polymerization is performed to a certain degree, the reactor preferably begins rotating at a constant or variable speed until polymerization is completed. Finally, a preform for a plastic optical fiber with a continuous refractive index gradient in a radial direction is provided. Thus, even if the reaction part 20 and the introduction part 10 are filled with only one kind of reactant, a monomer having a low refractive index and high density may be diffused to the outer part of the reactor under the rotation of a reactor to provide a preform for a plastic optical fiber, with a refractive index distribution, wherein a refractive index corresponding to the central part of the preform is higher than that corresponding to the outer part of the preform.
According to a third preferred embodiment of the present invention, prior to forming a core part, by filling partly the reaction part 20 with a reactant 36 and polymerizing the reactant 36 by rotating the reactor 8 , a clad part is preferably formed.
In a first step, a reactant having a low refractive index is fed into reaction part 20 of a reactor 8 and is polymerized under the rotation at a constant speed to be formed as a clad part having desired thickness. Secondly, when the clad part is completely polymerized to be glassified, the reaction part 20 and the introduction part 10 are respectively filled with different monomer mixtures distinguished from each other in mixing ratio of monomers as in the first preferred embodiment of the present invention or only a single monomer mixture in the same manner as in the second preferred embodiment of the present invention. Finally, the reactant is polymerized under the rotation in a constant or variable speed to provide a preform for a plastic optical fiber, with a continuous refractive index gradient in a radial direction.
A fourth preferred embodiment of the present invention, features a first step, wherein crushed fragments of a polymer having a lower refractive index and higher density than those of a monomer mixture are preferably swelled or dissolved in the monomer mixture. In a second step, the reactant of the polymer-dissolving monomers is fed into a reaction part 20 and an introduction part 10 of a reactor 8 , and then is polymerized. When the reactant in the reaction part 20 is polymerized under the rotation of the reactor, the dissolved polymer having a higher density than that of the monomer mixture moves to the outer region of the reactor to form a clad part.
This preferred embodiment of the present invention has the following advantages:
a clad part may be formed by only one reactant introduction;
relatively less heat is emitted during the polymerization process; and
the volume shrinkage is significantly reduced, such that the fabrication process becomes more stable.
In this preferred embodiment of the present invention, a reaction part and an introduction part are respectively filled with different monomer mixtures distinguished from each other in mixing ratio of monomers in the same manner as the first preferred embodiment of the present invention or with only one monomer mixture in the same manner as the second preferred embodiment of the present invention.
In a fifth preferred embodiment of the present invention, a monomer mixture and a prepolymer are used together as reactants.
In a first step, the prepolymer, which has a lower refractive index and higher density than those of the monomer mixture, is prepared. Secondly, the prepolymer is mixed into the monomer mixture, and then is fed into reaction part 20 and introduction part 10 . Alternatively, a reaction part may be party filled with the prepolymer, and then the remainder of the whole reactor is filled with the monomer mixture. Thirdly, polymerization is carried out under the rotation of the reactor at a constant or variable speed to provide a preform for a plastic optical fiber with a continuous refractive index gradient in a radial direction. At this time, a composition ratio of the mixture filling the introduction part 10 may be controlled differently from that of the mixture filling the reaction part 20 as in the first preferred embodiment of the invention. The viscosity of a prepolymer is preferably 500 to 500,000 cps (at 25° C.), more preferably 1,000 to 10,000 cps (at 25° C.). If viscosity of a prepolymer is less than 500 cps, it is difficult to obtain effective prepolymer addition. If viscosity of a prepolymer is more than 500,000 cps, many bubbles may be formed in a preform and it may take a long time to introduce it to the reactor.
The fifth preferred embodiment of the present invention, wherein a prepolymer is used, has the following advantages, which are similar to those of the fourth preferred embodiment of the present invention, wherein a polymer is dissolved:
a clad part can be formed using only one reactant introduction;
relatively less heat is emitted during the polymerization process; and
the volume shrinkage is significantly reduced, such that the fabrication process becomes more stable.
In a sixth preferred embodiment of the present invention, a reactor is preferably rotated while set at an angle from −90 to 90 degrees relative to the horizontal surface (see FIG. 5 ) in order to eliminate the refractive index gradient in an axial direction of a preform, which is caused by gravity.
FIG. 4 illustrates a cross-sectional view showing a cavity 34 formed in a reactor 8 rotating about a vertical axis z. In a cavity-preventing type reactor, as the reactant 36 in a reaction part 20 is polymerized, its volume is shrunk to provide an imaginary meniscus. If this imaginary meniscus is taken into account, we can estimate the amount of the reactant 36 that flows from an introduction part 10 to a reaction part 20 . This estimation can also provide a standard for a refractive index distribution profile and uniformity of refractive index gradient in an axial direction of a preform.
The meniscus of the cavity 34 of reactor 8 preferably satisfies the formula:
z + z 0 = ( Ω 2 2 g ) r 2 ( 1 )
wherein Ω is a rotation speed (rad/s); g is a gravitational acceleration constant (about 9.8 m/s 2 ); and z 0 is a height(m) from the bottom of the imaginary meniscus to the real bottom of the reactor.
If a 20% volume shrinkage occurs when the reaction part 20 of the reactor 8 is filled with a monomer mixture, Z 0 may be induced according to the formula:
z 0 = Ω 2 R 2 10 g - L ′ 2 ( 2 )
A radius r 1 at z=0 and a radius r 2 at z=L′ may be calculated using the formula:
r 1 = 2 g Ω 2 z 0 r 2 = 2 g Ω 2 ( L ′ + z 0 ) ( 3 )
By using these radii r 1 and r 2 of the above formula 3, for example, the condition under which r 2 −r 1 <0.01R is satisfied is calculated as the formula:
Ω 2 > 223.6 gL ′ R 2 = 223.6 gL · sin θ R 2 ( 4 )
As seen in the above formula 4, not only raising the rotation speed (Ω) of the reactor, but also reducing the height L′ along to the gravitational direction, contributes to obtaining uniformity of a refractive index gradient in an axial direction. In order to reduce the height L′, a reactor can be inclined as depicted in the FIG. 5 , wherein the smaller the angle θ, the smaller the height L′. When the angle θ is sufficiently small, uniformity of refractive index gradient in an axial direction can be obtained even with a small rotation speed.
In all the preferred embodiments of the present invention, a cavity due to volume shrinkage generated by polymerization is formed only in an introduction part 10 . Thus, the volume of reactant 36 charged into the introduction part 10 must be regulated to secure the condition that when volume shrinkage is completed, the diameter of the bottom of the cavity 34 formed in the introduction part 10 must be less than that of the cavity preventing structure 30 in order to prevent the cavity 34 from extending into the reaction part 20 .
Furthermore, it is preferable to pressurize the introduction part 10 of reactor 8 with inert gas such as argon. Such pressurization has the following advantages: reactant flow from the introduction part 10 to the reaction part 20 is aided, thus preventing a cavity 34 from forming in the reaction part 20 of a reactor 8 ; the polymerization reaction is made more stable; and the boiling temperature of monomer is raised. Thus, a reaction may be carried out at a higher temperature, allowing for shortened reaction time, and allowing for the reaction to be carried out without formation of bubbles due to vaporization of unreacted substances.
At this time, if a cavity-preventing type reactor is made of fragile material such as glass, quartz, ceramics or plastics and so forth, it is difficult to pressurize an inner part of the reactor, i.e., an interior of the reactor, to more than 4 bars. However, if the outer part of the cavity-preventing type reactor, i.e., an area surrounding the reactor, is pressurized at the same time, the inner pressure of a reactor may be raised to 10 bars.
FIG. 6 illustrates a cross-sectional view of an apparatus used for pressurizing both the inner part and the outer part of a cavity-preventing type reactor. The apparatus of FIG. 6 may be employed using the following procedure: firstly, a rotation reaction apparatus is preferably connected to an argon gas bomb through a quick connector 1 which is positioned in the upper part of the apparatus; secondly, a height-controllable lid 2 is raised; thirdly, argon gas is fed through a pressurization path 3 to an inner part of a cavity-preventing type reactor 5 and an inner part of the reaction apparatus 6 . In a fourth step, the lid 2 is lowered and an O-ring ( 4 ) is pressed to seal the reaction apparatus. Thus, inner and outer parts may be simultaneously pressurized.
According to the present invention, in principle, a cavity 34 originating due to volume shrinkage in a reaction part 20 would not be formed. However, if a radical polymerization, wherein a monomer can be vaporized due to the heat generated during the radical polymerization, is carried out in a reaction part, the vaporized gas bubbles may gather together to form a cavity in the reaction part 20 under the rotation of a reactor 8 . As mentioned above, pressurizing the reaction part 20 prevents bubbles from collecting in the reaction part 20 , and thus a cavity-free preform may be fabricated. In all of the preferred embodiments of the present invention, polymerization in a reaction part may be carried out by using either heat or UV light.
FIG. 7 illustrates a cross-sectional view of a reaction apparatus wherein UV light is used for polymerization. When UV light is used in polymerization, a photo initiator is preferably used instead of a thermal initiator to start the reaction.
There are two significant advantages to using UV photopolymerization: 1) since there is no need to raise the temperature of a reactor, the vaporization of a monomer may be prevented thereby preventing formation of a cavity; and 2) since only the reaction part 20 is exposed to the UV light, there is no possibility that the reactant in the introduction part 10 may become classified and stop the flow of the reactant 36 to the reaction part 20 . Thus, the UV photopolymerization, provides a more stable fabrication process for creating cavity-free preforms for plastic optical fiber.
In all of the preferred embodiments of the present invention, in order to obtain an improved refractive index profile, diverse changes may be given to rotation speed of the reactor 8 . For example, diverse changes in the rotation speed may be the simple repetition of rotating and stopping the reactor 8 , according to a sinusoidal function or a function having a variable period, phase and/or amplitude.
In general, the preferred radius of the preform is about 1 to 10 cm in order to make heat transfer for polymerization easy. The preferred length of the preform is 100 cm or less in order to achieve a proper thermal drawing.
In the foregoing, two kinds of monomers having different refractive index used in the present invention are preferably selected from the group consisting of methylmethacrylate, benzylmethacrylate, phenylmethacrylate, 1-methylcyclohexylmethacrylate, cyclohexylmethacrylate, chlorobenzylmethacrylate, 1-phenylethylmethacrylate, 1,2-diphenylethylmethacrylate, diphenylmethylmethacrylate, furfurylmethacrylate, 1-phenylcyclohexylmetha-crylate, pentachlorophenylmethacrylate, pentabromophenylmetha-crylate, styrene, TFEMA(2,2,2-trifluoroethylmethacrylate), PFPMA (2,2,3,3,3-pentafluoropropylmethacrylate), HFIPMA(1,1,1,3,3,3-hexafluoroisopropylmethacrylate) and HFBMA(2,2,3,3,4,4,4-heptafluorobutylmethacrylate).
Homopolymers or copolymers may be used as the polymers in the fourth preferred embodiment of the present invention.
The homopolymer may be polymerized from a monomer such as methylmethacrylate, benzylmethacrylate, phenylmethacrylate, 1-methylcyclohexylmethacrylate, cyclohexylmethacrylate, chlorobenzylmethacrylate, 1-phenylethylmethacrylate, 1,2-diphenyl-ethylmethacrylate, diphenylmethylmethacrylate, furfurylmethacrylate, 1-phenylcyclohexylmethacrylate, pentachlorophenylmethacrylate, pentabromophenylmethacrylate, styrene, TFEMA (2,2,2-tri-fluoroethylmethacrylate), PFPMA (2,2,3,3,3-pentafluoropropylmetha-crylate), HFIPMA(1,1,1,3,3,3-hexafluoroisopropylmethacrylate) and HFBMA(2,2,3,3,4,4,4-heptafluorobuthylmethacrylate).
The copolymer may include one or more selected form the group consisting of, for example, methylmethacrylate(MMA)-benzyl-methacrylate(BMA) copolymer, styrene-acrylonitrile copolymer(SAN), MMA-TFEMA(2,2,2-trifluoroethylmethacrylate) copolymer, MMA-PFPMA (2,2,3,3,3-pentafluoropropylmethacrylate) copolymer, MMA-HFIPMA (1,1,1,3,3,3-hexafluoroisopropylmethacrylate) copolymer, MMA-HFBMA (2,2,3,3,4,4,4-heptafluorobuthylmethacrylate) copolymer, TFEMA-PFPMA copolymer, TFEMA-HFIPMA copolymer, styrene-methylmethacrylate(SM) copolymer and TFEMA-HFBMA copolymer.
The prepolymer used in the fifth preferred embodiment of the present invention may be made from one or more monomers selected from the group consisting of methylmethacrylate, benzylmethacrylate, phenylmethacrylate, 1-methylcyclohexylmetha-crylate, cyclohexylmethacrylate, chlorobenzylmethacrylate, 1-pheny-lethylmethacrylate, 1,2-diphenylethylmethacrylate, diphenylmethylmethacrylate, furfurylmethacrylate, 1-phenylcyclohexylmethacrylate, pentachlorophenylmethacrylate, pentabromophenylmethacrylate, styrene, TFEMA(2,2,2-trifluoroethylmethacrylate), PFPMA(2,2,3,3,3-pentafluoropropylmethacrylate), HFIPMA(1,1,1,3,3,3-hexafluoro-isopropylmethacrylate), and HFBMA(2,2,3,3,4,4,4-heptafluorobutylmethacrylate).
The thermal initiator which is introduced for thermal polymerization may include, for example, 2,2′-azobis(iso-butyronitrile), 1,1′-azo-bis(cyclohexanecarbonitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(methyl-butyro-nitrile), acetyl peroxide, lauroyl peroxide, benzoyl peroxide, tert-butyl peroxide, tert-butyl hydroperoxide, azo-tert-butane, azo-normal-butane and tert-butyl peracetate.
The photo initiator that is introduced for photopoly-merization may include, for example, 4-(p-tolylthio)benzophenone, 4,4′-bis(dimethylamino)benzophenone and 2-methyl-4′-(methylthio)-2-morpholino-propiophenone, 1-hydroxyl-cyclohexyl-phenyl-ketone.
The chain transfer agent that is introduced for regulating molecular weight may include, for example, n-butyl mercaptan, lauryl mercaptan and dodecyl mercaptan.
A preform for a plastic optical fiber fabricated by the above process may be subjected to a thermal drawing to transform it to a graded index plastic optical fiber (GI-POF) having a desired diameter, or may be processed to a relatively thick strand to provide a refractive index-graded lens and an image guide for picture transmission.
The present invention is now described in more detail using Examples and Comparative Examples. The Examples are intended to be only illustrative and, therefore, not intended to limit the scope of the present invention.
EXAMPLES
The cavity-preventing type reactors used in the following examples are of the same shape as depicted in FIG. 1 , wherein the diameter of reactor 8 is 40 mm, the height of the introduction part 10 of the reactor is 100 mm, the height of the reaction part 20 of reactor is 120 mm, and the total height of the cavity-preventing reactor, inducing 25 mm-high inlet, is 245 mm. At least 2 monomers were selected from the group consisting of styrene monomer(SM), methyl methacrylate(MMA) and trifluoroethyl methacrylate(TFEMA). As a thermal initiator, 2,2′-azobis isobutyronitrile(AIBN) was used in MMA-SM reaction and tert-butyl peroxybenzoate(t-BPOB) was used in MMA-TFEMA reaction. As a chain transfer agent, 1-butanethiol (1-BuSH) was used.
In a UV photoreaction, as a photo initiator, 4,4′-bis (dimethylamino) benzophenone (DMABP) was used. The loss of light of a plastic optical fiber was measured by using an optical power meter using a light source having the wavelength of 660 nm after the preform was transformed into an optical fiber having a thickness of 1 mm.
Example 1
A solution consisting of 150 g of the monomer mixture made of SM and MMA at a weight ratio of 20:80, 0.066% by weight of AIBN and 0.2% by weight of 1-BuSH, based to the weight of the resultant mixed solution was charged into the reaction part 20 of the cavity-preventing type reactor 8 to the full. A solution consisting of 110 g of the monomer mixture made of SM and MMA at a weight ratio of 40:60, 0.066% by weight of AIBN and 0.2% by weight of 1-BuSH, based to the weight of the resultant mixed solution was charged into the introduction part 10 of the cavity-preventing type reactor 8 up to a height of 85 mm. The unoccupied space of the introduction part 10 was charged with argon gas having the purity of 99.999% until the inner pressure reached 1 bar. After the reactor was closed with a lid, the reaction was performed at a rotation speed of 2,500 rpm at a temperature of 70° C. for 12 hours. Subsequently, the rotation of the reactor was paused for 5 minutes, followed by rotation in a rotation speed of 2,500 rpm for 10 minutes. These procedures were repeated several dozens of times to obtain a cavity-free preform for a plastic optical fiber. The loss of light of the resultant fiber was measured at 300 dB/km.
Example 2
A solution consisting of 260 g of the monomer mixture made of SM and MMA at a weight ratio of 30:70, 0.066% by weight of AIBN and 0.2% by weight of 1-BuSH, based to the weight of the resultant mixed solution was charged into the reaction part 20 of the cavity-preventing type reactor 8 to the full. Simultaneously, the solution was charged into the introduction part 10 of the cavity-preventing type reactor up to a height of 85 mm. The unoccupied space of the introduction part 10 was charged with argon gas having the purity of 99.999% until the inner pressure reached 1 bar. After the reactor was closed with a lid, the reaction was performed in a rotation speed of 2,500 rpm at a temperature of 70° C. for 12 hours. Subsequently, the rotation of the reactor was paused for 5 minutes, followed by rotation in a rotation speed of 2,500 rpm for 10 minutes. These procedures were repeated several dozens of times to obtain a cavity-free preform for a plastic optical fiber. The loss of light of the resultant fiber was measured at 300 dB/km.
Example 3
A solution consisting of 50 g of methylmethacrylate (MMA), 0.066% by weight of AIBN and 0.2% by weight of 1-BuSH, based to the weight of the resultant solution was charged into the reaction part 20 of the cavity-preventing type reactor 8 up to a height of 40 mm. The unoccupied space of the reactor was charged with argon gas having the purity of 99.999% until the inner pressure reached 1 bar. After the reactor was closed with a lid, the reaction was performed in a rotation speed of 2,500 rpm at a temperature of 70° C. for 12 hours to form a clad layer. Subsequently, a solution consisting of 110 g of the monomer mixture made of SM and MMA at a weight ratio of 20:80, 0.066% by weight of AIBN and 0.2% by weight of 1-BuSH, based to the weight of the resultant mixed solution was heated to a temperature of 70° C., and then was charged into the reaction part 20 of the cavity-preventing type reactor 8 . Subsequently, a solution consisting of 110 g of the monomer mixture made of SM and MMA at a weight ratio of 40:60, 0.066% by weight of AIBN and 0.2% by weight of 1-BuSH, based to the weight of the resultant mixed solution was heated to a temperature of 70° C., and then was charged into the introduction part 10 of the cavity-preventing type reactor 8 up to a height of 85 mm. The unoccupied space of the introduction part 10 was charged with argon gas having the purity of 99.999% until the inner pressure reached 1 bar. After the reactor was closed with a lid, the reaction was performed in a rotation speed of 2,500 rpm at a temperature of 70° C. for 12 hours. Subsequently, the rotation of the reactor was paused for 5 minutes, followed by rotation in a rotation speed of 2,500 rpm for 10 minutes. These procedures were repeated several dozens of times to obtain a cavity-free preform for a plastic optical fiber. The loss of light of the resultant fiber was measured at 260 dB/km.
Example 4
A solution of 50 g of methylmethacrylate (MMA), 0.066% by weight of AIBN and 0.2% by weight of 1-BuSH, based to the weight of the resultant solution was reacted at a temperature of 70° C. for 24 hours to provide a polymer. Subsequently, the polymer was dissolved in a solution consisting of 110 g of the monomer mixture made of SM and MMA at a weight ratio of 20:80, 0.066% by weight of AIBN and 0.2% by weight of 1-BuSH, based to the weight of the resultant mixed solution. The polymer-dissolved solution was charged into the reaction part 20 of the cavity-preventing type reactor 8 . Subsequently, A solution consisting of 110 g of the monomer mixture made of SM and MMA at a weight ratio of 40:60, 0.066% by weight of AIBN and 0.2% by weight of 1-BuSH, based to the weight of the resultant mixed solution was heated to a temperature of 70° C., and was charged into the introduction part 10 of the cavity-preventing type reactor 8 up to a height of 85 mm. The unoccupied space of the introduction part was charged with argon gas having the purity of 99.999% until the inner pressure reached 1 bar. After the reactor was closed with a lid, the reaction was performed in a rotation speed of 2,500 rpm at a temperature of 70° C. for 12 hours. Subsequently, the rotation of the reactor was paused for 5 minutes, followed by continuous rotation having a rotation speed of 2,500 rpm for 10 minutes. These procedures were repeated several dozens of times to obtain a cavity-free preform for a plastic optical fiber. The loss of light of the resultant fiber was measured at 250 dB/km.
Example 5
50 g of methylmethacrylate (MMA), 0.066% by weight of AIBN and 0.2% by weight of 1-BuSH, based to the weight of the resultant solution were polymerized at a temperature of 70° C. for 4 hours to provide a prepolymer. The resultant prepolymer was introduced into the reaction part of the cavity-preventing type reactor to a height of 40 mm. Subsequently, a solution consisting of 110 g of the monomer mixture made of SM and MMA at a weight ratio of 20:80, 0.066% by weight of AIBN and 0.2% by weight of 1-BuSH, based to the weight of the resultant mixed solution was charged into the remaining reaction part 20 of the cavity-preventing type reactor 8 to the full. After that, a mixed solution consisting of 110 g of the monomer mixture made of SM and MMA at a weight ratio of 40:60, 0.066% by weight of AIBN and 0.2% by weight of 1-BuSH, based to the weight of the resultant mixed solution was charged into the introduction part 10 of the cavity-preventing type reactor 8 . The unoccupied space of the introduction part 10 was charged with argon gas having the purity of 99.999% until the inner pressure reached 1 bar. After the reactor was closed with a lid, the reaction was performed in a rotation speed of 2,500 rpm at a temperature of 70° C. for 9 hours. Subsequently, the rotation of the reactor was paused for 5 minutes, followed by continuous rotation in a rotation speed of 2,500 rpm for 10 minutes. These procedures were repeated several dozens of times to obtain a cavity-free preform for a plastic optical fiber. The loss of light of the resultant fiber was measured at 230 dB/km.
Example 6
A solution consisting of 260 g of the monomer mixture made of SM and MMA at a weight ratio of 30:70, 0.066% by weight of AIBN and 0.2% by weight of 1-BuSH, based to the weight of the resultant mixed solution was charged into the reaction part 20 of the cavity-preventing type reactor 8 and simultaneously, was introduced into the introduction 10 part of the cavity-preventing type reactor 8 up to a height of 85 mm. The unoccupied space of the introduction part 10 was charged with argon gas having the purity of 99.999% until the inner pressure reached 1 bar. After the reactor was closed with a lid, the reactor was set to an angle of +15 degrees relative to the horizontal surface and then, was rotated in a rotation speed of 1,000 rpm at a temperature of 70° C. for 12 hours. Subsequently, the rotation of the reactor was paused for 5 minutes, followed by continuous rotation in a rotation speed of 2,500 rpm for 10 minutes. These procedures were repeated several dozens of times to obtain a cavity-free preform for a plastic optical fiber. The loss of light of the resultant fiber was measured at 290 dB/km.
Example 7
A solution consisting of 260 g of the monomer mixture made of SM and MMA at a weight ratio of 30:70, 0.066 wt % of DMABP and 0.2 wt % of 1-BuSH, based to the weight of the resultant solution was charged into the reaction part 20 of the cavity-preventing type reactor 8 and simultaneously, into the introduction part 10 of the cavity-preventing type reactor 8 up to a height of 85 mm. The unoccupied space of the introduction part 10 was charged with argon gas having the purity of 99.999% until the inner pressure reached 1 bar. After the reactor was closed with a lid, the reactor was rotated in a rotation speed of 2,500 rpm at a temperature of 40° C. for 12 hours with being exposed to UV by use of the same UV radiation apparatus as depicted in FIG. 7 . Subsequently, the rotation of the reactor was paused for 5 minutes, followed by continuous rotation in a rotation speed of 2,500 rpm for 10 minutes. These procedures were repeated several dozens of times to obtain a cavity-free preform for a plastic optical fiber. The loss of light of the resultant fiber was measured at 300 dB/km.
Example 8
A solution consisting of 170 g of the monomer mixture made of MMA and TFEMA at a weight ratio of 70:30, 0.066 wt % of t-BPOB and 0.25 wt % of 1-BuSH, based to the weight of the resultant solution was charged into the reaction part 20 of the cavity-preventing type reactor 8 . After the reactor was closed with a lid, the reaction was carried out at a temperature of 70° C. for 12 hours without rotation. Additionally, the reaction was carried out in a rotation speed of 2,500 rpm at a temperature of 70° C. for 12 hours to form a clad layer. Subsequently, a solution consisting of 150 g of the monomer mixture made of MMA and TFEMA at a weight ratio of 90:10, 0.066 wt % of t-BPOB and 0.25 wt % of 1-BuSH, based to the weight of the resultant solution was heated up to 70° C. and then charged into the reaction part 20 of the cavity-preventing type reactor 8 . After that, a mixed solution consisting of 120 g of MMA, 0.066% by weight of t-BPOB and 0.2% by weight of 1-BuSH, based to the weight of the resultant solution was heated to a temperature of 70° C., and was charged into the introduction part 10 of the cavity-preventing type reactor 8 up to a height of 85 mm. The unoccupied space of the introduction part 10 was charged with argon gas having the purity of 99.999% until the inner pressure reached 1 bar. The reactor was closed with a lid, the reaction was carried out in a rotation speed of 2,500 rpm at a temperature of 70° C. for 12 hours. After that, the rotation of the reactor was paused for 5 minutes, followed by rotation in a rotation speed of 2,500 rpm for 10 minutes. These procedures were repeated several dozens of times to obtain a cavity-free preform for a plastic optical fiber. The loss of light of the resultant fiber was measured at 150 dB/km.
Example 9
A solution consisting of 150 g of the monomer mixture made of SM and MMA at a weight ratio of 10:90, 0.066 wt % of AIBN and 0.2 wt % of 1-BuSH, based to the weight of the resultant solution was charged into the reaction part 20 of the cavity-preventing type reactor 8 to the full. Subsequently, a solution consisting of 110 g of the monomer mixture made of SM and MMA at a weight ratio of 20:80, 0.066 wt % of AIBN and 0.2 wt % of 1-BuSH, based to the weight of the resultant solution was charged into the introduction part 10 of the cavity-preventing type reactor 8 up to a height of 85 mm. The same rotation reaction apparatus as depicted in FIG. 6 was equipped with the cavity-preventing type reactor 8 , and then argon gas was led through a pressurization path ( 3 ) to an inner part of the cavity-preventing type reactor ( 5 ) and an inner part of the reaction apparatus ( 6 ) and was simultaneously pressurized to 10 bars. After that, the lid ( 2 ) was lowered and an O-ring ( 4 ) was pressed. After the reaction was carried out in a rotation speed of 2,500 rpm at a temperature of 110° C. for 4 hours, the temperature was lowered to 90° C. The rotation of the reactor was paused for 5 minutes, followed by rotation in a rotation speed of 2,500rpm for 10 minutes at a temperature of 110° C. The procedures were repeated several dozens of times. After 8 hours, a cavity-free preform for a plastic optical fiber was obtained. The loss of light of the resultant fiber was measured at 250 dB/km.
The reactivity of SM is so analogous to that of MMA that the preform made therefrom is an amorphous random copolymer. Even if the reactivity of TFEMA is lower to that of MMA, a transparent amorphous copolymer is made therefrom in all the aforementioned composition ratios.
The present invention provides a new cavity-preventing type reactor and a method for fabricating a preform for a plastic optical fiber having a continuous refractive index gradient and thus no discontinuity of refractive index profile in a radial direction by using the same wherein it is needless to introduce reactants additionally.
A preferred embodiment of the present invention has been disclosed herein and, although specific terms are employed, they are used in a generic and descriptive sense only and not for purpose of limitation. Accordingly, it will be understood by those of ordinary skill in the art that various changes in form and details may be made without departing from the spirit and scope of the invention as set forth in the following claims.
|
A cavity-preventing type reactor and a method for fabricating a preform for a plastic optical fiber using the same, wherein post-process charging of additional monomer or prepolymer into rotationally-induced central cavities is avoided by forming void-free plastic fibers using special geometric flow controllers combined with special materials combinations, pressures, and rotational techniques.
| 1
|
CROSS-REFERENCE TO RELATED APPLICATION
This application claims priority from Provisional Application No. 61/470,188 filed Mar. 31, 2011, the contents of which are hereby incorporated by reference.
BACKGROUND OF THE INVENTION
Temperature swing adsorption molecular sieve units are used in a variety of industries to remove contaminants from liquids and gas streams. This is a batch-wise process consisting of two basic steps which are adsorption and regeneration. In the adsorption step, contaminants are removed by being adsorbed on the solid molecular sieve material and then the treated stream leaves the unit with contaminant levels below the required specification limit or further treatment is necessary. In the regeneration step, contaminants are desorbed from the solid molecular sieve material by means of a regeneration stream (typically gas).
The regeneration step consists of two major parts—heating and cooling. In the heating part of the process, the regeneration stream, which is contaminant free, is heated to an elevated temperature (290° C. in one embodiment of the invention) and flows over the molecular sieve material. Due to the heat of the gas, mainly used as heat of desorption, and the difference in partial pressure of the contaminants on the molecular sieve material and in the regeneration gas stream, the contaminants desorb from the solid material and leave the unit with the regeneration gas. A cooling step is then necessary. As a result of the heating step the molecular sieve material heats up. To prepare the material again for the next adsorption step and since adsorption is favored at lower temperatures than desorption, the molecular sieve material needs to be cooled by means of a stream typically flowing over the molecular sieve at a temperature very close to the feed stream temperature.
Hence, the most basic form of temperature swing molecular sieve process unit consists of two vessels with one vessel in adsorption mode and the other vessel in regeneration mode. However, dependant on the amount of the feed stream to be treated as well the amount of contaminants to be removed from the feed stream, several vessels, which operate in a parallel mode, could be required. In a more complicated form of operation, the regeneration step can also be split over two vessels in a series-heat-and-cool cycle, where one of the vessels would be in the heating step and another would be in the cooling step.
Apart from the basic adsorption and regeneration steps described above, additional steps may need to be included dependent on the pressure levels of the feed stream versus the regenerant stream. For instance, if adsorption is carried out at a higher pressure than regeneration (note that a lower pressure will favour desorption of contaminants from the molecular sieve material), at a minimum, two additional steps are required: a depressurization step where the pressure is reduced from adsorption pressure to the regeneration pressure; and a repressurization where the pressure is increased from the regeneration pressure to adsorption pressure. Note that sometimes the opposite is true, with regeneration carried out at a higher pressure than adsorption, but in this case again a depressurization and repressurization step need to be included. If depressurization and repressurization steps are present they are typically part of the regeneration cycle.
All of the above steps are typically programmed into a so-called “switching sequence”, either in a Programmable Logic Controller (PLC) or Distributed Control System (DCS) to allow this in essence batch-process to work as a semi-continuous process.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a typical set-up of a molecular sieve process unit adsorber vessel and its associated valves.
FIG. 2 shows a typical molecular sieve unit switching sequence for a system with 4 beds in parallel adsorption.
FIG. 3 shows the incorporation of a purge gas step in the switching sequence with the purge step executed after the repressurization step.
FIG. 4 shows the use of a dedicated purge valve and restriction orifice.
FIG. 5 shows the switching sequence with a purge step before repressurization.
DETAILED DESCRIPTION OF THE INVENTION
In natural gas plants, for instance for Natural Gas Liquids (NGL) recovery or methane liquefaction (LNG), temperature swing adsorption molecular sieve processes are used to remove water and sulphur compounds from the natural gas so that the gas can be fed to the cryogenic NGL recovery or liquefaction section of the plant. The regenerant that is used is typically lean methane rich treated gas from downstream of the NGL Recovery unit in NGL recovery type facilities or nitrogen rich end flash gas/boil-off gas in LNG facilities.
The valve switching sequence in a typical system as shown in FIG. 2 inherently causes some operational disturbances on the downstream cryogenic units (NGL Recovery Process or LNG Liquefaction). Typically, the heating and cooling steps use a regeneration gas with significantly different composition from the actual feed gas stream. Either the regeneration gas stream is lean in the heavier hydrocarbon components (C 2+ ) or is rich in nitrogen (for instance for LNG facilities). In the case of a nitrogen-rich gas, after finishing the cooling, the vessel is filled with a significant amount of nitrogen, which, once the bed goes back into its adsorption step, will end up in the treated product gas from the unit and will be sent to the downstream cryogenic units. These cryogenic processes are typically very sensitive to a change in feed gas nitrogen content as it results in temperature and pressure fluctuations on units' exchangers and compressors. This could lead eventually to thermal stress fatigue (and eventually, failure). It is further known that molecular sieve products have a certain adsorption capacity for the hydrocarbons in the feed gas stream. During regeneration, these hydrocarbons are driven off of the material such that once an adsorber vessel comes back into its adsorption step, for a certain amount of time, hydrocarbon species adsorb on the molecular sieve material up to the point where the adsorption for a specific component reaches its saturation level. For some time this causes operational disturbances, i.e. not meeting product recoveries for specific hydrocarbon components, in for instance an NGL Recovery process. The duration of this disturbance is dependent on a number of factors, including but not limited to the amount and type of adsorbent loaded in the adsorber, the feed gas hydrocarbon speciation and feed gas flow through the adsorber in the adsorption step.
When repressurizing an adsorber vessel to prepare it to go into its adsorption step, the gas in the vessel heats up due to the adiabatic compression effect. The temperature increase of the gas in the vessel is more outspoken for adsorber vessels that are internally lined with refractory as there is even less chance for the heat to dissipate out of the vessel through the metal vessel shell compared to an externally insulated vessel. Thus once this adsorber vessel comes into adsorption, the heat will be purged out of the vessel with the product gas causing a sudden temperature increase on the product gas to the downstream cryogenic systems, again leading to operational upsets in the unit and thermal stress on some of the equipments installed in these units. The magnitude of these effects on the downstream systems depends also on the number of beds that are in parallel adsorption as eventually the product gas coming from the bed that just moved to its adsorption step is mixed with product gas from vessels that have been on adsorption already for a certain period of time and for which these initial effects are no longer present. In essence this attenuates some of the disturbances.
This purge step can be executed in two ways: through the depressurization valves or through a dedicated purge flow valve and restriction orifice. The purge step is generally through the depressurization valves which are typically already included in molecular sieve applications. Executing the purge step after the repressurization step, i.e. at high adsorption pressure, allows for a greater flow through the restriction orifices downstream the depressurization valves than executing it before repressurization step, at low regeneration gas pressure, as the high pressure case is the design point for the depressurization restriction orifices. This eventually would lead to a better purge operation. The purge can also be through a dedicated purge flow valve and restriction orifice. Although this would add extra piping and equipment to the unit, the capital expense implication is considered to be minimal (see FIG. 4 ). Further this approach allows designing the restriction orifice and sequence purge time for the optimal purge flow requirement. In order to avoid the vessel from depressurizing during the purge step resulting in an additional, although likely only very short, repressurization step after the purging, the purge gas needs to be supplied through the main feed gas valve.
The main advantages for this purge are removal of nitrogen from the vessel before it moves to its adsorption step, preloading of the molecular sieve material with key hydrocarbon components before the adsorber vessel moves to its adsorption step and removal of the adiabatic compression heat from the vessel before it moves to its adsorption step.
Overall the advantage will be that pressure, temperature and compositional fluctuations on the downstream cryogenic units can be avoided, resulting in more stable operation of the NGL recovery and LNG liquefaction processes with respect to meeting hydrocarbon product recovery specifications (resolved due to the hydrocarbon preloading), less thermal stress on the NGL recovery and LNG liquefaction processes equipment, resulting in a more reliable long-term operation (resolved due the combination of purging the adiabatic compression heat out of the system, and limiting the compositional—nitrogen and hydrocarbon—disturbances and less pressure fluctuations in the final stages of the LNG liquefaction process, which is typically the nitrogen rejection step (resolved due to purge of nitrogen out of the bed, which minimize the compositional nitrogen changes to the cryogenic units).
One skilled in the art would assess the amount of purge gas required to remove sufficient nitrogen from the vessel, preload the molecular sieve material sufficiently with key components and remove the heat from vessel to a level acceptable for minimal (i.e. no downstream unit effects).
While there have been some projects where a purge step has been employed, in all known cases this purge step is executed before the repressurization step, at the lower regeneration pressure, and not after the repressurization step, the latter being the subject of the present invention. The switching of the sequence of the purge step before the repressurization step in the sequence is shown in FIG. 5 . The purge step is either executed with feed gas being supplied through the repressurization valves and the purge gas leaving through the depressurization valves or with lean methane rich gas supplied through the regeneration gas valve(s) installed at the top of the vessel and again purge gas leaving through the depressurization valves. In both cases, by design, purge gas flow is limited by the restriction orifices installed downstream the depressurization valves (see FIG. 1 for set up).
DETAILED DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a typical set-up of a molecular sieve process unit adsorber vessel and its associated valves. A feed gas 2 is shown passing through feed gas inlet 4 and continuing in line 6 and continuing to adsorbent bed 20 where the gas is treated. A portion of the feed gas is shown passing through lines 8 and 10 to repressurization valves 12 and 16 and then to lines 14 and 18 to rejoin the feed gas in line 6 . The treated gas 28 then proceeds to line 30 to product gas valve 32 and a product gas is shown exiting in line 34 . There are provisions for the depressurization valves 44 , 50 with a portion of gas 42 , 48 shown passing through depressurization valves 44 , 50 in lines 46 , 52 , respectively. Also shown are two regeneration heating and cooling valves for the adsorbent bed. A portion of gas 22 is shown passing through regeneration and heating valve 24 and passing into line 26 similarly regeneration heating and cooling valve 38 is shown with gas flow in line 36 and line 40 either entering or exiting the product gas stream. The system provides several options for a the regeneration gas. In one embodiment of the invention, a portion of product gas 36 is removed from the product gas stream and can be introduced at a point not shown into the adsorbent bed 20 . Then following the regeneration a portion of the gas stream may be removed and introduced into line 26 for introduction into the gas stream six.
FIG. 2 shows a typical molecular sieve unit switching sequence free system with four beds in parallel adsorption. A first adsorber 100 is operated from 00:00 to 02:30, a second adsorber 102 from 02:30 to 05:00, a third adsorber 104 from 05:00 to 07:30, a fourth adsorber 106 from 07:30 to 10:00, depressurization zone 108 from 10:00 to 10:15, heating zone 110 from 10:15 to 12:30, cooling zone 112 from 12:30 to 13:55, repressurization zone 114 from 13:55 to 14:15 and standby and overall valve switching zone 116 from 14:15 to 15:00.
FIG. 3 shows the incorporation of a purge gas step in the switching sequence with the purge step executed after the repressurization step. A first adsorber 100 is operated from 00:00 to 02:30, a second adsorber 102 from 02:30 to 05:00, a third adsorber 104 from 05:00 to 07:30, a fourth adsorber 106 from 07:30 to 10:00, regeneration zone 120 from 10:00 to 15:00, depressurization zone 122 from 10:00 to 10:10, heating zone 124 from 10:10 to 12:30, cooling zone 126 from 12:30 to 13:55, repressurization zone 128 from 13:55 to 14:05, purge zone 130 from 14:05 to 14:25 and standby and overall valve switching zone 132 from 14:25 to 15:00.
FIG. 4 shows the use of a dedicated purge valve and restriction orifice. A lower portion of adsorbent bed 200 is shown with product gas 202 exiting the adsorbent bed and passing into line 204 to product gas valve 206 into line 208 . A portion of product gas 202 may go to either line 210 to depressurization valve 212 and then to line 214 or it may pass through line 216 to depressurization valve 218 into line 220 shown rejoining the gas in line 214 . A purge out valve 222 is also shown in this figure with the gas exiting in line 224 . A portion of the product gas may exit in line 226 through the regeneration heating and cooling valve 228 into line 230 .
FIG. 5 shows the switching sequence with a purge step before repressurization. A first adsorber 200 is operated from 00:00 to 02:30, a second adsorber 202 from 02:30 to 05:00, a third adsorber 204 from 05:00 to 07:30, a fourth adsorber 206 from 07:30 to 10:00, regeneration zone 208 from 10:00 to 15:00, depressurization zone 210 from 10:00 to 10:10, heating zone 212 from 10:10 to 12:30, cooling zone 214 from 12:30 to 13:55, purge zone 216 from 13:55 to 14:15, repressurization zone 218 from 13:55 to 14:05 and standby and overall valve switching zone 220 from 14:25 to 15:00.
This invention is applicable in temperature swing adsorption applications in NGL recovery/sales gas complexes and LNG Facilities, where both the compositional effects (nitrogen/hydrocarbon adsorption) and the heat bump are typically present. It is also applicable for all temperature swing adsorption (molecular sieves and silica gel) applications where regeneration is performed at a lower pressure than the adsorption pressure. All of these applications will, to a certain extent which is dependent on the actual regeneration and adsorption pressure levels, experience the adiabatic heat rise during repressurization and thus the heat bump on the downstream systems when the freshly regenerated bed goes into its adsorption step. Compositional effects may not necessarily be present in these applications.
|
A temperature swing adsorption process to purify a gas comprising at least one adsorption step and at least one regeneration step wherein the regeneration step takes place at a lower pressure than the adsorption step. The pressure is increased by a repressurization step between the regeneration step and the adsorption step, and then a purge step takes place after said repressurization step.
| 1
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
In general, the present invention relates to counterbalance systems for windows that prevent open window sashes from moving under the force of their own weight. More particularly, the present invention system relates to the structure of the brake shoe component of counterbalance systems for tilt-in windows and the manner in which springs connects to the brake shoe.
2. Description of the Prior Art
There are many types and styles of windows. One of the most common types of window is the double-hung window. Double-hung windows are the window of choice for most home construction applications. A double-hung window consists of an upper window sash and a lower window sash. Either the upper window sash or the lower window sash can be selectively opened and closed by a person sliding the sash up and down within the window frame.
A popular variation of the double-hung window is the tilt-in double-hung window. Tilt-in double-hung windows have sashes that can be selectively moved up and down. Additionally, the sashes can be selectively tilted into the home so that the exterior of the sashes can be cleaned from within the home.
The sash of a double-hung window has a weight that depends upon the materials used to make the window sash and the size of the window sash. Since the sashes of a double-hung window are free to move up and down within the frame of a window, some counterbalancing system must be used to prevent the window sashes from constantly moving to the bottom of the window frame under the force of their own weight.
For many years, counterbalance weights were hung next to the window frames in weight wells. The weights were attached to window sashes using a string or chain that passed over a pulley at the top of the window frame. The weights counterbalanced the weight of the window sashes. As such, when the sashes were moved in the window frame, they had a neutral weight and friction would hold them in place.
The use of weight wells, however, prevents insulation from being packed tightly around a window frame. Furthermore, the use of counterbalance weights on chains or strings cannot be adapted well to tilt-in double-hung windows. Accordingly, as tilt-in windows were being developed, alternative counterbalance systems were developed that were contained within the confines of the window frame and did not interfere with the tilt action of the tilt-in windows.
Modern tilt-in double-hung windows are primarily manufactured in one of two ways. There are vinyl frame windows and wooden frame windows. In the window manufacturing industry, different types of counterbalance systems are traditionally used for vinyl frame windows and for wooden frame windows. The present invention is mainly concerned with the structure of vinyl frame windows. As such, the prior art concerning vinyl frame windows is herein addressed.
Vinyl frame, tilt-in, double-hung windows are typically manufactured with guide tracks along the inside of the window frame. Brake shoe assemblies, commonly known as “shoes” in the window industry, are placed in the guide tracks and ride up and down within the guide tracks. Each sash of the window has two tilt pins or tilt posts that extend into the shoes and cause the shoes to ride up and down in the guide tracks as the window sashes are opened or closed.
The shoes contain a brake mechanism that is activated by the tilt post of the window sash when the window sash is tilted inwardly away from the window frame. The shoe therefore locks the tilt post in place and prevents the base of the sash from moving up or down in the window frame once the sash is tilted open. Furthermore, the brake shoes are attached to curl springs inside the guide tracks of the window assembly. Curl springs are constant force coil springs, made from wound length of metal ribbon, that supply the counterbalance force needed to suspend the weight of the window sash.
Small tilt-in windows have small relatively light window sashes. Such small sashes may only require a single coil spring on either side of the window sash to generate the required counterbalance forces. However, due to the space restrictions present in modern tilt-in window assemblies, larger springs cannot be used for heavier window sashes. Rather, multiple smaller coil springs are ganged together to provide the needed counterbalance force. A large tilt-in window sash may have up to eight coil springs to provide the needed counterbalance force. Counterbalance systems that use ganged assemblies of coil springs are exemplified by U.S. Pat. No. 5,232,208 to Braid, entitled Springs For Sash Frame Tensioning Arrangements.
The metal ribbons of coil springs in a window counterbalance system usually experience tension as they support the weight of the window sash. However, this is not always the case. When a window sash is rapidly opened, the upward speed of the window sash may exceed the recoil speed of the counterbalance springs. In such a situation, the metal ribbons of the coil springs may experience a brief period of compression. The ribbons of coil springs are typically uniform in width, except for the free ends of the spring ribbon. The free ends of the spring ribbon are often stamped and shaped so that the end of the spring can engage the structure of the brake shoe. Since the areas near the ends of the spring ribbons are reduced in width, the repeating tension and compression stresses tend to concentrate in these reduced areas. The cycles of tension forces and compressive forces cause the metal ribbon of the coil spring to fatigue. Eventually, the fatigue forces can cause the coil spring to break, thereby disconnecting the coil spring from the brake shoe. This causes the overall counterbalance system to fail.
A need therefore exists in the field of vinyl, tilt-in, double-hung windows, for a counterbalance system with a brake shoe that can attach to a coil spring in such a way that the structure of the brake shoe prevents fatigue stresses from compromising the coil spring. This need is met by the present invention as described and claimed below.
SUMMARY OF THE INVENTION
The present invention is an assembly of components that are use in a counterbalance system for a tilt-in window. A coil spring of wound ribbon is provided that has a free end that terminates with a shaped head. A brake shoe housing is provided that connects to the coil spring in such a manner that fatigue stresses are reduced in the coil spring as the tilt-in window is repeatedly opened and closed.
The brake shoe housing has a receptacle slot formed into one of its side surfaces. The receptacle slot is formed low on the side of the brake shoe housing. An open relief is formed immediately above the receptacle slot. The open relief abuts against and supports the ribbon of the coil spring just behind the shaped head. By engaging the shaped head of the coil spring and supporting the coil spring adjacent to the shaped head, stresses experienced by the shaped head are greatly reduced. The result is a coil spring that has a much longer service life. Furthermore, the connection between the coil spring and the housing also assist in preventing excessive cocking of the brake shoe housing. This prevents wear of the brake shoe housing and increases its operational life.
BRIEF DESCRIPTION OF THE DRAWINGS
For a better understanding of the present invention, reference is made to the following description of an exemplary embodiment thereof, considered in conjunction with the accompanying drawings, in which:
FIG. 1 is an exploded perspective view of a section of a tilt-in window assembly containing a counterbalance system in accordance with the present invention;
FIG. 2 is a cross section of the embodiment of the counterbalance system shown in FIG. 1 , viewed along line 2 - 2 ;
FIG. 3 is an exploded perspective view of the brake shoe housing and cam element of the counterbalance system;
FIG. 4 is a front view of the brake shoe housing and cam element shown with the cam element holding a tilt post of a vertically oriented window sash;
FIG. 5 is a front view of the brake shoe housing and cam element shown with the cam element holding a tilt post of a tilted window sash;
FIG. 6 is a perspective view of the brake shoe assembly and the free end of the coil spring to show interconnection features; and
FIG. 7 is a cross-sectional view of the subassembly of FIG. 6 .
DETAILED DESCRIPTION OF THE INVENTION
The claimed features of the present invention brake shoe can be incorporated into many window counterbalance designs. However, the embodiment illustrated shows only one exemplary embodiment of the counterbalance system for the purpose of disclosure. The embodiment illustrated is selected in order to set forth one of the best modes contemplated for the invention. The illustrated embodiment, however, is merely exemplary and should not be considered a limitation when interpreting the scope of the appended claims.
Referring to FIG. 1 , in conjunction with FIG. 2 , there is shown an exemplary embodiment of a counterbalance system 10 that is used to counterbalance the sashes 12 contained within a window assembly 14 . The counterbalance system 10 utilizes a brake shoe housing 16 , a cam element 18 , and at least one coil spring 20 on either side of each window sash 12 . The brake shoe housing 16 engages a tilt post 22 that extends from the bottom of the window sash 12 . As the window sash 12 is opened and closed, the brake shoe housing 16 travels up and down in vertical guide tracks 24 . It will be understood that each window sash 12 typically utilizes two counterbalance systems on opposite sides of the sash 12 . However, for the sake of simplicity and clarity, only one counterbalance system 10 is illustrated.
The brake shoe housing 16 receives the cam element 18 to form a brake shoe assembly 19 . The brake shoe assembly 19 rides up and down in its guide track 24 . The brake shoe assembly 19 is biased upwardly within the guide track 24 by at least one coil spring 20 . The guide track 24 has a rear wall 26 and two side walls 27 , 28 . The brake shoe assembly 19 is sized to be just narrow enough to fit between the side walls 27 , 28 of the guide track 24 without causing excessive contact with the guide track 24 as the brake shoe assembly 19 moves up and down with the window sash 12 .
Referring to FIG. 3 in conjunction with FIG. 1 and FIG. 2 , it can be seen that the brake shoe housing 16 is a unistructurally molded unit that requires no assembly. The brake shoe housing 16 is generally U-shaped, having a first arm element 30 and a second arm element 32 that are interconnected by a thin bottom section 34 . In the shown embodiment, the coil spring 20 attaches to the first arm element 30 . In the preferred embodiment, the second arm element 32 has a length that is at least twenty-five percent longer than that of the first arm element.
A generally circular cam opening 36 is formed between the first arm element 30 , the second arm element 32 and the bottom section 34 . Above the cam opening 36 , the first arm element 30 and the second arm element 32 are separated by a gap space 38 . The first arm element 30 has a first sloped surface 39 that faces the gap space 38 . Likewise, the second arm element 32 has a second sloped surface 41 that faces the gap space 38 . Taken together, the first sloped surface 39 and the second sloped surface 41 diverge away from each other as they ascend above the cam opening 36 . The result is that the gap space 38 has tapered sides that lead into the cam opening 36 .
A catch finger 40 protrudes from the first sloped surface 39 of the first arm element 30 . The catch finger 40 extends into the gap space 38 between the first arm element 30 and the second arm element 32 . The catch finger 40 is integrally molded as part of the first arm element 30 and the overall brake shoe housing 16 . The catch finger 40 has a first section 42 that extends away from the first sloped surface 39 at an acute angle. This causes the catch finger 40 to extend in a downward direction. The catch finger 40 then curves into a nearly vertical orientation proximate its free end 44 . The free end 44 is molded to be slightly bulbous in order to prevent the catch finger 40 from hanging up on the tilt post 22 , as will later be explained.
The cam opening 36 , although generally circular, is not round. Rather, the cam opening 36 has a rounded bottom section 46 . On the first arm element 30 , the rounded bottom section 46 transitions into a first curved section 48 that has a larger radius of curvature than the rounded bottom section 46 . On the opposite second arm element 32 , there is a second curved section 49 with the same general radius of curvature as the first curved 48 section. However, the second curved section 49 does not transition directly into the rounded bottom section 46 . Rather, the second curved section 49 is offset from the rounded bottom section 46 with a flat ridge 50 . The flat ridge 50 acts as a stop for the cam element 18 , as will later be explained.
The brake shoe housing 16 has a face surface 52 and a rear surface 54 . The cam opening 36 extends from the face surface 52 back to the rear surface 54 . The dimensions of the cam opening 36 decrease just behind the face surface 52 and the rear surface 54 of the brake shoe housing 16 . The decreases in dimensions create ledges 56 in the cam opening 36 just behind the face surface 52 and the rear surface 54 . The ledges 56 are used to help retain the cam element 18 , which will be later described in more detail.
A key projection 58 protrudes into the cam opening 36 from the second curved section 49 . The key projection 58 is positioned approximately midway between the face surface 52 and the rear surface 54 . Again, the key projection 58 is used to help retain the cam element 18 , which will be later described in more detail.
The cam element 18 is generally cylindrical in shape. The cam element 18 , however, does not have a circular cross-sectional profile. Rather, the cross-sectional profile of the cam element 18 is oblong, being mildly elliptical in its general shape. The cam element 18 has a midsection 60 positioned between a front flange 62 and a back flange 64 . The midsection 60 of the cam element 18 has a long axis 61 and a short axis 63 when viewed in cross-section from either end. The front flange 62 and the back flange 64 are slightly larger than the midsection 60 , therein providing the cam element 18 with a slight spool configuration.
A tilt post receiving slot 66 is formed in the cam element 18 . The receiving slot 66 extends from the front flange 62 to the back flange 64 . However, the receiving slot 66 is not symmetrically positioned. Rather, the receiving slot 66 is eccentrically positioned, so that the receiving slot 66 is closer to one side of the cam element 18 than to the other. For the purposes of this description, the side of the cam element 18 that contains most of the receiving slot 66 shall be referred to as the narrow side 68 of the cam element 18 . Conversely, the side of the cam element 18 that does not retain much of the receiving slot 66 is referred to as the wide side 69 of the cam element 18 .
A groove 70 is formed in the exterior of the midsection 60 of the cam element 18 in the wide side 69 of the cam element 18 . The groove 70 is sized to receive the key projection 58 formed into the cam opening.
Referring to FIG. 4 , in conjunction with FIG. 1 and FIG. 3 , it can be seen that the cam opening 36 receives and retains the cam element 18 . During manufacture in the factory, the cam element 18 is inserted into the cam opening 36 by forcing the cam element 18 into the gap space 38 between the first arm element 30 and the second arm element 32 of the brake shoe housing 16 . When pressed into the gap space 38 , the cam element 18 spreads the first arm element 30 and the second arm element 32 apart. This is achieved by the elastic flexing of the thin bottom section 34 of the brake shoe housing 16 , which acts as a living hinge. The cam element 18 also elastically deforms the catch finger 40 down until the cam element 18 passes. Once the cam element 18 is inside the cam opening 36 , the first arm element 30 and the second arm element 32 rebound to their original positions. Likewise, the catch finger 40 returns to its original orientation. The presence of the catch finger 40 helps hinder the removal of the cam element 18 from the cam opening 36 .
Once the cam element 18 is displaced into the cam opening 36 of the brake shoe housing 16 , the front flange 62 and the back flange 64 of the cam element 18 engage the ledges 56 inside the cam opening 36 and prevent the cam element 18 from exiting the cam opening 36 either through the face surface 52 of the brake shoe housing 16 or the rear surface 54 of the brake shoe housing 16 . Furthermore, the key projection 58 in the cam opening 36 engages the groove 70 of the cam element 18 . This interconnection helps retain the cam element 18 in place, while still enabling the cam element 18 to rotate within the cam opening 36 . The length of the groove 70 and the presence of the flat ridge 50 within the cam opening 36 limit the range of rotation achievable by the cam element 18 in the cam opening 36 . In this manner, the over-rotation of the cam element 18 can be prevented.
The narrow side 68 of the cam element 18 is positioned toward the bottom of the brake shoe housing 16 . This causes the tilt post receiving slot 66 to lie close to the thin bottom section 34 of the brake shoe housing 16 . The tilt post receiving slot 66 receives the tilt post 22 . Consequently, the tilt post 22 of the window sash 12 is held close to the thin bottom section 34 of the brake shoe housing 16 . The result is that the window sash 12 can move to a lower position in the window frame than prior art brake shoe assemblies that support tilt posts in a cam near the center of the brake shoe housing.
Referring to FIG. 5 in conjunction with FIGS. 1-4 , it can be seen that when the window sash 12 is tilted inwardly, the tilt posts 22 of the window sash 12 causes the cam element 18 to turn. Prior, the long axis 61 of the cam element 18 had been vertically oriented. When the window sash 12 is tilted, that orientation changes toward the horizontal. The cam element 18 is oblong in shape since it has a long axis 61 and short axis 63 . Consequently, when the cam element 18 turns, the cam element 18 spreads the first arm element 30 from the second arm element 32 of the brake shoe housing 16 . As the cam element 18 spreads the brake shoe housing 16 , the brake shoe housing 16 flexes in its bottom section 34 . The first arm element 30 and the second arm element 32 engage the side walls 27 , 28 of the track 24 . The result is that the brake shoe assembly 19 becomes locked in position within the guide track 24 .
As the cam element 18 spreads open the brake shoe housing 16 , the gap space 38 between the first arm element 30 and the second arm element 32 increases. The tilt post 22 can therefore be removed from the cam element 18 through the widened gap space 38 . Removal of the cam element 18 in such a manner is hindered by the presence of the catch finger 40 . The catch finger 40 extends into the gap space 38 and provides a physical barrier that prevents the tilt post 22 from exiting the cam element 18 . In this manner, the catch finger 40 prevents a user from inadvertently pulling the tilt post 22 out of the cam element 18 while tilting the window sash 12 inwardly.
It will be understood that if the window sash 12 is broken or otherwise is intended to be removed from the window assembly, such a removal is possible. A person intending to remove the window sash 12 can simply depress the catch finger 40 while pulling up on the window sash 12 . If the catch finger 40 is depressed, it will not block the gap space 38 above the tilt post 22 and the tilt post 22 can be freely removed.
Alternately, since the receiving slot 66 that retains the tilt post 22 is eccentrically positioned toward the narrow side 68 of the cam element 18 , it will be understood that the catch finger 40 will not align directly above the tilt post 22 . Rather, as is shown in FIG. 5 , the enlarged free end 44 of the catch finger 40 aligns above one side of the tilt post 22 . This enables the catch finger 40 to prevent most accidental removals of the tilt post 22 . However, if the window sash 12 is pulled upwardly with a sufficient and determined force, the tilt post 22 will contact the catch finger 40 at an angle. Provided the upward force exceeds a predetermined threshold force of at least five pounds, for example, the catch finger 40 will then elastically yield to the tilt post 22 and the window sash 12 can be removed. Once the window sash 12 is removed, the temporarily displaced catch finger 40 will return to its original position. In this manner, a serviceman or homeowner can intentionally pull the window sash 12 out of the window assembly without any tools or manual brake shoe manipulations. The requirement of sufficient and sustained force required for the removal eliminates most all inadvertent removals of the window sash 12 .
FIGS. 2 and 4 show the brake shoe housing 16 , cam element 18 and tilt post 22 when the window sash 12 is vertical and in its regular operating position. FIG. 5 shows the brake shoe housing 16 , cam element 18 and tilt post 22 when the window sash 12 is tilted and the brake shoe housing 16 is locked in the guide track 24 . The shape of the cam opening 36 varies between the regular operating position of FIG. 4 and the locked position of FIG. 5 . As can be seen from FIG. 4 and FIG. 5 , the shape of the cam element 18 is designed to more precisely fit the cam opening 36 when the cam opening 36 is in its locked position. The result is fewer gaps 75 where no contact exists. In this manner, the cam opening 36 better engages the brake shoe housing 16 and is more resistant to accidental replacement while the window sash 12 is being tilted in. This helps prevent the cam element 18 from being advertently pulled, pushed or otherwise displaced from the brake shoe housing 16 .
In the shown embodiment, the coil spring 20 attaches to the first arm element 30 of the brake shoe housing 16 . This causes the brake shoe housing 16 to have a rotational bias in the clockwise direction as it travels up and down the guide track 24 . To prevent the brake shoe housing 16 from cocking in the guide track 24 , the second arm element 32 is provided with an extension 72 . The extension 72 elongates the second arm element 32 and provides more surface contact with the side walls 27 , 28 of the window guide track 24 . This extended contact prevents the brake shoe assembly 19 from cocking to the bias of the coil spring 20 and binding in the guide track 24 .
Referring to FIG. 6 and FIG. 7 , it can be seen that the coil spring 20 is made of a wound ribbon 81 of steel. The free end of the ribbon 81 is shaped into a T-shaped head 80 that is more narrow than the ribbon 81 . The T-shaped head has a length L 1 . The T-shaped head 80 interconnects with the first arm element 30 of the brake shoe housing 16 . The first arm element 30 of the brake shoe housing 16 is specially designed to receive both the T-shaped head 80 of the coil spring 20 and a length of the ribbon 81 proximate the T-shaped head 80 so as to reduce fatigue stresses in the coil spring 20 .
A receptacle slot 82 is formed in a side wall 83 of the first arm element 30 . The receptacle slot 82 is sized to receive and retain the T-shaped head 80 of the coil spring 20 . A relief area 84 is formed in the side wall 83 of the first arm element 30 just above the receptacle slot 82 . The receptacle slot 82 has a transition section 86 that smoothly leads the receptacle slot 82 into the relief area 84 . When the coil spring 20 is engaged with the brake shoe housing 16 , the T-shaped head 80 of the coil spring 20 enters the receptacle slot 82 , therein mechanically interconnecting the coil spring 20 with the brake shoe housing 16 . Once in this position, a length of the ribbon 81 proximate the T-shaped head 80 lays flush in the relief area 84 . The length of the ribbon 81 supported by the relief area 84 is preferably at least as long as the length L 1 of the T-shaped head 80 . As a consequence, the receptacle slot 82 and the relief area 84 combine to form an anchor structure 85 that engages both the T-shaped head 80 of the coil spring 20 and the length of ribbon 81 behind the T-shaped head 80 .
The T-shaped head 80 of the coil spring 20 is much narrower than the remaining ribbon 81 of the coil spring 20 . As such, as a window sash 12 ( FIG. 1 ) is opened and closed, changing tension forces and even some compression forces can be experienced by the coil spring 20 . These changing forces create stresses that tend to concentrate in the thin T-shaped head 80 of the coil spring 20 . The stresses fatigue the metal of the coil spring 20 and can eventually cause the T-shaped head 80 to break. By supporting both the T-shaped head and the segment of ribbon 81 behind the T-shaped head 80 , the stress forces are prevented from concentrating in the T-shaped head 80 . The result is that the coil spring 88 does experiences far less fatigue forces and therefore has a much longer operating life.
In order to accommodate both the receptacle slot 82 and the relief area 84 , the receptacle slot 82 must be positioned low on the side wall 83 of the first arm element 30 . The brake shoe housing 16 has a bottom surface 87 at the bottom of the bottom section 34 . The cam opening 36 in the brake shoe housing 16 has a center point CP a predetermined distance D 1 above the bottom surface 87 . The receptacle slot 82 is positioned on the first arm element 30 at a height above the bottom surface 87 that is no higher than that of the center point CP of the cam opening 36 .
Attaching the coil spring 20 to the brake shoe housing 16 at this low point of attachment has secondary advantages. The T-shaped head 80 of the coil spring 20 is generally horizontally aligned with the center of the cam element 18 . Since the brake shoe housing 16 can rotate relative the cam element 18 , this horizontal alignment minimizes the rotational torque experienced by the brake shoe housing 16 . As a result, the cocking forces on the brake shoe housing 16 are minimized.
It will be understood that the embodiment of the present invention counterbalance system that is described and illustrated herein is merely exemplary and a person skilled in the art can make many variations to the embodiment shown without departing from the scope of the present invention. All such variations, modifications, and alternate embodiments are intended to be included within the scope of the present invention as defined by the appended claims.
|
An assembly of components that are use in a counterbalance system for a tilt-in window. A coil spring of wound ribbon is provided that has a shaped head. A brake shoe housing is provided that connects to the coil spring in such a manner that fatigue stresses are reduced in the coil spring as the tilt-in window is operated. The brake shoe housing has a receptacle slot formed into one of its side surfaces. An open relief is formed immediately above the receptacle slot. The open relief abuts against and supports the ribbon of the coil spring just behind the shaped head. By engaging the shaped head of the coil spring and supporting the coil spring adjacent to the shaped head, stresses experienced by the shaped head are greatly reduced. The result is a coil spring that has a much longer service life.
| 4
|
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority from Korean Patent Application No. 10-2009-106497, filed on Nov. 5, 2009, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference in its entirety.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] Films and methods consistent with what is described herein relate to a multi-layer thin film for encapsulation and a method thereof.
[0004] 2. Description of the Related Art
[0005] Generally, a multi-layer thin film for encapsulation is produced by coating organic and inorganic substances in an alternate sequence on top of a device. Function of an organic thin film of the multi-layer thin film is to absorb film stress and regulate the surface roughness so that an inorganic thin film can have a planarizing layer when the inorganic thin film that blocks oxygen and moisture is coated.
[0006] U.S. Pat. No. 6,570,325 discloses a planarizing film that is used as an organic thin film attached to upper portion of the device. This organic thin film reduces defects in the substrate to improve surface roughness and cover the particles that may be located at upper portion of the device, thereby improving the characteristics of the inorganic thin film.
[0007] As disclosed in U.S. Pat. No. 5,902,641, a liquid monomer is evaporated by a heat source to be then formed on upper portion of the device, and then subjected to a phase change of the liquid monomer into a solid phase and polymerization by UV curing, thereby manufacturing a thin film for encapsulation.
[0008] The effect from improvement in surface roughness and particle coverage achieved by reducing defects in the substrate is outstanding. However, it is impossible to obtain a planarizing layer, since the liquid monomer gathers toward the relatively larger surface. Furthermore, controlling penetration of oxygen and moisture through upper portion of the particle is very hard.
[0009] Whereupon, we developed a multi-layer thin film for encapsulation and a method thereof, the multilayer thin film comprising: a protective layer composed of aluminum oxide produced by a chemical method; a single or double barrier layer composed of silicon nitride (SiN x ); and a mechanical protective layer composed of silicon dioxide (SiO 2 ). The multi-layer thin film can be economically fabricated by using the existing equipment, and has a high level of light transmission over 85% while showing a low level of oxygen and moisture penetration. Additionally, due to superior adhesive strength between the thin films, and high resistance against impacts by heat or ion during a fabricating process, reliability of fabrication is enhanced, and it can thus efficiently used in encapsulating an organic light-emitting device (OLED), a flexible organic light emitting device (FOLED) in a display field, and the cells such as a thin film battery and a solar cell.
SUMMARY OF THE INVENTION
[0010] It is an object of the present invention to provide a multi-layer thin film for encapsulation with a great safety.
[0011] It is another object of the present invention to provide a method for producing the multi-layer thin film for encapsulation.
[0012] According to one embodiment, a multi-layer thin film for encapsulation including a protective layer, a barrier layer, and a mechanical protective layer is provided.
[0013] According to another embodiment, a method for producing the film is provided.
[0014] The multi-layer thin film can be economically fabricated by using the existing equipment, and has a high level of light transmission over 85% while showing a low level of oxygen and moisture penetration. Additionally, due to superior adhesive strength between the thin films, and high resistance against impacts by heat or ion during a fabricating process, reliability of fabrication is enhanced, and it can thus efficiently used in encapsulating an organic light-emitting device (OLED), a flexible organic light emitting device (FOLED) in a display field, and the cells such as a thin film battery and a solar cell.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] The above and/or other aspects of what is described herein will be more apparent by describing certain exemplary embodiments with reference to the accompanying drawings, in which:
[0016] FIG. 1 illustrates an embodiment according to the present invention;
[0017] FIG. 2 illustrates an embodiment according to the present invention;
[0018] FIG. 3 illustrates an embodiment according to the present invention;
[0019] FIG. 4 illustrates an embodiment according to the present invention;
[0020] FIG. 5 illustrates a graphical representation of the result of Experiment 1 which measured life span of the organic light emitting device (OLED) according to an embodiment.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
[0021] Certain exemplary embodiments will now be described in greater detail with reference to the accompanying drawings.
[0022] In one embodiment, a multi-layer thin film for encapsulation may include a protective layer composed of aluminum oxide, a single or double barrier layer composed of silicon nitride (SiN x ), and a mechanical protective layer composed of silicon dioxide (SiO 2 ), which are deposited on one another in sequence.
[0023] According to one embodiment, the multi-layer thin film for encapsulation includes a protective layer, a barrier layer, and a mechanical protective layer, and this is able to prevent substrate damages caused by heat or ion during a fabrication process, avoid short and dark spots on the device by preventing a Joule heating phenomenon, and provide a high level of light transmission over 85%, and subsequently low level of oxygen and moisture penetration.
[0024] According to one embodiment, the thin film for encapsulation includes the protective layer composed of aluminum oxide with thickness of 1˜30 nm located bottom the barrier layer. If the thickness is under 1 nm, the substrate or device can be damaged while the encapsulated film is deposited. If the thickness is over 30 nm, time to deposit the aluminum oxide protective layer is extended.
[0025] Damages to a substrate, a metal electrode, or a transparent conductive oxide (transparent electrode) caused by heat or ion when forming a protective layer by using the conventional plasma technology can be prevented through deposition of an aluminum oxide atomic layer on the substrate, the metal electrode, or the transparent conductive oxide (transparent electrode) using a chemical method. The protective layer may be preferably aluminum oxide (Al 2 O 3 ).
[0026] A single or double barrier layer blocks oxygen and moisture from permeating into the device. Without the barrier layer, the mechanical protective layer alone may not prevent the device from breakage and deteriorated performance. Thickness of the barrier layer may be preferably between approximately 100˜500 nm.
[0027] The mechanical protective layer is formed on the outer-most portion of the device to protect the device from mechanical and physical impacts from outside as well as permeation of oxygen and moisture. The thickness of the barrier layer may be preferably between approximately 1μ20 μm. If the thickness is under 1 μm, the device can be damaged by the external factors. If the thickness is over 20 μm, the mechanical protective layer may have cracks.
[0028] In one embodiment, a thin film for encapsulation may be formed on the substrate and upper portion of the device located on upper portion of the substrate to seal the device. The thin film for encapsulation may also be sealed on the side or lower portion of the substrate.
[0029] In one embodiment, a method for fabricating a multi-layer film for encapsulation may include the steps of: S(1) forming an aluminum oxide protective layer; S(2) forming a single or double silicon nitride (SiN x ) barrier layer; and S(3) forming a mechanical protective layer.
[0030] According to one embodiment, at (S1), an aluminum oxide protective layer is formed. This process is performed to protect the substrate or device from possible damages when the film for encapsulation is formed, and from permeation of oxygen and moisture. The aluminum oxide protective layer may be coated through an atomic layer deposition (ALD) by using ozone (O 3 ) as an oxidant source. More specifically, the aluminum oxide layer may be fabricated by heating the substrate or the OLED device approximately at 30˜80° C., supplying a tri-methyl aluminum (TMA) source to a reaction chamber with Ar carrier gas, and supplying ozone thereto. Herein, the thickness of the thin film may be increased by regularly supplying tri-methyl aluminum and ozone. After supplying the individual source, by regularly supplying Ar gas, non-reaction source is eliminated. Ozone is supplied through an external ozone generator. The thickness of the aluminum oxide layer may be preferably between approximately 0.05˜0.1 nm/cycle, and 1˜30 nm.
[0031] According to one embodiment, at S(2), a barrier layer composed of silicon nitride (SiN x ) is performed.
[0032] Accordingly, the aluminum oxide layer may be formed at S(1) and the silicon nitride barrier layer may be formed by a plasma enhanced chemical vapor deposition (PECVD). Specifically, a silicon nitride layer with thickness of approximately 100˜500 nm may be formed in a condition where silane gas (SiH 4 ) and nitrogen gas (N 2 ), or silane gas, nitrogen gas, and ammonia gas are injected.
[0033] According to the method for producing a multi-layer film for encapsulation, at S(3), a mechanical protective layer is formed.
[0034] At S(3), a mechanical protective layer with thickness of approximately 1˜20 μm may be formed by spraying an oxide silicon solution in a sol-gel phase while exerting a pressure with air or nitrogen.
[0035] In one embodiment, an organic light emitting device may include: (a) a substrate/a transparent conductive oxide/an organic layer/a metal electrode/the thin film for encapsulation; (b) a substrate/a metal electrode/an organic layer/a transparent conductive oxide/the thin film for encapsulation; (c) a substrate/the thin film for encapsulation/a transparent conductive oxide/an organic layer/a metal electrode; or (d) a substrate/the thin film for encapsulation/a metal electrode/an organic layer/a transparent conductive oxide, which are laminated on one another in sequence.
[0036] The substrate may be a flexible polymer substrate selected from the group consisting of polyethyleneterephthalate (PET), polyethylenenaphthalate (PEN), polyethylen (PE), polyether sulfone (PES), polycarbonate (PC), polyarylate (PAR), and polyimide (PI), a metal substrate selected from a group consisting of steel use stainless (SUS), aluminum, steel, and copper, or a glass substrate. The transparent conductive oxide (TCO) may be one selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), indium zinc tin oxide (IZTO), aluminum zinc oxide (AZO), indium tin oxide-silver-indium tin oxide (ITO—Ag—ITO), indium zinc oxide-silver-indium zinc oxide (IZO—Ag—IZO), indium zinc tin oxide-silver-indium zinc tin oxide (IZTO—Ag—IZTO), and aluminum zinc oxide-silver-aluminum zinc oxide (AZO—Ag—Azo), or a mixture thereof.
[0037] The metal electrode may be one selected from a group consisting of a lithium fluoride-aluminum (LiF/Al) layer, a calcium-aluminum (Ca/Al) layer, a calcium-silver (Ca/Ag) layer, aluminum (Al), silver (Ag), gold (Au), and copper (Cu), or a mixture thereof.
[0038] The organic layer may preferably include a hole transport layer (HTL), a light emitting layer, an electron transport layer, and an exciton inhibition layer. The organic layer may be one selected from a group consisting of N,N′-Di (naphthalene-1-yl)-N, N′-diphenyl-benzidine (NPB); copper phthalocyanine (CuPc); 4, 4′, 4″-tris (2-naphthylphenylamino) triphenylamine(2-TNATA); 1, 1-BIS-(4-bis(4-tolyl)-aminophenyl)cyclohexene(TAPC); tris-8-hydroxyquinoline aluminum (Alq3), spiro-TAD, TAZ, Ir (ppz) 3, bathophenanthroline (BPhen), and bathocuproine (BCP), or a mixture thereof.
[0039] FIGS. 1 and 2 illustrate embodiment of the present invention concept.
[0040] In another embodiment, an organic solar cell may include: (a) a substrate/a transparent conductive oxide/an organic layer/a metal electrode/the thin film for encapsulation; (b) a substrate/a metal electrode/an organic layer/a transparent conductive oxide/the thin film for encapsulation; (c) a substrate/the thin film for encapsulation/a transparent conductive oxide/an organic layer/a metal electrode; or (d) a substrate/the thin film for encapsulation/a metal electrode/an organic layer/a transparent conductive oxide, which are deposited on one another in sequence.
[0041] The substrate may be a flexible polymer substrate selected from the group consisting of polyethyleneterephthalate (PET), polyethylenenaphthalate (PEN), polyethnlen (PE), polyether sulfone (PES), polycarbonate (PC), polyarylate (PAR), and polyimide (PI), a metal substrate selected from a group consisting of steel use stainless (SUS), aluminum, steel, and copper, or a glass substrate. The transparent conductive oxide (TCO) may be one selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), indium zinc tin oxide (IZTO), aluminum zinc oxide (AZO), indium tin oxide-silver-indium tin oxide (ITO—Ag—ITO), indium zinc oxide-silver-indium zinc oxide (IZO—Ag—IZO), indium zinc tin oxide-silver-indium zinc tin oxide (IZTO—Ag—IZTO), and aluminum zinc oxide-silver0 aluminum zinc oxide (AZO—Ag—Azo), or a mixture thereof. The metal electrode may be one selected from a layer composed of lithium fluoride and aluminum (LiF/Al), a layer composed of calcium and aluminum (Ca/Al), a layer composed of calcium and silver (Ca/Ag), and aluminum (Al), silver (Ag), gold (Au), and copper (Cu), or mixture of these elements.
[0042] The metal electrode may be one selected from the group consisting of a lithium fluoride-aluminum (LiF/Al) layer, a calcium-aluminum (Ca/Al) layer, a calcium-silver (Ca/Ag) layer, aluminum (Al), silver (Ag), gold (Au), and copper (Cu), or a mixture thereof.
[0043] The organic layer may preferably include a p-type conductive layer, a light absorbing layer, and a n-type conductive layer. The organic layer may be one selected from the group consisting of NiO, PEDOT:PSS, a polythiophene derivative, a polypyrrole derivative, a poly vinyl carbarzole derivative, a polyaniline derivative, a polyacetylene derivative, a polypenylen vinylen derivative, a fullerene derivative, ZnO, TiO 2 , and WO 3 , or a mixture thereof.
[0044] FIGS. 3 and 4 illustrate embodiment of the present invention concept.
[0045] The present inventive concept will be explained in detail below, with reference to embodiments. However, it is apparent that the present inventive concept is not confined to the specific embodiments explained below.
Embodiment 1
[0046] Fabricating A Multi-Layer Thin Film For Encapsulation Including An Aluminum Oxide Protective Layer
[0047] Step 1: Forming An Aluminum Oxide Protective Layer.
[0048] An aluminum oxide layer was formed by heating substrate or the OLED device at 30˜80° C., supplying a tri-methyl aluminum (TMA) source to a reaction chamber through Ar carrier gas, and supplying ozone thereto. Rate of forming the aluminum oxide layer was 0.05˜0.1 nm/cycle, and the aluminum oxide protective layer with thickness of 10 nm was formed at 100˜200 cycle.
[0049] Step 2: Forming a silicon nitride barrier layer.
[0050] The silicon nitride barrier layer with thickness of 500 nm was formed by injecting silane gas (SiH 4 ) and nitrogen gas (N 2 ) respectively at 100 sccm, carried out PECVD, at 150 W (10 W/cm 2 ) of RF power and under 100 mTorr of processing pressure for 25 minutes.
[0051] Step 3: Forming a silicon dioxide mechanical protective layer.
[0052] Using a spray method, oxide silicon solution in a sol-gel phase was discharged at 1˜100 ml/min and while exerting pressure of 10˜100 psi of air or nitrogen (N 2 ). Thereafter, the discharged oxide silicon solution was dried at 80° C., leaving a silicon dioxide mechanical protective layer. The hardness of the formed layer was about 9 H by pencil hardness.
[0053] The film for encapsulation fabricated by the above-mentioned process exhibited a high level of light transmission over 90%.
Embodiment 2
[0054] Fabricating A Multi-Layer Thin Film For Encapsulation Including An Aluminum Oxide Protective Layer
[0055] The film was fabricated in the same manner as embodiment 1, except that the aluminum oxide protective layer of 20 nm was formed at step 1.
Embodiment 3
[0056] Fabricating A Multi-Layer Thin Film For Encapsulation Including An Aluminum Oxide Protective Layer
[0057] The film was fabricated in the same manner as embodiment 1, except that the aluminum oxide protective layer of 30 nm was formed at step 1.
Comparative Example 1
[0058] An Organic Light Emitting Device Sealed By A Glass Can
[0059] An OLED was fabricated by depositing 2-TNATA of 60 nm on ITO, depositing NPB of 20 nm and Alq3 of 60 nm with a thermal evaporator, and depositing LiF of 1 nm and 100 nm Al with a cathode. The OLED was sealed by a glass can.
Experiment 1
[0060] Measuring Life-Time of the OLED Wherein the Thin Film For Encapsulation Is Formed.
[0061] Life-times were measured by measuring the rate of reduction of brightness of the OLED by time in which the thin film for encapsulation is fabricated through embodiments 1˜3 and the comparative example 1, and the result is shown in FIG. 5 .
[0062] As shown in FIG. 5 , it took 205 hours of half life-time, time to reach 50% of the initial brightness, for the OLED sealed with a glass cap (comparative example 1). In embodiment 1, it took 190 hours, in embodiment 2, it took 230 hours, and in embodiment 3, it took 240 hours.
[0063] Although the present invention has been described with reference to preferred embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention.
|
A multi-layer thin film for encapsulation and the method thereof are provided. The multi-layer thin film for encapsulation includes a protective layer composed of aluminum oxide, a single or double barrier layer composed of silicon nitride (SiN x ), and a mechanical protective layer composed of silicon dioxide (SiO 2 ). The multi-layer thin film can be economically fabricated by using the existing equipment, and has a high level of light transmission over 85% while showing a low level of oxygen and moisture penetration. Additionally, due to superior adhesive strength between the thin films, and high resistance against impacts by heat or ion during a fabricating process, reliability of fabrication is enhanced, and it can thus efficiently used in encapsulating an organic light-emitting device (OLED), a flexible organic light emitting device (FOLED) in a display field, and the cells such as a thin film battery and a solar cell.
| 8
|
CROSS REFERENCE TO RELATED APPLICATION
[0001] The present application claims the benefit of U.S. Provisional Application No. 60/661,955 filed on Mar. 15, 2005, which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] Lockstep ladders were first introduced over fifty years ago. A lockstep is used to raise a rolling ladder, also commonly know as a rolling staircase, into its rolling position and when stepped on, drops the ladder's feet to the ground thereby locking it in the climbing position.
[0003] Since their inception all locksteps have functioned basically the same way. A lever is used to raise the ladder into the rolling position and it is held in place by a hook which is generally kept in place by a tension spring. The original design of the lockstep uses the bottom step as a lever. The step pivots on its rear edge and the front of the step is raised when the ladder is in the rolling position. When the user steps on the first step of the ladder the front of the step is rotated down by the weight of user, releasing the lockstep and dropping the feet to the floor putting the ladder in the climbing position.
[0004] This design worked well for many years but had significant functional and safety problems. Functionally, the ladder was difficult to put in the rolling position for taller, heavier ladders. The step needed to be lifted up with the top of the foot to put the ladder in the rolling position, the heavier the ladder the more difficult this was to do. The safety problem came into play primarily when the ladder was left on a retail store floor unattended and in the rolling position. In this position the front of the step was up. Shoppers, often children, would sit on the lowest step and generally grab the step as they were sitting. The ladder was released by their body weight as they were sitting and would severely pinch and in some cases sever shoppers' fingers.
[0005] In the late 1990's ladder manufactures all became painfully aware of this problem as accident victims sued the manufacturers. Since that time most manufactures changed to a new design which involves two separate levers, a pedal to lift the ladder into the rolling position and a trip bar to release the ladder, dropping it to the floor. In this prior art design the step does not move. The trip bar is positioned in front of the step so that when the user steps on the bottom step his foot pushes the trip bar down releasing the lockstep and the ladder feet drop to the ground for climbing. This design eliminates the safety problem and works well, however this prior art lockstep has two areas where improvement would be desirable. First, it has two levers: the pedal and the trip bar. Users get confused and try to lift the ladder by pushing on the trip bar breaking the lockstep. Second, the trip bar can be easily stepped over or bent out of position from stepping on it as described above. This action allows the ladder to be climbed in the rolling position a violation of OSHA and ANSI safety regulations. This also creates a durability problem since the lockstep is designed to support the weight of the ladder in the rolling position not a ladder and person.
BRIEF DESCRIPTION OF THE INVENTION
[0006] A novel lockstep mechanism for a rolling ladder is described. The weight-releasing ladder lockstep allows a ladder to be relocated on wheels but when a person climbs the ladder, the front wheels are automatically retracted and the ladder rests firmly with its front feet on the floor. When in the climbing (stationary) position the front wheels of the lockstep are retracted and the ladder rests on the lockstep's feet. When in the rolling position, the ladder is tilted slightly back on its rear wheels and the wheels of the lockstep are pushed down to allow the ladder to roll. When in the rolling position, the lockstep wheels are held in place via a latch which is isolated from rolling vibrations through pivoting shock links and springs.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 is a perspective view of the lockstep in the rolling position.
[0008] FIG. 2 is a perspective view of the lockstep from underneath in the rolling position.
[0009] FIG. 3 is a side view of the lockstep in the rolling position.
[0010] FIG. 4 is a side view of a rolling ladder incorporating the lockstep.
[0011] FIG. 5 is a perspective view of the lockstep base.
[0012] FIG. 6 is a perspective view of the lockstep frame.
[0013] FIG. 7 is a perspective view of a shock link.
[0014] FIG. 8 is a series of side views of the lockstep showing the stages of movement of the lockstep invention from rolling position to stationary position.
[0015] FIG. 9 is a series of side views of the lockstep showing the stages of movement of the lockstep invention from stationary position to rolling position.
DETAILED DESCRIPTION OF THE INVENTION
[0016] The improved lockstep 2 is shown in FIGS. 1, 2 and 3 . In this preferred embodiment, the ladder 1 (shown in FIG. 4 ) is put in the latched or rolling position using a single pedal 3 . While in the stationary position (wheels retracted) the base step 22 is supported through legs 16 and feet 17 . Preferably, there is no trip bar in this improved design. The ladder stairs 18 are moved into rolling position using a foot pedal 3 and rollers 6 to provide leverage, thereby lifting even the largest ladders easily. In the rolling position, compression springs 5 in combination with shock links 12 are used to support the weight of the ladder 1 and to function as shock absorbers allowing the ladder 1 to be rolled over rough surfaces without activating the release of the lockstep 2 . As a user steps on the base step 22 his weight tilts the ladder stairs 18 forward and towards the ground. The compression springs 5 are calibrated using spacers in such a way that as soon as the user applies a predetermined amount weight (in one preferred embodiment seventy pounds) to the base step 22 , the shock link 12 pivots up causing the release bar 27 to mechanically release a latch 25 allowing the lockstep frame 20 to swing free dropping the feet 17 to the floor and making the ladder 1 ready for climbing. This prevents anyone from being on the ladder 1 without the ladder dropping into a safe climbing position.
[0017] This invention is a major improvement over existing weight actuated locksteps which all tend to fall into the stationary position when rolled across floors due to vibration. In prior art designs, it was difficult to adjust latch or spring tension so that it would be tense enough not to release from rolling vibrations yet sufficiently relaxed so that the weight of a smaller person or child (about seventy pounds) would cause it to release. If the tension was set too high, lighter users could step on the ladder without it falling into non-moveable position, thus creating a safety hazard. If the tension was set too low, the ladder feet would fall to the ground while the ladder was being moved thus creating a major nuisance and making the ladder impractical for many environments. The present invention overcomes this limitation.
[0018] With reference to FIGS. 1, 2 and 3 , a lockstep base 14 is made up of legs 16 , feet 17 and lockstep base frame 15 , all rigidly attached to the bottom ladder step 22 (also referred to herein as a base step). FIG. 5 shows a perspective view of the lockstep base 14 (base step 22 not shown). A caster wheel frame 8 supports caster wheels 4 and is pivotally attached to the lockstep base frame 15 at the caster pivots 30 on the base frame extension arms 13 , said base frame extension arms 13 forming a portion of the lockstep base frame 15 . A lockstep frame 20 with a pedal 3 (preferably shaped to easily allow a user to apply pressure through his foot) moves across the caster frame 8 on rollers 6 and is pivotally attached to two shock links 12 (one on each side of the lockstep base 14 ) at the lockstep frame pivots 31 . FIG. 6 shows lockstep frame alone. Two rollers 6 (not shown in FIG. 6 ) are mounted through the roller pivots 33 viewable in FIG. 6 . Preferably, the two shock links 12 are attached by a cross bar 9 to stabilize the shock links 12 , as shown in FIG. 1 . FIG. 7 shows one of the two shock links alone.
[0019] The lockstep frame 20 further has a latch mount 23 to which a latch arm 26 is attached for engaging into a latch catch 24 underneath the caster frame 8 . The latch mount 23 , latch arm 26 , latch catch 24 and latch spring 28 , together form a latch 25 .
[0020] The shock links 12 are pivotally connected to the lockstep base frame 15 at the shock link pivots 32 . The shock links 12 are held in place against the lockstep base frame 15 by springs 5 that press the two together via a bolt 7 that passes through the lockstep base frame 15 and the shock links 12 . In this manner as the shock links 12 pivot up, the bolt 7 pulls the bottom of the spring 5 up and compresses it against the lockstep base frame 15 . The result is that as the shock links 12 pivot upwards, the springs 5 apply a downward force to pull the shock links 12 back towards the lockstep base frame 15 .
[0021] In order to show the working of the invention, FIGS. 8 a through 8 d show the lockstep moving from the rolling (wheels down) position to the stationary (feet down) position, and FIGS. 9 a through 9 d show the lockstep moving back to the rolling position. To more clearly describe the invention, certain stages have been repeated so that FIGS. 8 a and 9 d (and FIG. 3 ) are the same and FIGS. 8 d and 9 a are the same.
[0022] In the wheels-down rolling position ( FIGS. 1, 2 , 3 , 4 , 8 a and 9 d ), the latch 25 is engaged and holds the caster wheel frame 8 to keep the wheels 4 in the down position. The weight of the ladder 1 is supported by the caster wheels 4 on the caster frame 8 which is held down by the lockstep frame 20 through the rollers 6 . In this position the ladder stairs 18 and ladder frame 40 are rotated slightly back on the rear wheels 41 of the ladder 1 . While the ladder 1 is being relocated on its wheels 4 , 41 , the ladder 1 might encounter bumps in the floor surface. The bumps cause the caster wheels to “push up” on the ladder. The “pushing up” is absorbed to a great extent by the shock link springs 5 , thus preventing the latch 25 from decoupling from the caster wheel frame 8 and lowering the lockstep base 14 onto its feet 17 . In all known prior art weight releasing locksteps, the combination of heavy stairs and rough surfaces would often cause the latching mechanism to release thus raising the front wheels and preventing further rolling of the ladder. By isolating the caster wheel frame 8 from the lockstep base 14 through shock links 12 and springs 5 , the ladder 1 can be rolled across bumpy surfaces without the vibrations causing the latch 25 to release.
[0023] When a user steps on the ladder 1 (usually on the base step 22 ), his weight causes the shock link springs 5 to compress and shock links 12 to pivot up at the shock link pivots 32 ( FIG. 8 b ). As the shock links 12 pivot up, they pull up the lockstep frame 20 with them which in turn pulls the caster frame 8 upwards. During this upward movement of the lockstep frame 20 and the caster frame 8 , the latch arm 26 is forced against the latch release bar 27 causing the latch arm 27 to disengage from the latch catch 24 , releasing it from the caster frame 8 ( FIG. 8 c ). At this point, the lockstep frame 20 is free to move on its rollers 6 across the caster frame 8 and the lockstep frame 20 pivots up allowing the caster frame 8 to freely pivot up via the caster pivots 30 . With the casters 4 unable to support the weight of the ladder 1 , the ladder rests firmly on the feet 17 and legs 16 of the lockstep base 14 ( FIG. 8 d ). It should be noted that the same disengagement would occur if a user skipped the base step 22 and tried to stand on any of the lower stairs 18 of the ladder 1 .
[0024] As shown in FIG. 9 , to put the ladder 1 back into the rolling position a user presses, preferably with his foot, on the lockstep frame pedal 3 . This causes the lockstep frame 20 to pivot, via the lockstep frame pivots 31 , causing a downward force on the caster frame 8 through the rollers 6 as the lockstep frame 20 moves down and towards the back (the lockstep base feet 17 being the front) rolling across the caster frame 8 ( FIG. 9 a ). This downward force causes the caster frame 8 to pivot down, via the caster pivots 30 , forcing the caster wheels 4 onto the ground and the lockstep base 2 up (along with the ladder stairs 18 ). The caster wheels 4 then support the weight of the ladder 1 ( FIG. 9 b ). The latch arm 26 extending from the lockstep frame 20 to the caster frame 8 is forced down (by the downward movement of the lockstep frame 20 ) as the lockstep arm passes over latch catch 24 , thereby compressing the latch spring 28 ( FIG. 9 c ). Eventually the latch arm 26 slides over the latch catch 24 and into the locked position ( FIG. 9 d ). With the latch 25 closed, the lockstep frame 20 is prevented from pivoting back to the up position. The latch 25 is held in place by the latch spring 28 pressing the latch arm 26 against the latch catch 24 . Engaging the caster wheels 4 as described involves lifting the ladder stairs 18 by rotating the ladder stairs 18 and ladder frame 40 about the rear wheels 41 . This lifting task is made easier by the rollers 6 and the leverage created by the lockstep frame 20 and foot pedal 3 .
[0025] In one embodiment, the compression springs 5 are calibrated so that when in the rolling position they support the weight of the ladder plus seventy pounds, but remain essentially decompressed thus allowing the shock link to function.
[0026] The lockstep 2 is attached, preferably rigidly, to the ladder stairs 18 and the ladder frame 40 as shown in FIG. 4 to form the rolling ladder 1 . The rear wheels 41 are connected rotationally to the ladder frame 40 .
[0027] The terms wheels and casters are used interchangeably herein and the use of either term herein is not meant to exclude the other term and is meant to include any rolling mechanism. Likewise the latch is not meant to be limited to the spring loaded latch described but may be any type of latching mechanism, including mechanical or magnetic.
[0028] The particularly embodiment described herein is provided by way of example and is not meant in any way to limit the scope of the claimed invention. It is understood that the invention is not limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Without further elaboration, the foregoing will so fully illustrate the invention, that others may by current or future knowledge, readily adapt the same for use under the various conditions of service
|
A novel lockstep mechanism for a rolling ladder is described. The weight-releasing ladder lockstep allows a ladder to be relocated on wheels but when a person climbs the ladder, the front wheels are automatically retracted and the ladder rests firmly with its front feet on the floor. When in the climbing (stationary) position the front wheels of the lockstep are retracted and the ladder rests on the lockstep's feet. When in the rolling position, the ladder is tilted slightly back on its rear wheels and the wheels of the lockstep are pushed down to allow the ladder to roll. When in the rolling position, the lockstep wheels are held in place via a latch which is isolated from rolling vibrations through pivoting shock links and springs.
| 4
|
CROSS REFERENCE TO RELATED APPLICATION
[0001] The application is a continuation of U.S. Patent Application Publication 2005/0000043, filed on Apr. 16, 2004, which claims the benefit of U.S. Provisional Application No. 60/464,787, filed Apr. 23, 2003, each of which is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to the field of toothbrushes, and more particularly, the invention relates to the field of electrically powered toothbrushes.
BACKGROUND OF THE INVENTION
[0003] Most known electric toothbrushes utilize a single bristle carrier that is powered or otherwise driven by an electric motor incorporated in the toothbrush. The bristle carriers in these toothbrushes generally undergo rotary motion. Although satisfactory in certain respects, a need still exists for an improved powered toothbrush design.
[0004] Numerous attempts have been made to improve the design, efficiency, cleaning efficacy, simplicity, and/or commercial viability of electric toothbrushes. One approach has been the provision of multiple powered bristle carriers. Most artisans have grouped multiple sets of bristles along an end of a brush and incorporated a drive mechanism for simultaneously rotating each of the bristle sets, together. Exemplary designs include those disclosed in U.S. Pat. Nos. 3,242,516; 4,156,620; 4,845,795; 5,088,145; 5,020,179; 4,827,550; and 4,545,087.
[0005] A related strategy is to group sets of bristles on multiple rotating bristle carriers, as disclosed in U.S. Pat. Nos. 2,140,307 and 5,170,525. Rather than rotating each individual bristle set about its center, i.e. the approach adopted in the previously noted patents, the designs described in the '307 and '525 patents rotate multiple groups of bristle sets about the center of a bristle carrier. Specifically, multiple groups of bristle sets are disposed on a circular bristle carrier and that bristle carrier, typically one of several, is rotated about its own axis.
[0006] U.S. Pat. No. 5,070,567 describes a design combining the two previously noted strategies. A rotating bristle carrier is provided along with multiple individually rotatable bristle sets. Although this design likely provides many of the advantages associated with each of its predecessors, the cleaning efficacy of spinning bristle sets, alone, is somewhat limited.
[0007] Yet another design is disclosed in U.S. Pat. No. 5,617,603. The '603 patent describes an assembly of “staggered swing” brushes. Apparently, the two bristle carriers move along a complex path within the plane of the toothbrush.
[0008] Although dual bristle carriers that undergo various combinations of movement have been disclosed in the prior art, there remains a need to provide an electric toothbrush with a plurality of bristle carriers in which at least one carrier undergoes a reciprocating or pivotal type of motion. Additionally, there is a need to provide an electric toothbrush with multiple bristle carriers in which at least one of the carriers reciprocates while another component of the brush undergoes a particular type of motion that assists in the brushing operations.
SUMMARY OF THE INVENTION
[0009] In some embodiments of the present invention, a toothbrush has a handle and a head attached to the handle. The head has a top face and a bottom face, wherein the top face comprises a plurality of cleaning members and the bottom lace comprises an elastomeric surface. The elastomeric surface forms a hill and wherein the hill comprises a plurality of protrusions.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The present invention may take form in various components and arrangements of components, and in various techniques, methods, or procedures and arrangements of steps. The referenced drawings are only for purposes of illustrating preferred embodiments, they are not necessarily to scale, and are not to be construed as limiting the present invention.
[0011] It is believed that the present invention will be better understood from the following description taken in conjunction with the accompanying drawings in which:
[0012] FIG. 1 is a perspective view of a preferred embodiment toothbrush in accordance with the present invention illustrating various planes and their orientation with respect to the toothbrush.
[0013] FIG. 2 is a perspective view of another preferred embodiment toothbrush in accordance with the present invention.
[0014] FIG. 3 is a perspective view of another preferred embodiment toothbrush in accordance with the present invention.
[0015] FIG. 4 is a perspective view of another preferred embodiment toothbrush in accordance with the present invention.
[0016] FIG. 5 is a perspective view of the front and rear of a brush head of another preferred embodiment toothbrush in accordance with the present invention.
[0017] FIG. 6 is a detailed view of several preferred massaging elements utilized by the preferred embodiment toothbrush depicted in FIG. 5 .
[0018] FIG. 7 is a detailed cross sectional view of the brush head of the preferred embodiment toothbrush shown in FIG. 5 .
[0019] FIG. 8 is a detailed view of the front and rear of a brush head of another preferred embodiment toothbrush in accordance with the present invention.
[0020] FIG. 9 is a detailed view of several preferred massaging elements utilized by the preferred embodiment toothbrush depicted in FIG. 8 .
[0021] FIG. 10 is a detailed cross sectional view of the brush head of the preferred embodiment toothbrush shown in FIG. 8 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0022] Before describing the various preferred embodiments, it is instructive to define the various types of motions that the movable bristles of the various toothbrushes may undergo. As used herein, the term “angular motion” refers to any angular displacement. “Linear motion” is movement along a straight or substantially straight, line or direction. “Curvilinear motion” is movement that is neither completely linear nor completely angular but is a combination of the two (e.g., curvilinear). These motions can be constant or periodic. Constant motion refers to motion that does not change direction or path (i.e., is unidirectional). Periodic motion refers to motion that reverses direction or path. Constant angular motion is referred to as rotary motion, although features herein may be described as “rotatably mounted” which is intended to merely mean that angular motion, whether periodic or constant, is possible. Periodic angular motion is referred to as oscillating motion. Curvilinear motions can also be either constant (i.e., unidirectional) or periodic (i.e., reverses direction). Periodic linear motion is referred to as “reciprocation”. “Orbital motion” is a type of angular motion about an axis that is distinct from and is some distance apart from the center of the moving component, e.g. a shaft. This distance is referred to herein as the extent of offset of the orbital motion. Orbital motion may be either constant angular motion or periodic angular motion.
[0023] The above-described motions can occur along one or more axes of a bristle carrier, a toothbrush, a toothbrush head, etc. Accordingly, motion is described herein as being either one, two, or three dimensional motion depending upon the number of axial coordinates required to describe the position of a bristle carrier during its movement. The axes, X, Y, and Z, are shown in FIG. 1 . One dimensional motion is motion that can be described by a single coordinate (e.g., X, Y, or Z coordinates). Typically, only linear motion can be one dimensional. For example, periodic linear motion substantially along only the Y axis is one dimensional motion (referred to herein as a “pulsing motion” or an “up and down motion”). Two dimensional motion is movement by a bristle carrier that requires two coordinates (e.g., X and Y coordinates) to describe the path of travel of the bristle carrier. Angular motion that occurs in a single plane is two dimensional motion since a point on a bristle carrier would need two coordinates to describe the path of travel. Three dimensional motion is movement by a bristle carrier that requires three coordinates (e.g., X, Y, and Z coordinates) to describe the path of travel of the bristle carrier. An example of three dimensional motion is movement by a bristle carrier in the path of a helix.
[0024] Since most of the bristle carrier motions described herein can be modified by adjusting various structural features, the description of a motion herein shall be automatically understood to accommodate these variations. For example, a motion that is described as oscillating about an axis can also include components of other motions (e.g., a reciprocating linear motion), especially where it is noted that modifications can be made to provide this second component of motion. Motions that are intended to exclude such modifications shall be described herein with the modifier “primarily” (e.g., “primarily oscillating” or “primarily reciprocating”) and are intended to exclude significant other types motion, but not other motions that might be incidental from manufacturing tolerances or variabilities or where it is difficult to completely eliminate another type of motion completely from the bristle carrier, as is sometimes the case. All motions described herein may be restricted to primarily the motion described if desired.
[0025] FIG. 1 is a perspective view of a preferred embodiment toothbrush 2 in accordance with the present invention. The toothbrush 2 comprises an elongated body 10 having a handle 30 , a head 50 , and a neck 40 extending between the handle 30 and the head 50 . A switch 20 is provided or made accessible along the outer region of the body 10 . As will be appreciated, the switch 20 actuates an electrical motor contained within the body 10 of toothbrush 2 . The motor (not shown) and a drive mechanism as described herein (not shown) drive one or more bristle carriers disposed near a distal end of the toothbrush. Specifically, the toothbrush 2 further includes a first bristle carrier 60 located adjacent a distal-most first end 52 and a second bristle carrier 70 . As described in greater detail herein, upon activation of the drive mechanism, the first and second bristle carriers undergo a particular combination of motions. The motions are best described in terms of the axes X, Y, and Z.
[0026] The X axis is generally referred to herein as the longitudinal axis and generally extends along a longitudinal or lengthwise dimension (as seen from the top planar view of the toothbrush) of the toothbrush head or the bristle carrier. For example, a longitudinal axis is an axis passing through the longest dimension of the toothbrush head. The Y axis is transverse, orthogonal or perpendicular to the X axis and generally bisects the toothbrush head into its left and right halves. The Z axis is transverse, orthogonal or perpendicular to the X and Y axes. It will be appreciated that axis orientations need not be exactly orthogonal or perpendicular to another axis and that some deviation from 90 degrees between the axes, particularly when these axes are used to describe a direction of motion. It should be understood that any axis orientation herein can be modified by the terms “generally” or “substantially” (e.g., “generally transverse” or “substantially transverse”). The word “substantially” implies some angular deviation, but not as much angular deviation from 90 degrees as the word “generally”. No modifier indicates slight to no deviation from 90 degrees. Thus, a motion that is described as occurring along a first axis transverse to a second axis implies that the motion occurs at a 90 degree angle to the second axis with some slight deviation permitted (e.g., from manufacturing tolerances, etc.). If the motion is generally transverse or substantially transverse, a greater deviation from 90 degrees is contemplated. All the axes described herein can intersect another axis either generally or substantially transverse to said other axis.
[0027] Plane X contains the X axis and is generally referred to herein as the plane of the toothbrush or the plane of the toothbrush head. This plane generally extends along the longitudinal dimension of the toothbrush. The Y plane contains the Y axis and extends through the toothbrush and is perpendicular to the X plane. The Y plane either bisects the toothbrush or is parallel to a plane that does. The Z plane is perpendicular to both the X plane and the Y plane and contains the Z axis.
[0028] Furthermore, it is useful to address the terminology used in describing the preferred embodiment toothbrushes, bristle carriers, and the various drive mechanisms. As used herein, the term “forward” refers to the direction from the handle to the head while the term “rearward” refers to the direction from the head to the handle. A longitudinal direction is a direction that generally corresponds to a longitudinal or X axis but which may not lie in the same plane as the axis. For example, the longitudinal axes of a shaft and a bristle carrier may not extend in the same plane but generally extend in the same direction from a top planar view. Similarly, a neck and head that are angled with respect to each other may not have longitudinal axes that extend in the same plane, but do have axes that extend in the same general longitudinal direction from a top planar view. Many of the preferred embodiment electric toothbrushes typically have an elongated head with a longitudinal axis passing through the longest dimension thereof. This axis typically extends in the same general direction as the longitudinal axes of the toothbrush neck and/or shaft. This axis is generally referred to as the longitudinal axis of the toothbrush. By the phrase “same general direction,” some angular deviation is contemplated between the axes.
[0029] Generally, the preferred embodiment toothbrushes according to the present invention comprise an elongated hollow body containing an electrically powered motor and drive mechanism that is used to drive one, two, three or more moveable bristle carriers. The elongated hollow body also includes an interior chamber or cavity for containing one or more batteries for powering the motor. And, one or more switches are provided along the outer region of the body for activating the motor and drive mechanism. As will be appreciated, a removable end cap is provided to enclose the interior chamber and provide a seal against external agents for the components inside the toothbrush body. As described in detail herein, the preferred embodiment toothbrushes comprise one, two, three or more movable bristle carriers. Each of the bristle carriers undergoes particular types of motion and the resulting combinations of movements provide unique cleaning efficacy.
[0030] Furthermore, it is useful to define the terms “fixed” or “static” bristles, and the term “movable” bristles. The terms fixed or static bristles refer to bristles that are secured or affixed to the brush head or body of the toothbrush or other component thereof so that the bristles, and specifically, the base of the bristles, do not move with regard to the longitudinal axis of the toothbrush. Restated, fixed or static bristles refer to bristles that are affixed to the toothbrush such that their base or point of attachment does not move with respect to the toothbrush. It is recognized that the tips or regions distal from the base of a bristle or group of bristles may move as a result of flexing of the bristle. However, the base of a stationary, static, or fixed bristle does not move with respect to the brush. The term movable bristle refers to a bristle in which the base of the bristle moves with respect to the toothbrush, and particularly with respect to the longitudinal axis of the brush. Generally, this configuration is accomplished by affixing or supporting the base of the bristle to a mounting component, i.e. a bristle carrier or holder, that is movable with respect to the brush. Restated, a movable bristle is a bristle that is movable with respect to the longitudinal axis of the brush.
[0031] FIG. 2 is a partial perspective view of a preferred embodiment toothbrush 100 in accordance with the present invention. The preferred embodiment toothbrush 100 includes a body 130 , a brush head 150 , and a neck 140 extending between the body and the head. The toothbrush 100 further includes a bristle carrier assembly that features a plurality of bristle carriers as follows. This preferred assembly includes a first bristle carrier 160 , a second bristle carrier 170 , and a third bristle carrier 180 . The first bristle carrier 160 includes a base 162 . The second bristle carrier 170 includes a base 172 . And, the third bristle carrier 180 includes a base 182 . Preferably, the first, second, and third bristle carriers, i.e. 160 , 170 , and 180 are pivotable (when incorporated in a toothbrush head) about an axis extending through one or more pivot members such as pivot members 183 and 163 . Each of the bases 162 , 172 , and 182 contain a camming member 161 , 171 , and 181 , each of which is received within a camming slot 136 defined within a cam member 134 . Each of the camming members 161 , 171 , and 181 preferably extends downward from a respective base, as shown in FIG. 2 . The cam member 134 is retained within the interior of the toothbrush head and is engaged with a drive shaft 116 . As can be seen, the drive shaft 116 preferably undergoes a reciprocating-type motion. Upon reciprocal movement of the drive shaft 116 ; reciprocal movement, however transverse to the movement of the drive shaft 116 , or periodic curvilinear movement is imparted to each of the bristle carriers 160 , 170 , and 180 . The specific type of motion imparted to each of the bristle carriers depends upon the configuration and engagement between the camming members and the camming slot.
[0032] FIG. 3 is a perspective view of another preferred embodiment toothbrush 200 in accordance with the present invention. The preferred embodiment toothbrush 200 includes a body 230 , a brush head 250 , and a neck 240 extending between the body and the head. The toothbrush 200 further includes a bristle carrier assembly that features a plurality of bristle carriers as follows. FIG. 3 illustrates the assembly as comprising a first bristle carrier 260 , a second bristle carrier 270 , and a third bristle carrier 280 . The first bristle carrier 260 includes a base 262 . The second bristle carrier 270 includes a base 272 . The third bristle carrier 280 includes a base 282 . Preferably, each of the bases, i.e., 262 , 272 , and 282 , provide a collar which defines an engagement slot or aperture. For example, as shown in FIG. 3 , the third bristle carrier 280 includes a collar 284 that defines an engagement slot or aperture 286 . Each of the slots or apertures of a respective collar is received along a cam region 218 of a drive shaft 216 . Preferably, the drive shaft 216 undergoes reciprocating motion such that lateral motion or other motion is imparted to each of the bristle carriers 260 , 270 , and 280 . As previously explained with regard to FIG. 2 , one or more of the bristle carriers 260 , 270 , 280 may include a pivot member such as member 283 in FIG. 3 . Depending upon their configuration and engagement with a retaining component of a toothbrush head within which the bristle carrier assembly is incorporated, the pivot members generally serve to cause the bristle carriers to undergo a pivotal motion about the axis of the pivot members.
[0033] FIG. 4 is a perspective view of another preferred embodiment toothbrush 300 in accordance with the present invention. This preferred embodiment toothbrush 300 comprises a body 330 , a head 350 , and a neck 340 extending between the body 330 and the head 350 . Disposed on the brush head 350 are a plurality of movable bristle carriers which in FIG. 4 as shown, include a first bristle carrier 360 and a second bristle carrier 370 . Each of the bristle carriers 360 and 370 undergo a reciprocating motion as shown upon activation of the brush. Specifically, linear reciprocating motion of a drive shaft 316 , such as from a drive mechanism (not shown) disposed in the body 330 is imparted to a second drive shaft 318 via linkage 317 . Movement of drive shaft 318 is further transmitted to a hinged component 319 and to a linking arm 320 extending between the hinged component 319 and one or both of the bristle carriers 360 and 370 .
[0034] In a most preferred aspect, a rocking arm 321 is utilized that extends between the first and second bristle carriers 360 and 370 . Most preferably, the rocking arm 321 is hinged about its center to a stationary member within the interior of the brush head 350 such that the arm 321 may move or pivot about that member. An end of the linking arm 320 is engaged to an end of the rocking arm 321 such that reciprocation of the linking arm 320 causes pivoting of the arm 321 about its center. As shown in FIG. 4 , since each bristle carrier 360 and 370 is engaged to an opposite end of the rocking arm 321 , pivoting of the arm 321 causes reciprocation of the carriers 360 and 370 . The reciprocation of each carrier 360 and 370 is out of phase with the other. Thus, when the carrier 360 moves in a forward direction, the carrier 370 moves in a rearward direction, and vice versa.
[0035] FIGS. 5 , 6 , and 7 illustrate yet another preferred embodiment toothbrush 400 in accordance with the present invention. The preferred embodiment toothbrush 400 includes a body 430 , a head 450 , and a neck 440 extending between the body 430 and the brush head 450 . Disposed on the brush head 450 are a plurality of movable bristle carriers such as a first bristle carrier 460 and a second bristle carrier 470 . A drive shaft 416 extends within the neck 440 and the body 430 and imparts motion to one or both of the bristle carriers 460 and 470 from a drive mechanism (not shown). Preferably, upon operation of the toothbrush 400 , the drive shaft 416 reciprocates as shown in FIG. 5 . The distal end of the drive shaft 416 is engaged with a base 472 of the second bristle carrier 470 . As will be appreciated, the first bristle carrier 460 may be directly powered from the drive shaft 416 or indirectly powered, such as via the second bristle carrier 470 .
[0036] The preferred embodiment toothbrush 400 of FIGS. 5 , 6 , and 7 features a massaging plate 480 movably disposed along a rear face of the brush head 450 . Upon operation of the toothbrush 400 , the massaging plate 480 is reciprocated generally along the longitudinal axis of the toothbrush 400 . The massaging plate is preferably formed from an elastomeric material, or other relatively soft pliable material. The outer surface of the massaging plate 480 may be formed so as to provide one or more outwardly extending ridges, protrusions, or other members that serve to provide specific massaging characteristics. FIG. 6 illustrates various alternative versions of the massaging plate 480 . A plate 480 a may be provided that has a plurality of raised protrusions or other projections extending from its outer surface. A plate 480 b may be used that features a plurality of outwardly extending ridges. And, a plate 480 c may be used that features a relatively smooth outer surface, free of any raised or outwardly extending projections.
[0037] FIG. 7 is a partial sectional elevational view of the brush head 450 of the toothbrush depicted in FIG. 5 taken along line VII-VII. FIG. 7 illustrates a linking component 418 that engages the distal end of the drive shaft 416 to the bristle carrier 470 and to the massaging plate 480 . Upon reciprocating motion of the drive shaft 416 , both the bristle carrier 470 and the massaging plate 480 are moved in similar fashion.
[0038] FIGS. 8 , 9 , and 10 illustrate yet another preferred embodiment toothbrush 500 in accordance with the present invention. The toothbrush 500 includes a body 530 , a brush head 550 , and a neck 540 extending between the body 530 and the brush head 550 . A first bristle carrier 560 is disposed on the brush head 550 . And, a second bristle carrier 570 is disposed on the brush head 550 . A drive shaft 516 extends within the neck 540 and upon activation of the brush, imparts motion to one or both of the bristle carriers 560 and 570 .
[0039] The toothbrush 500 provides a massaging plate 580 similar to the toothbrush 400 previously described. However, the massaging plate 580 of the toothbrush 500 does not reciprocate as does the massaging plate 480 of the toothbrush 400 . This is described in greater detail herein. The massaging plate 580 is preferably formed from an elastomeric or other suitable material. The plate 580 is preferably disposed along a rearward face of the toothbrush head 550 and secured thereto. The plate 580 may be provided with a variety of different surface configurations. FIG. 9 depicts a massaging plate 580 a having a plurality of outwardly extending raised regions; plate 580 b having a plurality of raised ridges; and plate 580 c having a smooth outer surface.
[0040] FIG. 10 is a partial sectional elevational view of the brush head 550 of the toothbrush 500 taken along line X-X in FIG. 8 . A linking component 518 is provided that engages the distal end of the drive shaft 516 to the bristle carrier 570 . The linking component 518 is provided with an outwardly extending bulb or region that contacts the underside of the massaging plate 580 . As will be appreciated, since the plate 580 is formed from a material that is flexible and pliable, motion is imparted to the outer surface of the plate 580 as the linking component 518 is displaced along the underside of the plate 580 . This configuration results in the outer surface of the massaging plate 580 exhibiting a pulsing motion and essentially vibrate upon operation of the toothbrush 500 .
[0041] It will be appreciated that in all of the embodiments of the present invention, one or more groups of static bristles or other cleaning members may be provided in conjunction with the moving bristles. It may, in many instances, be preferred to provide a collection of static bristles on the toothbrush head. For example, static bristles may be disposed in a gap between bristle carriers or may completely encircle the bristle carriers. Static bristles may also be disposed at the distal-most end of the head and/or at the rearward-most portion of the head and/or adjacent the sides of the toothbrush head. Further examples of static bristles that may be used with the present invention are described in U.S. patent application Ser. No. 10/274,40 and U.S. Pat. No. 6,360,395. Moving or static elastomeric bristles, formed for example from a thermoplastic elastomer or rubber, can also be provided on the moving bristle carriers or the toothbrush head. An example of one arrangement is described in U.S. Pat. No. 6,371,294.
[0042] While brush head embodiments of the present invention have been illustrated for simplicity with tufts of bristles that extend in a direction substantially perpendicular to the longitudinal axis of the head from which they extend, it is contemplated that the static and/or movable bristles might be arranged differently to compliment or further enhance the static bristles or the motion of the movable bristles. Some or all of the bristles might extend in a direction that forms an acute angle with a top surface of a bristle holder and may extend in a forward or rearward direction. In another embodiment, some of the bristles might extend outwardly away from the head, in another direction, again :forming an acute angle with respect to the top surface of the bristle holder. Examples of other suitable bristle arrangements are described in U.S. Pat. Nos. Des. 330,286, Des. 434,563; 6,006,394; 4,081,876; 5,046,213; 5,335,389; 5,392,483; 5,446,940; 4,894,880; and International Publication No. WO99/23910.
[0043] The toothbrushes of the present invention may be formed from a wide array of polymers. In the following description of the preferred polymer materials for use herein, the abbreviations that are commonly used by those of skill in the art to refer to certain polymers appear in parentheses following the full names of the polymers. The polymer is preferably polypropylene (“PP”), or may be selected from the group consisting of other commercially available materials, such as polystyrene (“PS”), polyethylene (“PE”), acrylonitrile-styrene copolymer (“SAN”), and cellulose acetate propionate (“CAP”). These materials may be blended with one or more additional polymers including a thermoplastic elastomer (“TPE”), a thermoplastic olefin (“TPO”), a soft thermoplastic polyolefin (e.g., polybutylene), or may be selected from other elastomeric materials, such as etheylene-vinylacetate copolymer (“EVA”), and ethylene propylene rubber (“EPR”). Examples of suitable thermoplastic elastomers herein include styrene-ethylene-butadiene-styrene (“SEBS”), styrene-butadiene-styrene (“SBS”), and styrene-isoprene-styrene (“SIS”). Examples of suitable thermoplastic olefins herein include polybutylene (“PB”), and polyethylene (“PE”). Techniques known to those of skill in the art, such as injection molding, can be used to manufacture the toothbrush of the present invention.
[0044] The present invention has been described with reference to particular preferred embodiments. Modifications and alterations may be made to these embodiments within the scope of the present invention. For example, certain combinations of bristle carriers have been described herein. It will be appreciated that the bristle carriers can be rearranged and the bristle carrier of one embodiment substituted for that of another. Further, while some bristle carriers may have a slot that engages a pin on the toothbrush head to guide the movement of the bristle carrier, it will be appreciated that these features can be reversed so that the pin is disposed on the bristle carrier and the slot is disposed on the head, and further that other structures known in the art can be used to guide the motion of any of the bristle carriers described herein. It is intended that all such modifications and alterations are included insofar as they come within the scope of the appended claims or equivalents thereof.
[0045] All documents cited in the Detailed Description of the Invention are, in relevant part, incorporated herein by reference; the citation of any document is not to be construed as an admission that it is prior art with respect to the present invention.
[0046] While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
|
A toothbrush has a handle and a head attached to the handle. The head has a top face and a bottom face, wherein the top face comprises a plurality of cleaning members and the bottom face comprises an elastomeric surface. The elastomeric surface forms a hill and wherein the hill comprises a plurality of protrusions.
| 0
|
FIELD OF THE INVENTION
The present invention relates to contactless IC cards to which a power supply voltage is supplied from outside in a noncontacting manner and, more particularly, to contactless IC cards in which a power supply voltage of an integrated circuit is stabilized.
BACKGROUND OF THE INVENTION
IC cards with CPUs featuring security functions, personal identification functions and the like are broadly divided into “IC cards with contacts” which communicate data with a reader/writer via contacts, and “contactless IC cards” which perform data transmission by electromagnetic induction or the like. Among these IC cards, contactless IC cards which transmit data via radio have greater durability because they do not need a connecting terminal to connect to an external device. Further, such contactless IC card rectifies received waves using a rectifier to generate a DC power supply that is required to activate the integrated circuit, eliminating the need of batteries, whereby it is effective in miniaturization of the system and reduction of the costs.
The conventional contactless IC card includes an analog circuit, a CPU, or a memory on one integrated circuit (for example, refer to “A 13.56 MHz CMOS RF Identification Transponder Integrated Circuit WithA Dedicated CPU” (Shoichi Masuiet al., ISSCC Digest of Technical Papers, pp. 162–163, FIG. 9.1.1 (Feb. 16, 1999)). There are also contactless IC cards to which a power supply voltage is supplied with stability even when a relative position between a reader/writer and the IC card varies (for example, refer to Japanese Patent No. 3376085, FIG. 3).
The operation of such contactless IC card will be described with reference to FIG. 9 . A contactless IC card 1 comprises a coil antenna L 1 and a semiconductor integrated circuit 2 . The semiconductor integrated circuit 2 comprises a rectifier 3 , a shunt regulator 4 , a demodulator 5 , a modulator 6 , a digital signal processing unit 7 , a linear regulator 8 , and a reference voltage circuit 9 . As the rectifier 3 , a full-wave rectification circuit that employs diodes D 1 to D 4 as shown in FIG. 10 is used.
A signal that is received by the coil antenna L 1 is rectified by the rectifier 3 to generate a power supply voltage VDDA. The demodulator 5 demodulates RX (receiving) data which is superimposed upon the power supply voltage VDDA. The RX data is transferred to the digital signal processing unit 7 , which is constituted by a CPU or a memory. The modulator 6 modulates an impedance between ends of the coil antenna L 1 in accordance with TX (transmission) data that is generated by the digital signal processing unit 7 . As the reference voltage circuit 9 , a band-gap reference circuit as shown in FIG. 11 is used. This circuit generates a reference voltage Vref. In the case of band-gap reference circuit, this circuit generates, for example, the reference voltage Vref=1.2V.
As the linear regulator 8 , a regulator circuit that employs an operational amplifier as shown in FIG. 8 is used. In the case of linear regulator as shown in FIG. 8 , a power supply voltage VDDD having a value of Vref×(1+R 1 /R 2 ) is generated as an output. For example, when it is assumed R 1 =R 2 , VDDD=2.4V. The power supply voltage VDDD is a power supply voltage for the digital signal processing unit 7 .
The shunt regulator 4 is a circuit that prevents the power supply voltage VDDA from increasing above a breakdown voltage. It is assumed here that the communication standard is ISO14443 TYPE B. According to this standard, the carrier frequency is 13.56 MHz, the data rate is 106 kbps, the data transmission from the reader/writer to the contactless IC card is done by means of the 10% ASK modulation, and the data transmission from the contactless IC card to the reader/writer is done by means of the BPSK modulation.
The power that is supplied to the contactless IC card is decided based on the intensity of a magnetic field that is applied to the card coil. Usually, when the card becomes closer to the reader/writer (not shown), the intensity of the magnetic field is increased, whereby the power that is supplied to the semiconductor integrated circuit 2 is increased. The supplied power is converted into a DC voltage by the rectifier 3 . Here, when the load to the semiconductor integrated circuit 2 is fixed, the power supply voltage is increased in proportion to the supplied power. The breakdown voltage of a transistor which is manufactured in the present semiconductor process is about 5V when the thickness of the gate oxide film is 10 nm. When the power supply voltage VDDA is increased above the breakdown voltage, the transistor would be broken.
The shunt regulator 4 that consumes an unnecessary power is employed to suppress an increase of the power supply voltage VDDA. For example, when the power supply voltage is increased above 4V, the shunt regulator 4 consumes excess energy and, as a result, the increase of the power supply voltage VDDA can be reduced. Further, the capability of the shunt regulator 4 is adjusted suitably to demodulate a modulated signal by the demodulator 5 .
The conventional contactless IC card is constructed as described above and, since there is no need for a connecting terminal to connect to an external device, it has greater durability, and further, as the batteries are not required, this is effective in miniaturization of the system or reduction of the costs. However, this conventional IC card has the following problem. The linear regulator 8 cannot supply the power supply voltage VDDD earlier than start-up of the reference voltage circuit 9 . This is because when the reference voltage Vref=0V, the voltage output from the above-mentioned linear regulator 8 becomes a power supply voltage VDDD=0. The start-up of the reference voltage circuit 9 takes time of above 100 μsec. For the above-mentioned reasons, when the energy that ought to be supplied to the power supply voltage VDDD is supplied to the power supply voltage VDDA, the potential of the power supply VDDA is increased, and when the power supply voltage voltage VDDA is increased above the breakdown voltage, the device would be broken. Such breakage of the device presents a more serious problem when the size of the digital signal processing unit 7 is larger, because the power supply voltage VDDA is increased more.
In order to suppress such increase of the power supply voltage VDDA, it is possible to increase the capacity of the shunt regulator 4 , but when an ASK signal is to be demodulated, the demodulator 5 detects variations in the power supply voltage VDDA to demodulate RX data and, thus, when the capacity of the shunt regulator 4 is simply increased, the amount of variations in the signal is reduced, whereby the demodulation of the ASK signal by the demodulator 5 becomes difficult.
SUMMARY OF THE INVENTION
The present invention provides a high-performance contactless IC card that can suppress a steep increase of the power supply voltage VDDA by supplying energy to the power supply voltage VDDD even when the reference voltage circuit is not started at the input of a strong electric field, thereby avoiding a problem of breakage of the device.
Other objects and advantages of the invention will become apparent from the detailed description that follows. The detailed description and specific embodiments described are provided only for illustration since various additions and modifications within the spirit and scope of the invention will be apparent to those of skill in the art from the detailed description.
According to a 1st aspect of the present invention, there is provided a contactless IC card which comprises a coil antenna and a semiconductor integrated circuit, and receives electromagnetic wave energy that is transmitted from an external device using the coil antenna and rectifies the received energy using a rectifier, thereby generating a power supply voltage. The semiconductor integrated circuit includes: a rectifier for rectifying an output signal from the coil antenna to generate a first supply voltage; a reference voltage circuit for generating a reference voltage; a judging circuit for judging whether the reference voltage is equal to or higher than a predetermined voltage; and a power supply voltage stabilization unit for controlling a potential of the first supply voltage on the basis of a determination by the judging circuit. Therefore, it is possible to suppress a steep increase of the first power supply by supplying energy to the second power supply even when the reference voltage circuit has not started at the input of a strong electric field, thereby realizing a high-performance contactless IC card.
According to a 2nd aspect of the present invention, in the contactless IC card of the 1st aspect, the power supply voltage stabilization unit includes a linear regulator for generating a second power supply voltage from the first power supply voltage on the basis of the potential of the reference voltage, and the power supply voltage stabilization unit controls the linear regulator to operate in a case where the reference voltage is equal to or lower than the predetermined voltage on the basis of the determination of the judging circuit. Therefore, it is possible to suppress a steep increase of the first power supply voltage by supplying energy to the second power supply voltage even when the reference voltage circuit has not started at the input of a strong electric field, thereby realizing a high-performance contactless IC card.
According to a 3rd aspect of the present invention, in the contactless IC card of the 1st aspect, the power supply voltage stabilization unit has a linear regulator, and the linear regulator generates a second power supply voltage from the first power supply voltage on the basis of comparison between the reference voltage and the predetermined voltage by the judging circuit. Therefore, it is possible to suppress a steep increase of the first power supply voltage by supplying energy to the second power supply voltage even when the reference voltage circuit has not started at the input of a strong electric field, thereby realizing a high-performance contactless IC card.
According to a 4th aspect of the present invention, in the contactless IC card of the 1st aspect, the power supply voltage stabilization unit has a shunt circuit, and an operation of the shunt circuit is controlled in accordance with the determination of the judging circuit. Therefore, it is possible to consume excess energy using the shunt circuit to suppress a steep increase of the first power supply voltage even when the reference voltage circuit has not started at the input of a strong electric field, thereby realizing a high-performance contactless IC card.
According to a 5th aspect of the present invention, in the contactless IC card of the 1st aspect, the predetermined voltage that is used for comparison in the judging circuit does not depend on the first power supply voltage, and is a fixed voltage which is lower than the reference voltage. Therefore, it is possible to suppress a steep increase of the first power supply voltage by supplying energy to the second power supply voltage even when the reference voltage circuit has not started at the input of a strong electric field, thereby realizing a high-performance contactless IC card.
According to a 6th aspect of the present invention, in the contactless IC card of the 1st aspect, the reference voltage circuit is a band-gap reference circuit. Therefore, it is possible to suppress a steep increase of the first power supply voltage by supplying energy to the second power supply voltage even when the reference voltage circuit has not started at the input of a strong electric field, thereby realizing a high-performance contactless IC card.
According to a 7th aspect of the present invention, in the contactless IC card of the 4th aspect, the shunt circuit comprises a resistor and a switch, the resistor and switch are connected in series between the first power supply voltage and a ground, and the switch is controlled in accordance with an output of the judging circuit. Therefore, it is possible to consume excess energy using the shunt circuit to suppress a steep increase of the first power supply voltage even when the reference voltage circuit has not started at the input of a strong electric field, thereby realizing a high-performance contactless IC card.
According to an 8th aspect of the present invention, in the contactless IC card of the 7th aspect, the judging circuit forcefully closes the switch in the shunt circuit when the reference voltage is lower than the predetermined voltage. Therefore, it is possible to consume excess energy using the shunt circuit to suppress a steep increase of the first power supply voltage even when the reference voltage circuit has not started at the input of a strong electric field, thereby realizing a high-performance contactless IC card.
According to a 9th aspect of the present invention, in the contactless IC card of the 3rd aspect, the judging circuit selects a higher voltage between the reference voltage and the predetermined voltage to be employed as the reference voltage. Therefore, it is possible to consume excess energy using the shunt circuit to suppress a steep increase of the first power supply voltage even when the reference voltage circuit has not started at the input of a strong electric field, thereby realizing a high-performance IC contactless IC card.
According to a 10th aspect of the present invention, in the contactless IC card of the 1st aspect, the predetermined voltage is a voltage across a forward-biased diode. Therefore, it is possible to consume excess energy using the shunt circuit to suppress a steep increase of the first power supply voltage even when the reference voltage circuit has not started at the input of a strong electric field, thereby realizing a high-performance contactless IC card.
According to an 11th aspect of the present invention, in the contactless IC card of the 1st aspect, the semiconductor integrated circuit includes a shunt regulator that is connected in series between the first power supply voltage and the ground. Therefore, it is possible to consume excess energy using the shunt circuit to suppress a steep increase of the first power supply voltage even when the reference voltage circuit has not started at the input in the first power supply voltage, thereby realizing a high-performance contactless IC card.
According to a 12th aspect of the present invention, in the contactless IC card of the 1st aspect, the semiconductor integrated circuit includes: a demodulator for demodulating RX (receiving) data which is superimposed upon the first power supply voltage; and a digital signal processing unit for processing the RX (receiving) data. Therefore, it is possible to consume excess energy using the shunt circuit to suppress a steep increase of the first power supply voltage even when the reference voltage circuit has not started at the input of a strong electric field, thereby realizing a high-performance contactless IC card.
According to a 13th aspect of the present invention, the contactless IC card of the 12th aspect further includes: a modulator for modulating an impedance between ends of the antenna coil in accordance with TX (transmission) data that is transmitted from the digital signal processing unit. Therefore, it is possible to consume excess energy using the shunt circuit to suppress a steep increase of the first power supply voltage even when the reference voltage circuit has not started at the input of a strong electric field, thereby realizing a high-performance contactless IC card.
According to a 14th aspect of the present invention, in the contactless IC card of the 1st aspect, the rectifier is a full-wave rectification circuit. Therefore, it is possible to consume excess energy using the shunt circuit to suppress a steep increase of the first power supply voltage even when the reference voltage circuit has not started at the input of a strong electric field, thereby realizing a high-performance contactless IC card.
According to a 15th aspect of the present invention, in the contactless IC card of the 12th aspect, the demodulator demodulates an ASK modulated signal. Therefore, it is possible to consume excess energy using the shunt circuit to suppress a steep increase of the first power supply voltage even when the reference voltage circuit has not started at the input of a strong electric field, thereby realizing a high-performance contactless IC card.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram illustrating a structure of a contactless IC card according to a first embodiment of the present invention.
FIG. 2 is a diagram illustrating a structure of a contactless IC card according to a third embodiment of the present invention.
FIG. 3 is a diagram illustrating an example of a power supply stabilization means, which is used for the contactless IC card according to the first embodiment.
FIG. 4 is a diagram illustrating an example of a judging circuit, which is used for the contactless IC card according to the first embodiment.
FIG. 5 is a diagram illustrating an example of a power supply stabilization means, which is used for the contactless IC card according to the second embodiment.
FIG. 6 is a diagram illustrating an example of a shunt circuit, which is used for the contactless IC card according to the third embodiment.
FIG. 7 is a diagram illustrating an example of a power supply stabilization means, which is used for the contactless IC card according to the third embodiment.
FIG. 8 is a diagram illustrating an example of a linear regulator.
FIG. 9 is a diagram illustrating a structure of a prior art contactless IC card.
FIG. 10 is a diagram illustrating an example of a rectifier.
FIG. 11 is a diagram illustrating an example of a reference voltage circuit.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Hereinafter, embodiments of the present invention will be described. The same or corresponding components in the following drawings are denoted by the same reference numerals.
Embodiment 1
A contactless IC card according to a first embodiment of the present invention will be described with reference to FIG. 1 .
This contactless IC card is different from the prior art in including a judging circuit 10 and a power supply voltage stabilization means (hereinafter, referred to as a power supply stabilization means) 11 . The power supply stabilization means 11 is constituted by a linear regulator 8 and a switch S 1 , as shown in FIG. 3 . The switch S 1 is connected to the gate of a current control transistorM 1 of the linear regulator 8 . The judging circuit 10 is constituted by a diode D 5 , a current source i 1 , and a comparator 12 , as shown in FIG. 4 . The diode D 5 and the current source i 1 are connected in series between the power supply voltage VDDA and the ground.
Next, the operation of the contactless IC card will be described. The basic operation is the same as that of the prior art. A signal that is received by the coil antenna L 1 is rectified by the rectifier 3 to generate a power supply voltage VDDA. The demodulator 5 demodulates RX (receiving) data which is superimposed upon the power supply voltage VDDA. The RX data is transferred to the digital signal processing unit 7 that is constituted by a CPU or a memory. The modulator 6 modulates an impedance between ends of the coil antenna L 1 in accordance with TX (transmission) data that is generated by the digital signal processing unit 7 . It is assumed here that a voltage Vd across the forward-biased diode D 5 has a predetermined value. For example, the positive voltage Vd is 0.8V. The comparator 12 included in the judging circuit 10 compares the predetermined voltage Vd and a reference voltage Vref with each other. When the reference voltage Vref is lower than the predetermined voltage Vd, which means that the reference voltage Vref has not sufficiently risen, the switch S 1 is forcefully turned ON, thereby supplying power from the power supply voltage VDDA to the power supply voltage VDDD. Conversely, when the reference voltage Vref is higher than the predetermined voltage Vd, the switch S 1 is turned OFF because it means that the reference voltage Vref has sufficiently risen, thereby normally operating the linear regulator 8 that is included in the judging circuit 10 .
In this way, even when a strong electric field is applied during a period until the reference voltage circuit 9 starts up, the power is continuously supplied to the power supply voltage VDDD, thereby preventing the power supply voltage VDDA from increasing above the breakdown voltage.
As described above, according to the contactless IC card of the first embodiment, the judging circuit 10 for monitoring the reference voltage Vref that is output from the reference voltage circuit 9 is provided, and then the power supply voltage VDDA is supplied to the power supply voltage VDDD by the power supply stabilization means 11 during a period until the reference voltage Vref of the reference voltage circuit 9 rises. Therefore, it is possible to suppress an increase of the power supply voltage VDDA even in a period while the reference voltage Vref has not risen yet, thereby preventing the device from being broken.
Embodiment 2
A contactless IC card according to a second embodiment of the present invention will be described.
The basic structure of the contactless IC card of the second embodiment is the same as that of the first embodiment. The difference from the first embodiment is that the power supply stabilization means 11 is replaced with a power supply stabilization means 11 a using a linear regulator 8 as shown in FIG. 5 , and the judging circuit 10 controls a reference voltage Va of the linear regulator 8 .
The judging circuit 10 selects a higher voltage between the reference voltage Vref and the diode voltage Vd as the reference voltage Va.
With the above-mentioned structure, the power according to the reference voltage Vref or the diode voltage Vd is continuously supplied to the power supply voltage VDDD even when a strong electric field is applied during a period until the reference voltage circuit 9 starts, thereby preventing the power supply voltage VDDA from increasing above the breakdown voltage.
Embodiment 3
A contactless IC card according to a third embodiment of the present invention will be described with reference to FIG. 2 .
This contactless IC card is different from the first embodiment in that the power supply stabilization means 11 is replaced with a linear regulator 8 , and further a shunt circuit 13 that is connected between the power supply voltage VDDA and the ground is provided between the shunt regulator 4 and the demodulator 5 .
Hereinafter, the operation of the contactless IC card will be described.
The shunt circuit 13 is constituted by a resistor R 6 and a switch S 2 which are connected in series between the power supply voltage VDDA and the ground, as shown in FIG. 6 . The judging circuit 10 turns the switch S 2 of the shunt circuit 13 ON to suppress an increase of the power supply voltage VDDA until the reference voltage circuit 9 starts up. When the reference voltage circuit 9 starts up, the judging circuit 10 turns the switch S 2 of the shunt circuit 13 OFF, thereby suppressing power consumption in the shunt circuit 13 .
With the above-mentioned structure, the excess energy is consumed by the shunt circuit 13 until the reference voltage circuit 9 starts up, thereby suppressing a steep increase of the power supply voltage VDDA at the input of a strong electric field.
The structures of the rectifier 3 , the linear regulator 8 , the reference voltage circuit 9 , the judging circuit 10 and the power supply stabilization means 11 , the predetermined voltage, and the communication standard, which are used in the first to third embodiments are only exemplary, and the present invention is not limited to these examples. For example, the full-wave rectification circuit has been employed as the rectifier 3 , while it is possible to employ a half-wave rectification circuit. As the rectifier 3 , any circuit can be used so long as it converts an AC signal into a DC signal. Further, the positive voltage Vd of the diode D 5 has been employed as the predetermined voltage, while it is possible to employ a voltage that is obtained by a diode connection of a bipolar or MOS transistor to a device. Further, as the predetermined voltage, any voltage may be used so long as it can rise before the reference voltage circuit 9 (a reference voltage source) will start up, and has a voltage value that is equal to or higher than the ground and equal to or lower than the reference voltage Vref at the normal operation. Further, the linear regulator 8 that is used in this third embodiment is not essential, and can be eliminated in the case of a system that can share the power supply voltage VDDD and the power supply voltage VDDA.
In the case of a system that does not require receiving and transmission, one of the demodulator 5 and the modulator 6 , or both of them can be eliminated.
When the supplied power is small, the shunt regulator 4 can be eliminated.
Further, in the third embodiment, the shunt circuit 13 is used as the power supply stabilization means 11 , while it is possible to provide a structure in which the drain and the source of a transistor M 2 are connected to the power supply voltage VDDA and the ground, respectively, as shown in FIG. 7 , thereby controlling the gate by the judging circuit 10 .
It is also possible that two rectifiers are employed as the power supply stabilization means 11 , and one or both of the two rectifiers are selected by the judging circuit 10 . In brief, the present invention encompasses all contactless IC cards which have a power supply stabilization means 11 that controls the voltage of the power supply voltage VDDA using the judging circuit 10 until the reference voltage circuit 9 starts up.
The contactless IC card according to the present invention supplies energy to the power supply voltage VDDD of the digital signal processing unit even when the reference voltage circuit is not starting at the input of a strong electric field, thereby suppressing a steep increase of the power supply voltage VDDA which is obtained by converting the energy using the coil antenna. Therefore, the power supply voltage can be stabilized, and thus a high-performance contactless IC card is realized.
|
A contactless IC card includes a reference voltage circuit, a judging circuit for monitoring a reference voltage that is outputted from the reference voltage circuit, and a power supply stabilization, unit. The judging circuit judges whether the reference voltage is equal to or higher than a predetermined voltage. When the reference voltage does not reach the predetermined voltage, the power supply stabilization unit supplies energy to the power supply to suppress a steep increase in the power supply voltage, thereby stabilizing the power supply in the contactless IC card and suppressing deterioration of the signal quality.
| 6
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention concerns a new treatment of fabric for imparting wrinkle resistance.
2. Description of the Prior Art
Prior finishing treatments to impart wrinkle resistance to cotton or other cellulosic fabric have employed the products from reaction of formaldehyde and an amido compound as finishing agents. These reaction products are methylol amides. Examples of these compounds are dimethylolurea, dimethylolethyleneurea, dihydroxydimethylolethyleneurea, and alkyl dimethylolcarbamates. These agents are applied to cotton, or other cellulose-containing fabric, with an acidic catalyst, and the fabric is heated. On heating the methylol amide reacts with two or more cellulose molecules forming crosslinks. The crosslinked cellulose makes a more resilient fiber than the untreated cellulose. The fiber is then less prone to suffer permanent deformations that appear in the fabric as wrinkles. To serve as a crosslinking agent the finishing agent must possess two or more methylolamide groups in the molecular structure.
The methylolamide crosslinking agents have been quite effective in producing wrinkle resistance. They do, however, suffer from a number of disadvantages. One disadvantage is that the agent and its reaction product on the fabric tend to decompose and release formaldehyde. Formaldehyde is very irritating and even small amounts are objectionable. It is also possible that even a small amount of free formaldehyde may be a hazard.
Another type of crosslinking treatment employs the application of unsaturated amides, such as acrylamide, with chemical or radiation initiation to promote reation of the amide with cellulose. The fabric with bound amide is then treated with formaldehyde to form chemical links between bound amide groups and thereby crosslink the cellulose. This treatment also suffers from the possibility of releasing free formaldehyde.
Formaldehyde-free finishing agents have been proposed before. One class of such agents is prepared from the reaction of glyoxal with amides. Examples of these reaction products are dihydroxyethyleneurea and dihydroxydimethylethyleneurea. These agents are of their nature formaldehyde-free. However, they suffer from lack of effectiveness, that is, they produce less wrinkle resistance, and also have other disadvantages, such as causing discoloration of the fabric. Still other formaldehyde-free crosslinking agents have been proposed. These contain different groups for reaction with cellulose, such as epoxy, chlorohydrin, isocyanate, and hydroxyethylsulfone. All of these have disadvantages that prevented their wide use in commercial practice.
SUMMARY OF THE INVENTION
The purpose of this invention is to provide a treatment for cotton fabric and other fabric composed entirely or in part of cellulose that will render the fabric resistant to wrinkling in use and in laundering and that will consist in applying a finishing agent or agents not made from formaldehyde. Therefore, there will be no release of formaldehyde from the treatment or treated fabric.
The treatment of this invention consists in first applying acrylamide to the fabric with a chemical initiator that will promote reaction of the acrylamide with the cellulose of the fabric on heating. The fabric is then heated to allow this reaction to proceed. After that, glyoxal is applied with an acidic catalyst. The fabric is heated to cause reaction of the glyoxal with the amide groups under the influence of the catalyst. Reaction of glyoxal among two or more amide groups produces crosslinks between cellulose molecules. The cellulosic fabric is thereby given increased resistance to wrinkling without the use of materials that are made from formaldehyde and that could revert to formaldehyde during treatment or on the treated fabric.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the application of the invention acrylamide is applied to fabric from an aqueous solution containing about 5-20% acrylamide. Approximately 10% was found to be suitable using the equipment for treating the fabric in our laboratory trials. Although acrylamide is the preferred compound, other unsaturated amides without substituents on the amide group may be used, for example, methacrylamide and crotonamide.
Included in the solution with the acrylamide is an initiator for the reaction between acrylamide and cellulose. This initiator can be an alkaline compound, to promote reaction by an ionic mechanism, or a peroxy compound, to promote reaction by a radical mechanism. If an alkaline compound is used, about 1.0% sodium carbonate is preferred although other alkaline compounds giving a similar degree of alkalinity may be substituted. If a peroxy compound is used as an initiator, 0.01-0.10% ammonium persulfate is used with about 0.02-0.03% preferred. Again, equivalent amounts of other persulfates may be substituted.
The solution of acrylamide and initiator may be applied to fabric by any convenient means. The most common method is by padding, where the fabric is soaked with the solution and passed between squeeze rolls to remove excess solution. In our application by padding, the fabric retained an amount of solution equal to 80-90% of dry fabric weight. Concentration of the solution can be adjusted in the fabric retains more or less of the solution in another application procedure.
After the solution is applied, the fabric is dried. Again, any convenient method may be used. In most instances the fabric will be heated to increase the rate of drying. With persulfate initiators it is advantageous to keep the temperature below 70° C. during drying to prevent premature reaction. With alkaline initiators a greater freedom in temperature is allowed.
After the fabric is dried, it is heated at 120°-160° C. for 3-5 minutes to promote reaction of the acrylamide with the cellulose. With alkaline initiators, heating at 160° C. for 3 minutes is preferred. This heating may be done in ordinary hot air. With persulfate initiators, the heating is preferably done in an inert atmosphere such as nitrogen. Equipment is used in which the fabric is sealed and the surrounding air replaced by nitrogen before heating. Under these conditions it usually takes longer for the fabric to reach the desired temperature. Therefore, a longer period of heating is desirable, for instance 5 minutes at 120° C.
After reaction with acrylamide the fabric is preferably washed to remove any acrylamide not bound to the fabric. However, this washing can be omitted with only a small diminution of the properties to be imparted to the fabric.
The fabric with bound acrylamide is then impregnated with a solution containing 2-20% glyoxal and 0.5-3.0% of an acidic catalyst. In most treatments 5-10% glyoxal is preferred. The catalyst is an acidic salt that will promote reaction of the glyoxal with amide groups but will not damage the fabric. Magnesium chloride in 1.5-2.0% concentration is preferred. Other salts that could be substituted are zinc nitrate, zinc fluoborate, and ammonium chloride.
The fabric is impregnated by padding as before and dried in hot air. The dried fabric is then heated at 150°-160° for 2-5 minutes with 160° C. for 3 minutes preferred. During this period of heating reaction of the glyoxal and formation of crosslinks occurs. It is preferable that the fabric be washed as a final step to remove unreacted agents.
After this treatment the fabric resists wrinkling from random bending in use or in the tumbling during washing and drying.
In the following examples, all percentages are percent by weight. The test methods used to evalulate fabric properties are from those described by the American Association of Textile Chemists and Colorists in the Technical Manual of the AATCC.
EXAMPLE 1
Cotton printcloth was impregnated with an aqueous solution of 12% acrylamide and 1.0% sodium carbonate by wetting the fabric with a solution and then passing the fabric through squeeze rolls to allow the fabric to retain an amount of solution equal to 80-90% of its weight. The fabric was dried at 70° C. for 7 minutes and then heated at 160° C. for 3 minutes. The fabric was divided, and one portion (A) was washed and the second portion (B) was left unwashed. Both portions of the fabric were impregnated as before with an aqueous solution of 10% glyoxal and 1.8% magnesium chloride hexahydrate to give 80-90% weight gain. The fabric was dried at 70° C. for 7 minutes and then heated at 160° C. for 3 minutes. Both portions and a sample of the untreated fabric were washed and tested for durable-press rating to show smoothness after washing and for wrinkle recovery angle to show resistance to wrinkling in use.
TABLE 1______________________________________ WRINKLE RECOVERY DURABLE-PRESS ANGLES (degrees,FABRIC RATING sum of warp of fill)______________________________________Portion A 3.4 272Portion B 3.2 261Untreated 1.5 189______________________________________
EXAMPLE 2
Cotton printcloth was impregnated, as in Example 1, with a solution of 12% acrylamide and 1.0% sodium carbonate. The fabric was dried at 70° C. for 7 minutes and heated at 160° C. for 3 minutes. The fabric was washed and then impregnated with a solution of 5.0% glyoxal and 1.8% magnesium chloride hexahydrate. The impregnated fabric was dried 7 minutes at 70° C. and heated 3 minutes at 160° C. After washing, the treated fabric had a durable-press rating of 3.3 and a wrinkle recovery angle of 280°, sum of warp and fill determinations.
EXAMPLE 3
Cotton printcloth was impregnated by padding through squeeze rolls with a solution of 10% acrylamide and 0.03% ammonium persulfate. The fabric was dried at 60° C. and then placed in a metal foil container. The foil container was flushed with nitrogen and sealed. The fabric was heated 5 minutes at 120° C. in the nitrogen atmosphere and then washed. The washed fabric was padded with a solution of 8.2% glyoxal and 1.8% magnesium chloride hexahydrate, dried, and heated 3 minutes at 160° C. After washing and tumble drying the treated fabric had a durable-press rating of 3.3 and a wrinkle recovery angle of 280°.
EXAMPLE 4
Cotton printcloth was treated as in Example 3 with a solution of 10% acrylamide and 0.02% ammonium persulfate and then, after washing, with a solution of 4.1% glyoxal and 1.8% magnesium chloride hexahydrate. After washing and tumble drying the treated fabric had a durable-press rating of 3.0 and a wrinkle recovery angle of 272°.
|
Cotton, or other fabric containing cellulose, is treated with acrylamide and a chemical initiator that promotes reaction of acrylamide with cellulose. The fabric, with bound acrylamide, is then treated with glyoxal and an acidic, metal salt catalyst to produce a fabric containing crosslinked cellulose. Thus, the fabric is given wrinkle resistance and durable-press properties by the treatment without using formaldehyde, free or combined, that could be released during treatment or from the treated fabric.
| 8
|
BACKGROUND OF THE INVENTION
Pneumatic conveying generally is utilized to transport dry, free-flowing, granular or pulverant material in suspension within a suitable conduit such as a pipe or duct by means of a high velocity airstream or by suction. A principal use of pneumatic conveying which has grown significantly in recent history is in the plastic processing industry wherein particulate such as plastic pellets or powdery resin is fluidized or suspended in a relatively contamination free airstream for transportation from bulk containers to a plurality of downstream plastic processing loaders.
With many prior pneumatic conveying systems, such as plastic material transporting systems, the primary material conduit is located upwardly of the receiving stations and branch conduits extend downwardly from the primary conduit and communicate with the material receivers. In such instances the primary conduit generally extends continuously across the juncture with the branch conduits and the selective material flow from the primary conduit to the respective receivers was often controlled by valves positioned in the primary conduit or the branch conduits adjacent the receivers.
The means of controlling material flow by the inclusion of a multiplicity of conduit valves is extremely expensive, requires constant maintenance and often results in clogging of the primary and/or branch transporting conduits. On this latter point it is noted that in the event of the cessation of vaccum by closing the valve of a downstream receiver for the purpose of directing the particulate stream to an upstream receiver, the inertia of the particulate in suspension will carry past the juncture of the primary conduit with the upstream receiver and settle and build up in the primary conduit at a location intermediate the upstream and downstream receiver. Such a settling and build up of particulate can result in subsequent rough material flow, decreased efficiency and, on occasion, complete system blockage. Furthermore, depending on exactly where the valves are located, or indeed if conduit valves are utilized, the particulate inertia, coupled with normal gravitational forces, may result in blockage of any one or more of the downwardly extending branch conduits.
SUMMARY OF THE INVENTION
The present invention utilizes a primary conduit having a series of diverter means disposed therein at the juncture of the primary conduit with the branch conduits, to overcome the hereinabove mentioned problems, or in the least, greatly alleviate them. More specifically the diverter means include a "Y" configuration juncture such that the flow path of the suspended particulate within the primary conduit will be stepped upwardly at the juncture. Thus the inertia of the particulate will be reduced at these juncture points to a degree that it will not be sufficient to carry over from the juncture when the vacuum to an adjacent downstream receiver is discontinued. Furthermore, by providing the diverter means with an elbow prior to connection to the branch conduit, the inertia of the particulate tending to enter the branch conduit is also reduced. This inertia reduction at the elbow will reduce the amount of particulate entering the branch conduit (and being acted upon by gravity to compact and perhaps clog the branch conduit) upon cessation of vacuum to the respective receiver therefore.
Accordingly, it is one object of this invention to provide a new and improved apparatus for the transportation of pneumatically suspended particulate through a single primary conduit to a plurality of spaced receivers having improved means for preventing the build up of particulate within the primary conduit.
Another object of this invention is to provide an improved means for inhibiting the build up of particulate within the branch conduits of receivers no longer having vacuum applied thereat.
A still further object of this invention is to provide a new and improved apparatus for the transportation of pneumatically suspended particulate through a primary conduit to a plurality of spaced receivers which does not require mechanical valving means at all of the junctures of the primary conduit with the branch conduits.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other objects of the present invention will become more readily apparent upon a reading of the following description and drawings in which:
FIG. 1 is a schematic representation of a multi-receiver pneumatic transporting system constructed and operational in accordance with the principles of the present invention;
FIG. 2 is a projection of diverter means of the present invention which is disposed in the primary conduit of the FIG. 1 system at the junctures thereof with the branch conduits;
FIG. 3 is a side elevational view of the diverter means illustrated in FIG. 2;
FIG. 4 is a top view of the diverter means as viewed on lines 4--4 of FIG. 3; and
FIG. 5 is an end view of the diverter means as viewed on lines 5--5 of FIG. 3.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 is a schematic representation of a multi-receiver pneumatic transporting system 10 of the present invention which, as shown, is of a type commonly used in the plastics processing industry.
System 10 comprises: an upstream material source 12, a plurality, as shown four material receivers which are located downstream of the source 12 and are consecutively identified at 14, 14', 14" and 14"', with receiver 14 being the receiver most closely adjacent source 12; a primary material transporting conduit 16 which communicates at one end thereof with source 12; and a plurality of branch delivery conduits 18 which extend generally between respective material receivers and conduit 16 for the delivery of material from conduit 16 to the material receivers. A suitable vacuum pump 20 communicates with receivers 14 through 14"' by means of an exhaust conduit assembly 22. Diverter means 24 of the present invention are disposed within primary conduit 16 at the respective junctures of the branch conduits 18 of receivers 14, 14' and 14".
Inasmuch as the invention herein is primarily to the configuration and utilization of diverter means 24 and further, that the general operation of multi-receiver pneumatic transporting systems are well known in the art, a detailed description of the components and operation of system 10 are not necessary to one skilled in the art for a full understanding of the invention herein.
System 10 is made operative by energizing vacuum pump 20 and opening one or more suitable valves (not shown) in or adjacent receivers 14 through 14"' to cause operative communication between pump 20 and material source 12, via conduit assembly 22, branch conduits 18 and the primary conduit 16. The particulate material, for example plastic pellets or the like, is entrained in the downstream flowing air stream and the particulate laden stream continuously enters primary conduit 16. If for example, the particulate material is to be fed solely to material receiver 14, the valves adjacent receivers 14', 14" and 14"' are suitably positioned to an off position to discontinue communication between these latter mentioned receivers and the exhaust conduit assembly 22. It is particularly to this type of condition (i.e. when an exhaust communication with a downstream receiver is discontinued) that one primary aspect of the diverter means 24 of this invention is directed.
Referring to FIGS. 2 through 5, diverter means 24 comprises: an elongated generally cylindrical main body member 26 having an upstream end 28 and a downstream end 30; an elongated generally cylindrical "Y" diverter or transition member 32 which has the upstream or lower end 40 thereof in open communication with member 26 intermediate ends 28 and 30 and which slopes upwardly and downstream therefrom at an acute angle with respect to the longitudinal axis of member 26 in a manner that the longitudinal axis of the uppermost end portion of member 32, passes through the downstream end 42 of member 32, is upwardly spaced from and extends in a direction generally parallel to the longitudinal axis of member 26; and an elbow member 34, shown as a 90° elbow, which has the upstream end 44. thereof secured in coaxial alignment to the downstream end 30 of member 26 and extends horizontally outwardly therefrom in a manner that the other or downstream end 46 thereof is displaced 90° from downstream end 30.
Diverter means 24 is disposed within the primary material conduit 16 at each takeoff therefrom to a material receiver 14 through 14"' in a manner that the upstream and downstream ends 28 and 30 are suitably sealingly secured, such as by friction fits or cylindrical sleeves, to respectively adjacent intermediate ends 40 and 42 of conduit 16 to thus provide a continuous flow path for the particulate laden stream from the material source 12 to the final downstream material receiver 14"'. Similarily, the downstream end 46 of elbow member 34 is suitably sealingly secured, such as by friction fits or cylindrical sleeves, to the upper or upstream end of the respective branch delivery conduits 18. As shown branch conduits 18 are formed of flexible material, such as corregated hollow cylindrical tubing. Thus conduits 18 may be flexed to provide the necessary routing of the takeoff flow path for the particulate laden airstream from the conduit 16 to the downwardly spaced material receivers 14 through 14"'. If such receivers are additionally spaced laterally from conduit 16 then the conduits 18 may be routed for a horizontal traverse and a subsequent vertical drop or may be sloped on a downwardly extending diagonal if preferred.
With such an arrangement and configuration of elements as discussed hereinabove, a means and method is provided for the selective conveying of pneumatically suspended particulate through the single primary conduit 16 to a plurality of spaced receivers 14 through 14"' with a minimum of buildup on clogging of particulate within the conduits 16 and 18. Specifically because of the greater density of the particulates relative to the fluid in the airstream within which they are suspended, the particulate has a greater inertia within the flowing stream and will resist switching. Thus, when it is desired to cease loading of, for example, a downstream receiver and the vacuum applied thereto through exhaust conduit assembly 22 is discontinued, the inertia of the particulate within the conduit 16 will result in the particulate flow not being immediately responsive to such a vacuum discontinuance. In the event that no means are provided within conduit 16 to slow or decrease the inertia of the particulate, the particulate, because of inertia, will carry over into the portion of conduit 16 which lends directly to the receiver for which vacuum feed is discontinued. Thus, the carryover particulate will settle in this portion of the conduit 16 and may clog the conduit 16 or cause uneven material flow therethrough when vacuum is again applied at the downstream receiver. However, the present invention provides a diverter means 24 at each juncture of the primary conduit 16 with a branch conduit 18. The diverter means 24 includes a "Y" diverter member 32 which steps up the elevation of the conduit 16 at each juncture. Thus, the change in elevation of conduit 16 will slow the inertia and inhibit the flow of particulate past the diverter means when downstream vacuum is discontinued. As discussed before the "Y" diverter member 32 slopes upwardly at an acute angle with respect to the longitudinal axis of the main body member 26. This angle, which is indicated at "A" in the Figures, should not be so large that it results in unduly inhibiting the relatively free flow of the particulate laden stream when vacuum is present at all receivers, nor should it be so small as to not substantially decrease the particulate inertia when vacuum to downstream receivers is decreased. It has been found that an angle "A" of the upward slope of the diverter member 32, with respect to the longitudinal axis of the main body member 26 in the general range of fifteen to sixty five degrees is preferred.
For similar reasons, the particulate inertia also creates a potential buildup problem in the branch conduits 18. For this reason the diverter means 24 is provided with the elbow member 34. Elbow member 34 acts to decrease the inertia of the particulate and thus prevent a substantial carryover into conduits 18 when the vacuum for the respective material receiver therefor is discontinued. The preferred range for elbow member 34 is a maximum elbow of ninety degrees and a minimum elbow of sixty degrees, the latter elbow providing a slight reversal in flow which even further reduces the particulate inertia.
The embodiment described herein is the presently preferred embodiment of a means for transporting pneumatically suspended particulates from a source to a plurality of receivers which is constructed in accordance with the principles of the invention; however, it is understood that various modifications may be made to the embodiments described herein by those knowledgeable in the art without departing from the scope of the invention as is defined by the claims setforth hereinafter. For example: connecting sleeves for members 26, 32 and 34 may be utilized rather than the weldment as illustrated; the diverter means 24 may be formed without the elbow member 34 if desired; the branch conduits 18 may be formed as rigid members, if desired; and the like.
|
An apparatus of transporting pneumatically suspended particulates from a source to a plurality of receivers and, more particularly, an apparatus for such conveying offering an improved means to minimize material blockage of the primary and branch delivery conduits when switching primary feed of the suspended particulates from one receiver to another.
| 1
|
BACKGROUND OF THE INVENTION
The present invention relates to implements used for tending ground areas, and more particularly to an implement for simultaneously moving and sifting sandy earth.
Ground areas not covered with grass or other plants are particularly noticeable when littered. They have a tendency to collect and hold debris not only on the surface, but to some depth as well. Vigilant policing of sandy ground areas, such as a beach in front of a hotel, can remove the visible debris. But when subsequent winds, pedestrians, and vehicles shift the top surface, additional debris may be exposed. As a result, sandy areas cannot be cleansed of debris by visual inspection and debris collection.
Sandy ground areas can be more thoroughly cleared of debris by using a screening box and shovel. The screening box is typically a shallow rectangularly shaped support having a screen fitted across the bottom. The screening box is elevated onto a support structure leaving the bottom screen portion free from obstruction, or is manually held by one person who performs the screening function. A second person shovels the sandy earth into the screening box, where the sand passes through while the debris remains trapped in the box by the screen for subsequent disposal.
This technique involves the expenditure of significant energy on behalf of the person shoveling the sand. In order to clean large sandy areas, many cubic yards of debris laden soil have to be elevated to the screening box's vertical level, then sifted and respread; the thorough cleaning of a given area requires hours of work.
With the screening box method, time must be taken to separately dump the debris collected from each few shovel-full of sand. If the screening box is not dumped often, two undesirable effects result. As greater amounts of debris begins to collect in the screening box, the debris itself begins to impede the sifting action of the screen and reduces the rate at which sand passes through the screen of the screening box. Secondly, the increased weight of larger amounts of debris, and the increasing weight of the sand which is backed up due to the slower rate of sand passage through the screen of the screening box, imparts tensive stress upon the screen. Tensive stress can result in tearing of the screen or failure of the points of attachment of the screen to the screening box.
What is needed is a device facilitating an easier method for effectively cleaning sandy soil areas of debris, both visible debris at the surface, and hidden debris within the volume. In order to reduce the expenditure of energy, the device should require the sandy soil to undergo a minimum of displacement during the cleaning process, and especially minimum vertical displacement. The needed device should not allow the debris to collect to the point that the cleaning action is impeded. Further the needed device should facilitate easy transfer of the debris into a container without having the operator stop to perform a different function. These and other objects of the present invention will be apparent to one skilled in this art from the following description of a preferred embodiment.
BRIEF SUMMARY OF THE INVENTION
The present invention provides a device which contains a screen surface and which is convertible to be configured as a rake or as a shovel. When configured as a rake, sandy soil can be cleaned of debris occurring above and below the surface by a raking action. When configured as a shovel, sandy soil can be cleaned of debris occurring above and below the surface with a shoveling action.
The lifting of the debris from the sandy soil surface is facilitated in either the rake or shovel configuration. In both configurations, the sandy soil is not significantly vertically displaced above ground level, thus minimizing the energy expenditure by the operator. In either configuration, the operator can easily control the depth of sandy soil which is to be cleaned.
BRIEF DESCRIPTION OF THE DRAWINGS
Other aspects, features and advantages of the invention, its configuration, construction and operation will be best understood from the following detailed description, taken in conjunction with the accompanying drawings in which:
FIG. 1 is a perspective view of the combination sand rake and shovel of the present invention assembled into the shovel configuration;
FIG. 2 is a partially exploded view of the combination sand rake and shovel shown in FIG. 1;
FIG. 3 is a cross-sectional view of the handle of the combination sand rake and shovel taken along line 3--3 of FIG. 1;
FIG. 4 is an exploded view of the screening frame of the combination sand rake and shovel shown in FIGS. 1 and 2;
FIG. 5 is a perspective view of the combination sand rake and shovel of the present invention assembled into the rake configuration; and
FIG. 6 is a side view of the combination sand rake and shovel shown in FIG. 5, illustrating the details of attachment of the handle support to the screening frame.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, the combination sand rake and shovel of the present invention has an elongate handle 11, engaging a handle support 13. Handle 11 is preferably a section of straight or linear, hollow metallic tube made of aluminum or some other light metal. Handle support 13 may be formed from a single or double length of metallic bar stock, preferably from a strong, light metal. Handle support 13 is attached to handle 11 by extension of portion 14 into handle 11. As the handle support extends away from handle 11 it forms a pair of wings, each of which extend in opposite directions.
The ends of the wings of the handle support 13 are bent slightly to form attachment plates 15 having surface planes generally parallel to each other. Attachment plates 15 flatly abut an elongate edge plate 17 at points near the ends of edge plate 17. Attachment plates 15 each has a pair of apertures 19 near its end, which apertures are in mating alignment with a pair of apertures 21 near the ends of elongate edge plate 17.
A pair of bolts 23 join the elongate edge plate 17 to attachment plates 15 of handle support 13, each of said bolts 23 receiving a wing nut 25. Attached to elongate edge plate 17 is a screen frame member 27. Elongate edge plate 17 may form a portion of the screen frame member 27. The elongate edge plate 17 has a plane which meets the plane of screen frame member 27 at a right angle.
Screen frame member 27 has a frame portion 29 securing a screen portion, or screen 31. Screen 31 is attached to frame portion 29 by any appropriate means such as welding or gluing, but the preferred method is by sandwiching the screen portion 31 between members comprising the frame portion 29.
Referring to FIG. 2, the handle 11, handle support 13, and edge plate 17 are shown in an exploded relationship. Handle support 13 is seen as being a single length of bar stock folded acutely at the center, although the center folded portion 14 could consist of two individual pieces of bar stock brought together in close proximity. The portion 14 of handle support 13 not forming the oppositely extending wings, is pressed together in close proximity for fitted insertion into the hollow end 33 of handle 11. The manner of insertion of bolts 23 through apertures 19 and 21 of attachment plates 15 and edge plate 17 is clearly shown.
Referring to FIG. 3, a cross-sectional view inside handle 11 at line 3--3 of FIG. 1, illustrates the preferred relationship between the internal diameter of handle 11 and the height of the two lengths of handle support 13 which reside within handle 11. The spacing between the two lengths of handle support 13 is dependent upon their height, the higher they are, the closer spacing between them is forced by the internal diameter of handle 11. Consequently, if the correct spacing is selected, the handle support 13 can be further anchored into handle 11 by using a wedge (not shown) inserted into the hollow end 33 of handle 11 between handle support 13, or by using a metal screw on the underside of handle 11 at the appropriate distance from the acute fold of handle support 13 to force the sides of the handle support 13 apart to increase the tightness of fit.
FIG. 4, an exploded view of frame portion 29, illustrates one possible configuration of the sand rake/shovel and its component parts. Here, the edge plate 17 is seen to be one side of an angle beam 35 having a 90° angle between its two planar surfaces. The bottom surface of angle beam 35 has a pair of apertures 37.
A first top frame bar 39 has a pair of apertures 41 in alignment with apertures 37 of the bottom surface of angle beam 35. A pair of side bottom frame bars 43 have apertures 45 which align with apertures 47 in a pair of side top frame bars 49. A front bottom frame bar 51 has apertures 53 in alignment with apertures 55 of a second top frame bar 57.
Screen 31 has edges which rest upon the bottom surface of angle beam 35, side bottom frame bars 43 and front bottom frame bar 51. Resting upon screen 31 and sandwiching screen 31 with respect to bottom surface of angle beam 35, side bottom frame bars 43 and front bottom frame bar 51, are first top frame bar 39, side top frame bars 49, and second top frame bar 57, respectively.
A set of short bolts 59 extend through apertures 37, 41, 45, 47, 53, and 55 to rigidly join, the aforementioned sandwich structure. Alternatively, a plurality of rivets can be used in lieu of short bolts. The ends of side bottom frame bars 43 closest to angle beam 35, overlap the bottom surface of angle beam 45 to lend rigidity and support to the side top frame bars 49.
The mesh size of screen 31 is typically large enough to admit 1/16th bolts through its apertures without damaging the screen. The ideal screen mesh size will be sufficient to permit sand and sandy soil to pass readily through the screen aperture without allowing debris to also pass. The material of screen 31 should also be sufficiently structurally stable to support itself under the stress of a single volume of sand.
Referring to FIG. 5, the members of FIGS. 1-4 can be repositioned or rearranged into a rake configuration. The handle support 13 has been removed from edge plate 17 of angle beam 35, and now the attachment plates 15 of handle support 13 attachably abut first top frame bar 39. In the configuration of FIG. 5, the apertures 19 are aligned with the apertures 37 and 41 at the outermost ends of angle beam 35 and first top frame bar 39. The same bolts 23 and wing nuts 25 are used to attach handle support 13 to first top frame bar 39 and the bottom of angle beam 35.
In the raking configuration of FIG. 5, as substantial force is applied to handle 11 in a raking type motion, the maximum loading will occur at the edge of screen frame member 27 opposite the edge attached to handle support 13. Consequently, an additional member, namely structural member 61 is attached between the edge of screen frame member 27 opposite the edge attached to handle support 13, and handle 11. Structural member 61 secures the angle of the plane of screen frame member 27 with respect to handle 11. Ideally, for economy, structural member 61 will be a threaded rod having slight bends at its extreme ends so that it may enter frame member 27 and handle 11 perpendicularly.
Structural member 61 is secured by wing nuts 63, one on each end of structural member 61, as structural member extends through aperture 65 in handle 11 and apertures 53 and 55 in front bottom frame bar 51 and second top frame bar 57, respectively. The spacing between the two lengths of handle support 13 within handle 11 shown in FIG. 3 could be created by virtue of the aforementioned metal screw (not shown) securing the handle supports 13 within handle 11, or via the use of a metal sleeve (not shown) pushed between the two lengths of handle support 13 into alignment with aperture 65.
Referring to FIG. 6, a side detail of the rake configuration illustrated in FIG. 5, bolts 23 are secured by wing nuts 25 to attachment plates 15 of handle support 13 onto side top frame bars 49 and further onto the bottom surface of angle beam 35. Also visible in phantom are the apertures 19 in the attachment plates 15 of the handle support 13. Apertures 21 on the edge plate 17 portion of the angle beam 35 are also shown in phantom, the apertures 21 to be utilized when screen frame member 27 assumes the shovel configuration of FIGS. 1-4.
In the operation of the combination sand rake and shovel of the present invention, the device of the Figures may be configured as a rake as shown in FIGS. 5 and 6 by inserting bolts 23 through the apertures 37 in the bottom portion of angle beam 35 and apertures 41 in first top frame bar 39 and through apertures 19 in attachment plates 15 and secure the bolts 23 by the wing nuts 25. Next, structural member 61 is extended through aperture 65 in handle 11 and apertures 53 and 55 in front bottom frame bar 51 and second top frame bar 57, respectively. The ends of structural member 61 are then secured with wing nuts 63, and the rake configuration is complete.
Referring to FIG. 7, an alternate construction of a portion of the sand rake and shovel of FIGS. 1-6 is illustrated. Here, the screen frame member 27' is made of an upper frame 71, including elongated edge plate 17, and a lower frame member 73. Upper frame member 71 has apertures 75 in alignment with apertures 77 on lower screen frame member 73. Screen 31 is sandwiched between the upper frame member 71 and lower frame member 73 and bolted with bolts 59. The use and operation of the screen frame member of FIG. 7 is identical with that of FIGS. 1-6.
The invention now is utilizable as a rake with which to separate debris from sand. In the rake configuration, the device and method of the present invention is pulled through the sand or sandy soil, the debris being urged along by the screen 31 while the sand passes through the screen 31. The angle of attack of the screen frame member 27 with respect to the ground is adjusted by the user by adjusting the horizontal offset angle of handle 11 during the raking motion. A more perpendicular angle with respect to the ground will yield a more shallow insertion of screen frame member 27 into the ground, while a more acute angle will yield a deeper insertion of screen frame member 27 into the ground. The screen frame member 27 can flex somewhat toward the handle 11 when pushed through the sand but its flexing motion away from the handle 11 is limited by structural member 61. This flexing assists in the siting action of screen 31 and assists in the performance of the invention.
With the raking motion, debris may be effectively gleaned from the first three to five inches of sand. The rake configuration facilitates a pulling motion which is not as difficult upon the operator. Very little sand is vertically elevated, thus conserving the user's energy, and increasing both the volume and surface area of sand which can be cleaned. Further, the raking motion facilitates the alignment of the debris along a raking line, which in turn facilitates the movement of the rake to form small piles of debris. This is particularly useful in instances where the volume of debris is small or large areas need to be cleaned, since less time will be spent disposing of a greater number of the smaller piles of debris which would result.
Further, in the operation of the combination sand rake and shovel of the present invention, the device of the Figures may be configured as a shovel as was shown in FIGS. 1-4 by inserting bolts 23 through the apertures 21 in edge plate 17 and through apertures 19 in attachment plates 15 and secure the bolts 23 by the wing nuts 25.
The invention now is utilizable as a shovel with which to pick up debris while letting the sand associated with and surrounding the debris fall through the screen 31. In the shovel configuration, the device and method of the present invention is well adapted to pick up debris lying on or near the surface as a result of using the rake in the raking configuration referred to above. With the shovel configuration, the collected debris, as a result of the raking operation, can be picked up and separated from the surrounding sand in one step. Thus, the only weight of material which it is necessary to lift is that of the debris, not the sand.
Although the invention has been derived with reference to particular illustrative embodiments thereof, many changes and modifications of the invention may become apparent to those skilled in the art without departing from the spirit and scope of the invention. Therefore, included within the patent warranted hereon are all such changes and modifications as may reasonably and properly be included within the scope of this contribution to the art.
|
A combination sand rake and shovel providing the ability to clean sandy with a tool having two configurations. When configured as a shovel, the debris may be lifted directly from the sand. When configured as a rake, the debris can be screened in a direction parallel to the grounds surface.
| 4
|
FIELD OF THE INVENTION
This invention relates to a machine which is suitable for use in squaring bundles of articles. The machine may be used for squaring bundles of cartons and is herein described in terms of such usage. However, it is to be understood that the machine may be used for squaring other articles which are stacked one upon the other to form a bundle.
In a typical carton producing plant, stacks of flat form cartons are delivered to a squaring machine from a preceding carton production line, with individual cartons in each stack being randomly orientated to a certain extent. Each stack of cartons is squared-up to a neat bundle in the machine, and then passed to a strapping machine where the squared bundle is strapped with one or more bands of a heat sealable plastics material.
DESCRIPTION OF THE PRIOR ART
Bundle squaring machines per se are well known and take various forms. One such machine, which is thought to be the most closely related to that now developed by the inventor, is manufactured by Ampag GmbH of Cologne, West Germany.
The Ampag machine comprises a series of horizontal driven rollers which transport a bundle of cartons in a longitudinal direction into, through and from a squaring zone. Whilst in the squaring zone, side squaring arms close onto the bundle in a lateral direction to square-up the sides of the bundle and, at the same time, an overhead pusher fork pivots downwardly against the trailing end of the bundle. The pusher fork then functions to push the bundles of cartons forward against vertically disposed rollers which are located adjacent the leading edge of the side squaring arms, the rollers being spring loaded to normally locate just inside the line of the side squaring arms and to inhibit (but not prevent) forward movement of the bundle. The action of the pusher fork moving the bundle longitudinally forward against the vertically disposed rollers results in squaring-up of the leading and trailing ends of the bundle, after which the side squaring arms (together with the vertically disposed rollers) and the pusher fork move away from the bundle and the squared bundle is then carried forward on the horizontal rollers.
SUMMARY OF THE PRESENT INVENTION
The squaring machine in accordance with the present invention is of the same general type as the Ampag machine above described, but it embodies features which distinguish over the Ampag type machine and which avoids problems inherent in that machine. These features are discussed in detail below.
In general terms, the present invention provides a bundle squaring machine comprising:
(a) a horizontally disposed conveyor system for conveying a bundle of articles in a longitudinal direction into and from a squaring zone of the machine,
(b) a pair of parallel spaced-apart vertically disposed side squaring arms located above the conveyor system, the squaring arms being actuable to move toward one another in a lateral direction, whilst maintaining their parallel relationship, to co-act against a bundle of articles when located therebetween, and the squaring arms defining side borders of the squaring zone,
(c) pusher means normally located in a retracted position below the level of the conveyor system intermediate the squaring arms, the pusher means being actuable to project upwardly above the level of the conveyor system and then to move in the longitudinal direction of the machine to push against a trailing end of a bundle of articles when located within the squaring zone,
(d) vertically disposed rollers pivotably mounted one to each of the squaring arms at the leading end thereof, the rollers being spring biased to normally locate within side borders of the squaring zone to engage with a leading end of a bundle of articles when located within the squaring zone and when pushed longitudinally forward by the pusher means,
(e) means actuable to cause the vertically disposed rollers to pivot away from their normal position and to a position outside of the side borders of the squaring zone following a period of contact between the vertically disposed rollers and a bundle when located within the squaring zone, and,
(f) means actuable to halt movement of the conveyor system during actuation of the squaring arms and the pusher means.
In operation of the above described machine, a bundle of cartons is conveyed longitudinally forward toward the squaring zone and, as the bundle is about to enter the squaring zone, the bundle actuates a sensor. This then results in de-energization of the conveyor and actuation of the side squaring arms. Such arms then move in a lateral direction toward one another to act against the sides of the bundle and effect squaring-up of those sides. At the same time, the pusher means are actuated to project upwardly behind the trailing edge of the bundle within the squaring zone and then to move forward against the bundle. This has the effect of driving the bundle forward, between the side squaring arms, and into contact with the vertically disposed spring biased rollers at the leading end of the arms. Having contacted the vertically disposed rollers, the bundle is squared-up, fore and aft, being pushed against the rollers, but no crushing force is exerted on the bundle because the rollers are able to pivot back against the spring bias and thereby permit longitudinal advancement of the squared bundle. As the bundle is pushed forward between the rollers a further sensor is actuated, and this results in the following sequence of events:
(1) The vertically disposed rollers are caused to pivot away from contact with the leading end of the bundle. The drive to effect this pivoting movement is preferably delivered by way of a fluid operated piston.
(2) The side squaring arms are then caused to move away from the sides of the bundle, and at the same time, the forward movement of the pusher means is halted.
(3) The pusher means is then moved longitudinally backwards to its starting position and retracted so that a further bundle may enter the squaring zone.
(4) The conveyor system is restarted to carry the squared bundle forward and to convey a waiting bundle to the squaring zone. During restarting of the conveyor system the initial acceleration is kept sufficiently low as to prevent slippage between articles forming the squared bundle and to thus prevent the bundle from being "jerked out of square".
A particularly significant feature of the present invention as above defined resides in the provision of the means (the fluid operated pistons) which are actuated to cause the vertically disposed rollers to pivot away from the their normal position after being contacted by the leading end of the bundle. Such means counter the effect of the spring bias on the rollers and move the rollers away from the leading end of the bundle prior to movement of the side squaring arms away from the bundle. This action is made to occur in the machine to guard against any lack of synchronization in movement of the two side squaring arms, because if movement of the arms is not completely synchronized, the roller associated with a slower moving one of the arms will tend to bias forward and push the previously squared bundle out of square.
A further important feature of the present invention is the provision made for halting movement of the conveyor system whilst the bundle is being subjected to a squaring operation. This avoids any rapid acceleration being imparted to the bundle after completion of the squaring operation.
A further, preferred, feature of the present invention resides in the provision of an angle diverter which is suitable for use in conjunction with the bundle squaring machine as above defined. Such angle diverter permits bundles of randomly orientated articles to be delivered to the bundle squaring machine (or to any other machine) at an angle, usually approximately 90° to the longitudinal direction of movement of the conveyor system of the squaring machine.
The angle diverter, which may be alternatively referred to as an article feed diverter, comprises first and second conveyor systems, the first system comprising a drivable conveyor system and the second system comprising an idler conveyor system, the second conveyor system being orientated at an angle (usually 90°) to the first conveyor system and being movable selectably to a level above or below the first conveyor system, and a buffer device being located in the path of the second conveyor system.
In operation of the angle diverter mechanism, the second conveyor system would normally be aligned with an infeed conveyor arrangement, and the first conveyor system would normally be aligned with a bundle squaring machine. Then, with the second conveyor system elevated to a height above that of the first conveyor system, bundles of articles would be fed to the angle diverter from the in-feed conveyor and at a velocity corresponding to that of the in-feed conveyor. This velocity would be sufficient to cause the bundles to idle along the first conveyor system of the angle diverter until the bundles hit the buffer device, which acts as a shock absorber and prevents further foward travel of the bundles. When a bundle of articles impacts with the buffer device an associated sensor causes actuation of the second conveyor system, whereupon the first (driven) conveyor system engages with the bundle of articles and therefore causes such bundle to be carried forward, at right angles to its original direction of travel, toward the bundle squaring machine as above defined.
The invention will be more fully understood from the following description of a preferred embodiment thereof, the description being given with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a side elevation view of a bundle squaring machine, including a conveyor system associated therewith,
FIG. 2 shows a detail of the conveyor system of the machine illustrated in FIG. 1,
FIG. 3 shows a plan view (from above) of the machine illustrated in FIG. 1,
FIG. 4 shows a perspective view of the leading end of a side squaring arm of the bundle squaring machine, including a vertically disposed roller associated with the squaring arm,
FIGS. 5a to 5d show sequential operations being performed on a bundle of articles in a squaring zone of the bundle squaring machine, FIG. 6 shows an electro-pneumatic circuit associated with various elements of the bundle squaring machine,
FIG. 7 shows a plan view (from above) of an angle diverter for use in conjunction with the bundle squaring machine, and,
FIG. 8 shows an end elevation view of the angle diverter as seen in the direction indicated by arrows 8--8 of FIG. 7.
DETAILED DESCRIPTION OF THE INVENTION
As is shown in FIGS. 1 to 4 of the drawings, the bundle squaring machine comprises two interconnected conveyor systems 10 and 11. The first conveyor system 10 is employed to convey a bundle 12 of randomly orientated flat-form cartons from a preceding stacking machine 13 to the second conveyor system 11 which forms a part of a bundle squaring zone.
The first conveyor system 10 has full width rollers 14, and the second conveyor system 11 has two-part rollers 15. The respective parts of each roller 15 are separated by a track 16 in which pusher fingers 17 (referred to below) are located. Alternative ones of the rollers 14 are coated with a material having a high co-efficient of friction.
The two conveyor systems 10 and 11 are powered by a single electric motor 18 and a chain/sprocket drive 19. Driving motion is transmitted to the rollers by friction belts 20 which pass below all of the rollers (see FIG. 2 for detail) and are pressed into frictional engagement with the rollers by pivotally mounted spring loaded pressure wheels 21. With this drive transmission to the rollers, if any object (such as a part of an operator's clothing) should jam in or wrap around one of the rollers, that roller will discontinue rotating (provided that the retarding force is greater than that of the driving friction force) to prevent any damage being sustained either by the machine or the interfering object.
A deflecting plate 22 is mounted to the first conveyor system 10 for the purpose of deflecting any misplaced bundle 12 into a path aligned with the center of the second conveyor system 11. The deflecting plate is provided with angled edges so that it can be used to cause turning of the bundle as it is conveyed past the deflecting plate. A hand wheel and lead screw arrangement 23 is provided to permit lateral adjustment of the position of the deflecting plate.
Located above the second conveyor system 11 are two spaced-apart, vertically disposed parallel side squaring plates 24. Each of the plates 24 is bearing mounted (at points 25) to pivotable parallel lever arm systems 26 and 27 which are respectively coupled to shafts 28 and 29. The shafts 28 are mounted for rotation in bearings 30 and the shafts 29 are similarly mounted in bearings 31, but the shafts 29 are further coupled, via lever arms 32, to pneumatic cylinders 33. When the cylinders 33 are actuated, the shafts 29 are turned to cause the lever mechanisms 27 to pivot inwardly. Then the squaring plates are moved inwardly and, because of the parallel relationship between the lever mechanisms 26 and 27, the squaring plates 24 move in a lateral direction and maintain their parallel relationship. This maintained relationship is indicated by the dash-dot lines in FIG. 3 and is described in greater detail below with reference to FIGS. 5a to 5d.
Each of the squaring plates 24 is fitted at its trailing end with a deflector plate 34.
A vertically disposed roller 35 is mounted via pivotable lever arms 36 to an axle 37 at the leading end of each squaring plate 24. The rollers are normally located inside the line of the squaring plates by a spring loaded piston/cylinder arrangement 39 which connects between each squaring plate and a bar 38 which bridges the lever arms 36. This arrangement is described in greater detail below, with reference to FIGS. 4 and 5.
Located between the side squaring plates 24 is the track 16 which includes three parallel channels. Three pusher fingers 17 are normally located in a retracted condition at the trailing end of these channels, as shown in FIG. 3. The pusher fingers are coupled to a pneumatic cylinder (not shown) which is located below the second conveyor system 11 and which is actuable to drive the fingers upwardly, so that they project above the level of the conveyor system as shown by the dash-dotted lines in FIG. 1. A further pneumatic cylinder (also not shown) is provided to drive the fingers 17 longitudinally forward (when in their projecting condition) in the direction indicated by the arrows in FIG. 1. The three fingers 17 may be replaced by a single plate which operates in the same way and for the same purpose as the fingers.
Reference is now made to FIG. 4 of the drawings which details the arrangement of the rollers at the leading end of each of the side squaring plates 24. As above mentioned, the roller 35 is pivotally mounted to the squaring plate 24 by way of pivotal arms 36, and a pneumatic piston/cylinder arrangement 39 connects the rollers to the squaring plates.
The cylinder 39 houses a spring 40 which normally functions to bias the roller 35 to lie within the inside line of the squaring plate 24, but the biassing effect of the spring may be countered by applying fluid pressure to the piston 41, whereby the roller is driven out from its normal position to lie outside the line of the squaring plate. This operation is now described with reference to FIGS. 5a to 5d.
FIG. 5a shows a bundle of randomly stacked cartons 12 entering a squaring zone 42 between the side squaring plates 24. Whilst the bundle is entering the squaring zone 42, the three pusher fingers 17 remain in their retracted position below the level of the second conveyor 11. When the bundle 12 has passed over and cleared the pusher finger 17, pneumatic circuits are energized (in a manner to be hereinafter described) and the side plates 24 are moved in a lateral direction toward one another, so as to close on the sides of the bundle of cartons 12. At the same time the pusher fingers 17 are projected upwardly to locate behind the bundle. For the period during which the squaring plates 24 are in their open and closing positions, the rollers 35 at the leading end of the squaring plates are biassed inwardly.
When the side squaring plates 24 have moved inwardly to their maximum extent they co-act with the side walls of the bundles 12 to cause squaring-up of those side walls, as is shown in FIG. 5b. At the same time the bundle 12 is pushed forwardly in a longitudinal direction by the pusher fingers 17, this causing the leading end of the bundle to engage with the rollers 35. Because of the pushing force from the fingers and a retarding force exerted by the spring biassed rollers 35 the leading and trailing ends of the bundle are squared-up. During this fore and aft squaring operation the fingers 17 continue to move forward and to avoid crushing of the bundle the rollers 35 are pivoted away against the action of the spring bias. This is shown in FIG. 5c of the drawings.
Thereafter, a further pneumatic circuit is energized and the pneumatic piston/cylinder arrangement 39 associated with the rollers 35 causes the rollers to pivot away from the leading end of the bundle 12 in the manner described with reference to FIG. 4 and as shown in FIG. 5d. Following the stage shown in FIG. 5d the side squaring arms 24 return to their initial (rest) position, the pusher fingers 17 move longitudinally backwards to their initial position and then retract below the level of the second conveyor system 11, and the conveyor system 11 is restarted to move the squared bundle 12 of cartons forward into a strapping machine which is located ahead of the above described bundle squaring machine.
An important feature of the invention as above described is that, during the period of forward movement of the pusher fingers 17 against the bundle 12, the first and second conveyor systems 10 and 11 are stopped by disengaging a clutch, referred to below, and are not restarted until the sequential steps shown in FIGS. 5a to 5d are completed.
Reference is now made to FIG. 6 of the drawings which shows a pneumatic circuit which is employed in conjunction with the bundle squaring machine as above described.
The circuit includes two pneumatic microswitches 60 and 61 which are located at the right hand end of the squaring zone as shown in FIG. 3 of the drawings. The switch 60 is the first one contacted by a bundle which is being conveyed toward the squaring zone and, when so contacted, the switch 60 causes a following spring loaded valve 62 to be activated to a valve-closed position. The switch 61 is then contacted as the bundle progresses further toward the squaring zone but, for as long as the bundle is in contact also with switch 60, pressurised fluid cannot pass through the valve 62 from the switch 61. However, when the bundle has been conveyed beyond switch 60, but still remains in contact with switch 61, pressure is released from the valve 62 and it returns to its normally open position. At this point in time, that is when the bundle has almost completely entered the squaring zone, the fluid pressure which passes via switch 61 and valve 62 is used to activate the following circuit.
Such circuit includes two detent valves 63 and 64. Valve 63 is coupled to a first double acting pneumatic cylinder 33 (see also FIG. 1) which serves to actuate the side squaring plates, to a second double acting pneumatic cylinder 65 which serves to drive the pusher fingers back and forth in the longitudinal direction, and to a third double acting pneumatic cylinder 66 which serves to extend and retract the pusher fingers above and below the conveyor.
Valve 64 is coupled to the spring loaded pneumatic cylinder 39 (see also FIG. 4) which serves to actuate the vertically disposed rollers, and to a pneumatic clutch 67 in the conveyor drive circuit.
In the circuit condition shown in FIG. 6, i.e., before a bundle passes over the switches 60 and 61, fluid pressure is applied via line 68 to cylinders 33, 65 and 66. Under this condition, the side squaring plates are held away from the squaring zone, the pusher fingers are held at the right hand end of their tracks (as shown in FIG. 3) and the fingers are held in their retracted position so as to permit entry into the squaring zone of a bundle. At the same time, the cylinder 39 and the clutch 67 are connected to atmosphere via line 69 and the valve 64. This enables spring biasing of the vertical rollers (as previously described) and drive transmission to the conveyor rollers.
When a bundle is conveyed into the squaring zone (i.e., when pressurised gas is delivered to the detent valves 63 and 64 via valve 62, as above described), the valves 63 and 64 are actuated. Valve 63 then delivers fluid to cylinders 33, 65 and 66 via line 70 and line 68 is connected to atmosphere. This results in the squaring plates being moved laterally toward one another, the pusher fingers being moved along their tracks toward the left hand end of the machine (as shown by the arrows in FIG. 1), and the pusher fingers being extended above the level of the conveyor rollers. The time taken for each of these functions is controlled by the adjustable restrictors shown located in the fluid lines connected to the respective cylinders.
During the same time interval over which the cylinders 33, 65 and 66 are actuated, the cylinder 39 and the clutch 67 are connected to the pressured supply. This results, initially, in disengagement of the clutch (halting the conveyor system) and, shortly later, in actuation of the cylinder 39. The belated actuation of the cylinder 39 effects pivoting of the vertical rollers at the leading end of the squaring arms after the rollers have been contacted by the advancing bundle.
When the bundle has been pushed beyond the vertical roller it contacts a further pneumatic microswitch 72 (see also FIG. 3) which is operated to apply fluid pressure to the valves 63 and 64 via line 73. This results in restarting of the conveyor system (i.e., clutch 67 is again engaged), and movement of the side squaring arms and pusher fingers back to their starting positions.
A manually operable control valve 74 is provided for overriding the effect of actuating the starting switches 60 and 61.
The switches 60, 61 and 72 may be replaced by photoelectric detectors or other similar proximity switching devices and other circuit adjustments be made as appropriate.
Reference is now made to FIGS. 7 and 8 of the drawings which show an angle diverter mechanism for use in conjunction with the bundle squaring machine previously described. The angle diverter is used to accommodate situations where the bundles must be fed to the bundle squaring machine at 90° from a preceding production line, such situation normally arising where insufficient factory space exists for a complete in-line system.
The angle diverter mechanism may be provided in addition to the first conveyor system 10 as above described or, as shown in FIGS. 7 and 8, it may be incorporated in the first conveyor system. Thus, as shown, the angle diverter mechanism comprises a first conveyor system 10 which is aligned with the squaring mechanism 50, the first conveyor system including a series of laterally extending rollers 14. The rollers 14 are driven in the manner above described with reference to FIGS. 1 to 3.
In addition to the driven conveyor system 10, the angle diverter mechanism includes a second conveyor system 51 consisting of an array of idler rollers 52 mounted to a subframe 53. The idler rollers are orientated at 90° C. to the driven rollers 14, in alignment with an in-feed conveyor system 54.
The sub-frame 53, together with the array of idler rollers 52, is mounted to a pneumatic piston/cylinder arrangement (not shown) which may be actuated either to lift the second conveyor system 51 to a level just above the first conveyor system 10 or to retract the second conveyor system 51 to a level below the first conveyor system 10. When in the elevated position, the sub-frame 53, together with the array of idler rollers 52, is inclined at a small angle θ to the infeed conveyor 54 and hence to the axis of the rollers 14 of the first conveyor 10 mechanism.
A buffer plate 55 is pivotably mounted to a post 56 which projects upwardly from the angle diverter mechanism, the buffer plate being aligned with the direction of feed of the second conveyor mechanism 51. A shock absorber 57 connects a lever arm 58 of the buffer plate 55 to the post 56, the shock absorber being provided to absorb kinetic energy possessed by bundles which pass from the in-feed conveyor 54 and impact with the buffer plate 55.
In operation of the angle diverter mechanism, bundles of articles (not shown) are conveyed along the infeed conveyor 54 and projected forward onto the idler rollers 52 of the second conveyor mechanism. During this operation the second conveyor mechanism 51 is elevated to a position above the level of the rollers 14 of the first conveyor system 10. Once deposited upon the rollers 52 of the second conveyor 51, the bundles travel forward along the rollers 52 until they impact with the buffer plate 55. Upon this happening a microswitch (not shown) is activated, by pivotal movement of the buffer plate, and the second conveyor mechanism is immediately retracted to its level below that of the first conveyor mechanism 10. As the second conveyor mechanism does retract, the bundle of articles carried thereby comes to rest on the rollers 14 of the first conveyor mechanism and these rollers 14 are then driven to convey the bundle in the direction toward the squaring machine 50.
Thereafter, the second conveyor mechanism 51 is again elevated to its original height in readiness to receive a further bundle of articles from the in-feed conveyor system 54.
|
A bundle squaring machine suitable particularly for squaring a bundle of cartons in readiness for strapping. The machine includes a conveyor system for conveying a bundle of randomly orientated stack of articles into a squaring zone, where the stack is squared-up laterally and fore and aft. While in the squaring zone, side squaring arms close in a lateral direction against the sides of the bundle, and a pusher device moves the bundle longitudinally forward against a pair of spring biased rollers which contact the leading edge of the bundle. Following a period of contact between the leading edge of the bundle and the rollers, the rollers are pivoted clear of the bundle and, thereafter, the side squaring arms move back to their initial position. During the squaring operation the conveyor system is halted, the bundle being advanced by the pusher device during this period, and following the squaring operation, the pusher device is retracted below the level of the conveyor system. An article feed diverter is also provided for use in conjunction with the squaring machine.
| 1
|
Subsets and Splits
No community queries yet
The top public SQL queries from the community will appear here once available.